National Library of Energy BETA

Sample records for roll-to-roll solution-processable small-molecule

  1. Roll-to-Roll Solution-Processible Small-Molecule OLEDs

    SciTech Connect

    Liu, Jie Jerry

    2012-07-31

    The objective of this program is to develop key knowledge and make critical connections between technologies needed to enable low-cost manufacturing of OLED lighting products. In particular, the program was intended to demonstrate the feasibility of making high performance Small-Molecule OLEDs (SM-OLED) using a roll-to-roll (R2R) wet-coating technique by addressing the following technical risks (1) Whether the wet-coating technique can provide high performance OLEDs, (2) Whether SM-OLED can be made in a R2R manner, (3) What are the requirements for coating equipment, and (4) Whether R2R OLEDs can have the same performance as the lab controls. The program has been managed and executed according to the Program Management Plan (PMP) that was first developed at the beginning of the program and further revised accordingly as the program progressed. Significant progress and risk reductions have been accomplished by the end of the program. Specific achievements include: (1) Demonstrated that wet-coating can provide OLEDs with high LPW and long lifetime; (2) Demonstrated R2R OLEDs can be as efficient as batch controls (Figure 1) (3) Developed & validated basic designs for key equipment necessary for R2R SM-OLEDs; (4) Developed know-hows & specifications on materials & ink formulations critical to wetcoating; (5) Developed key R2R processes for each OLED layer (6) Identified key materials and components such as flexible barrier substrates necessary for R2R OLEDs.

  2. Roll to Roll Manufacturing

    SciTech Connect

    Daniel, Claus

    2015-06-09

    ORNL researchers are developing roll to roll technologies for manufacturing, automotive, and clean energy applications in collaboration with industry partners such as Eastman Kodak.

  3. A modular molecular framework for utility in small-molecule solution-processed organic photovoltaic devices

    SciTech Connect

    Welch, Gregory C.; Perez, Louis A.; Hoven, Corey V.; Zhang, Yuan; Dang, Xuan-Dung; Sharenko, Alexander; Toney, Michael F.; Kramer, Edward J.; Nguyen, Thuc-Quyen; Bazan, Guillermo C.

    2011-07-22

    We report on the design, synthesis and characterization of light harvesting small molecules for use in solution-processed small molecule bulk heterojunction (SM-BHJ) solar cell devices. These molecular materials are based upon an acceptor/donor/acceptor (A/D/A) core with donor endcapping units. Utilization of a dithieno(3,2-b;2',3'-d)silole (DTS) donor and pyridal[2,1,3]thiadiazole (PT) acceptor leads to strong charge transfer characteristics, resulting in broad optical absorption spectra extending well beyond 700 nm. SM-BHJ solar cell devices fabricated with the specific example 5,5'-bis{7-(4-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine}-3,3'-di-2-ethylhexylsilylene-2,2'-bithiophene (6) as the donor and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) as the acceptor component showed short circuit currents above -10 mA cm-2 and power conversion efficiencies (PCEs) over 3%. Thermal processing is a critical factor in obtaining favorable active layer morphologies and high PCE values. A combination of UV-visible spectroscopy, conductive and photo-conductive atomic force microscopies, dynamic secondary mass ion spectrometry (DSIMS), and grazing incident wide angle X-ray scattering (GIWAXS) experiments were carried out to characterize how thermal treatment influences the active layer structure and organization.

  4. Efficient solution-processed small molecule: Cadmium selenide quantum dot bulk heterojunction solar cells

    SciTech Connect

    Gupta, Vinay; Department of Physics, University of California, Santa Barbara, California 93106 ; Upreti, Tanvi; Chand, Suresh

    2013-12-16

    We report bulk heterojunction solar cells based on blends of solution-processed small molecule [7,7?-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b?]dithiophene-2,6-diyl) bis(6-fluoro-4-(5?-hexyl-[2,2?-bithiophen]-5yl)benzo[c] [1,2,5] thiadiazole)] p-DTS(FBTTh{sub 2}){sub 2}: Cadmium Selenide (CdSe) (70:30, 60:40, 50:50, and 40:60) in the device configuration: Indium Tin Oxide /poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/p-DTS(FBTTh{sub 2}){sub 2}: CdSe/Ca/Al. The optimized ratio of p-DTS(FBTTh{sub 2}){sub 2}:CdSe::60:40 leads to a short circuit current density (J{sub sc})?=?5.45?mA/cm{sup 2}, open circuit voltage (V{sub oc})?=?0.727?V, and fill factor (FF)?=?51%, and a power conversion efficiency?=?2.02% at 100 mW/cm{sup 2} under AM1.5G illumination. The J{sub sc} and FF are sensitive to the ratio of p-DTS(FBTTh{sub 2}){sub 2}:CdSe, which is a crucial factor for the device performance.

  5. ADVANCED MANUFACTURING OFFICE HIGH VALUE ROLL TO ROLL (HV R2R...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    ADVANCED MANUFACTURING OFFICE HIGH VALUE ROLL TO ROLL (HV R2R) WORKSHOP DECEMBER 2-3, 2015 ADVANCED MANUFACTURING OFFICE HIGH VALUE ROLL TO ROLL (HV R2R) WORKSHOP DECEMBER 2-3, ...

  6. Manufacturing Demonstration Facility: Roll-to-Roll Processing

    SciTech Connect

    Datskos, Panos G; Joshi, Pooran C; List III, Frederick Alyious; Duty, Chad E; Armstrong, Beth L; Ivanov, Ilia N; Jacobs, Christopher B; Graham, David E; Moon, Ji Won

    2015-08-01

    This Manufacturing Demonstration Facility (MDF)e roll-to-roll processing effort described in this report provided an excellent opportunity to investigate a number of advanced manufacturing approaches to achieve a path for low cost devices and sensors. Critical to this effort is the ability to deposit thin films at low temperatures using nanomaterials derived from nanofermentation. The overarching goal of this project was to develop roll-to-roll manufacturing processes of thin film deposition on low-cost flexible substrates for electronics and sensor applications. This project utilized ORNL s unique Pulse Thermal Processing (PTP) technologies coupled with non-vacuum low temperature deposition techniques, ORNL s clean room facility, slot dye coating, drop casting, spin coating, screen printing and several other equipment including a Dimatix ink jet printer and a large-scale Kyocera ink jet printer. The roll-to-roll processing project had three main tasks: 1) develop and demonstrate zinc-Zn based opto-electronic sensors using low cost nanoparticulate structures manufactured in a related MDF Project using nanofermentation techniques, 2) evaluate the use of silver based conductive inks developed by project partner NovaCentrix for electronic device fabrication, and 3) demonstrate a suite of low cost printed sensors developed using non-vacuum deposition techniques which involved the integration of metal and semiconductor layers to establish a diverse sensor platform technology.

  7. Roll to Roll Processing Projects ITN Energy Systems

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Science and Technology for a Better World ENERGY SYSTEMS Brian Berland Chief Science Officer High Value Roll-to-Roll Workshop (HVR2R) December 2-3, 2015 ...Science and Technology for a Better World ITN Energy Systems Taking Technologies from Lab to the Marketplace Employing R2R Processing 2 ...Science and Technology for a Better World Applications for High Value R2R * Next Generation Batteries - Increased Energy Density, Cycle Life, and Safety with All Solid State Lithium Batteries * Low-Cost

  8. Vehicle Technologies Office Merit Review 2014: Roll-to-Roll Electrode

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Processing NDE for Advanced Lithium Secondary Batteries | Department of Energy Roll-to-Roll Electrode Processing NDE for Advanced Lithium Secondary Batteries Vehicle Technologies Office Merit Review 2014: Roll-to-Roll Electrode Processing NDE for Advanced Lithium Secondary Batteries Presentation given by Oak Ridge National Laboratory at 2014 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Office Annual Merit Review and Peer Evaluation Meeting about roll-to-roll electrode

  9. Roll-to-Roll Electrode Processing and Materials NDE for Advanced...

    Energy.gov [DOE] (indexed site)

    Lithium Secondary Batteries Vehicle Technologies Office Merit Review 2014: Roll-to-Roll Electrode Processing NDE for Advanced Lithium Secondary Batteries In-situ ...

  10. ADVANCED MANUFACTURING OFFICE HIGH VALUE ROLL TO ROLL (HV R2R) WORKSHOP

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    DECEMBER 2-3, 2015 | Department of Energy ADVANCED MANUFACTURING OFFICE HIGH VALUE ROLL TO ROLL (HV R2R) WORKSHOP DECEMBER 2-3, 2015 ADVANCED MANUFACTURING OFFICE HIGH VALUE ROLL TO ROLL (HV R2R) WORKSHOP DECEMBER 2-3, 2015 Draft Agenda (215.67 KB) More Documents & Publications WORKSHOP: SUSTAINABILITY IN MANUFACTURING AGENDA AND OVERVIEW Workshop: High Value Roll to Roll (HV R2R) Manufacturing Innovation, December 2-3, 2015 WORKSHOP: SUSTAINABILITY IN MANUFACTURING, JANUARY 6-7

  11. WORKSHOP: HIGH VALUE ROLL TO ROLL (HV R2R) MANUFACTURING INNOVATION...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    WORKSHOP: HIGH VALUE ROLL TO ROLL (HV R2R) MANUFACTURING INNOVATION, DECEMBER 2-3, 2015 December 2-3, 2015 in Alexandria, VA. The Advanced Manufacturing Office (AMO) hosted a ...

  12. Chapter 6: Innovating Clean Energy Technologies in Advanced Manufacturing | Roll-to-Roll Processing Technology Assessment

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Roll to Roll Processing Chapter 6: Technology Assessments NOTE: This technology assessment is available as an appendix to the 2015 Quadrennial Technology Review (QTR). Roll-to-Roll Processing is one of fourteen manufacturing-focused technology assessments prepared in support of Chapter 6: Innovating Clean Energy Technologies in Advanced Manufacturing. For context within the 2015 QTR, key connections between this technology assessment, other QTR technology chapters, and other Chapter 6 technology

  13. Roll-to-Roll Electrode Processing and Materials NDE for Advanced Lithium

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Secondary Batteries | Department of Energy 3 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting es165_wood_2013_p.pdf (4.5 MB) More Documents & Publications Vehicle Technologies Office Merit Review 2014: Roll-to-Roll Electrode Processing NDE for Advanced Lithium Secondary Batteries Lithium Ion Electrode Production NDE and QC Considerations Roll-to-Roll Electrode Processing and Materials NDE for Advanced Lithium Secondary

  14. Roll-to-Roll Electrode Processing and Materials NDE for Advanced Lithium

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Secondary Batteries | Department of Energy 2 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Program Annual Merit Review and Peer Evaluation Meeting es165_wood_2012_o.pdf (3.53 MB) More Documents & Publications Roll-to-Roll Electrode Processing and Materials NDE for Advanced Lithium Secondary Batteries Vehicle Technologies Office Merit Review 2014: Roll-to-Roll Electrode Processing NDE for Advanced Lithium Secondary Batteries In-situ characterization and diagnostics of

  15. AMO and FCTO to Partner on Roll-to-Roll Manufacturing Activities |

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Department of Energy AMO and FCTO to Partner on Roll-to-Roll Manufacturing Activities AMO and FCTO to Partner on Roll-to-Roll Manufacturing Activities October 11, 2016 - 5:44pm Addthis The U.S. Department of Energy's Advanced Manufacturing Office (AMO) and Fuel Cell Technologies Office (FCTO) celebrate in honor of back-to-back National Manufacturing Day (October 7) and National Hydrogen and Fuel Cell Day on October 8, commemorating the atomic weight of hydrogen (1.008)-the lightest and most

  16. Workshop: High Value Roll to Roll (HV R2R) Manufacturing Innovation,

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    December 2-3, 2015 | Department of Energy Workshop: High Value Roll to Roll (HV R2R) Manufacturing Innovation, December 2-3, 2015 Workshop: High Value Roll to Roll (HV R2R) Manufacturing Innovation, December 2-3, 2015 December 2-3, 2015 in Alexandria, VA. The Advanced Manufacturing Office (AMO) hosted a workshop in Alexandria, VA at the Westin Alexandria Hotel on 2-3 December, 2015. This 2 day workshop focused on the advanced manufacturing technology topic of HV R2R. Discussion topics

  17. Upscaling Perovskite Solar Cells via Industrial Roll-to-Roll Processes |

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    MIT-Harvard Center for Excitonics Upscaling Perovskite Solar Cells via Industrial Roll-to-Roll Processes April 7, 2016 at 3:00PM/34-401B Doojin Vak Commonwealth Scientific and Industrial Research Organisation, Australia Doojin_Vak-2 Perovskite solar cells have emerged as the most promising third-generation solar cells with a rapid increase in record efficiencies. However, most of these devices have been made by processes that are not scalable, typically spin coating. The next challenge in

  18. Roll-to-roll atomic layer deposition process for flexible electronics encapsulation applications

    SciTech Connect

    Maydannik, Philipp S. Kriinen, Tommi O.; Lahtinen, Kimmo; Cameron, David C.; Sderlund, Mikko; Soininen, Pekka; Johansson, Petri; Kuusipalo, Jurkka; Moro, Lorenza; Zeng, Xianghui

    2014-09-01

    At present flexible electronic devices are under extensive development and, among them, flexible organic light-emitting diode displays are the closest to a large market deployment. One of the remaining unsolved challenges is high throughput production of impermeable flexible transparent barrier layers that protect sensitive light-emitting materials against ambient moisture. The present studies deal with the adaptation of the atomic layer deposition (ALD) process to high-throughput roll-to-roll production using the spatial ALD concept. We report the development of such a process for the deposition of 20?nm thickness Al{sub 2}O{sub 3} diffusion barrier layers on 500?mm wide polymer webs. The process uses trimethylaluminum and water as precursors at a substrate temperature of 105?C. The observation of self-limiting film growth behavior and uniformity of thickness confirms the ALD growth mechanism. Water vapor transmission rates for 20?nm Al{sub 2}O{sub 3} films deposited on polyethylene naphthalate (PEN) substrates were measured as a function of substrate residence time, that is, time of exposure of the substrate to one precursor zone. Moisture permeation levels measured at 38?C/90% relative humidity by coulometric isostaticisobaric method were below the detection limit of the instrument (<5??10{sup ?4}?g/m{sup 2} day) for films coated at web moving speed of 0.25?m/min. Measurements using the Ca test indicated water vapor transmission rates ?5??10{sup ?6} g/m{sup 2} day. Optical measurements on the coated web showed minimum transmission of 80% in the visible range that is the same as the original PEN substrate.

  19. Continuous roll-to-roll amorphous silicon photovoltaic manufacturing technology. Semiannual subcontract report, 1 April 1993--30 September 1993

    SciTech Connect

    Izu, M.

    1994-06-01

    This report describes work for this reporting period under a 3-year program to advance Energy Conversion Device`s (ECD) roll-to-roll, triple-junction photovoltaic (PV) manufacturing technologies, to reduce the module production costs, to increase the stabilized module performance, and to expand commercial production capacity utilizing ECD technology. The specific 3-year goal is to develop advanced large-scale manufacturing technology incorporating ECD`s earlier research advances with the capability of producing modules with stable 11% efficiency at a cost of approximately $1.00 per peak watt. Major accomplishments during this reporting period include (1) the design, construction. amd testomg of a continuous roll-to-roll multipurpose amorphous silicon alloy solar cell deposition machine that incorporates improvements necessary to obtain higher efficiency solar cells; (2) development of a photothermal deflection spectroscopy (PDS) technique for evaluating back-reflector systems; (3) the development of an improved textured Ag/ZnO back-reflector system demonstrating 25% gain in J{sub sc} over previous textured Al back-reflector systems; and (4) the design of a serpentine web continuous roll-to-roll deposition chamber.

  20. Waveguide slot-excited long racetrack electron cyclotron resonance plasma source for roll-to-roll (scanning) processing

    SciTech Connect

    You, H.-J. [National Fusion Research Institute, Daejeon (Korea, Republic of)] [National Fusion Research Institute, Daejeon (Korea, Republic of)

    2013-07-15

    We present a SLot-excited ANtenna (SLAN) long racetrack ECR plasma source that is utilized for roll-to-roll plasma processing such as thin film encapsulation of large-area OLED (organic light emitting diode) panel or modification of fabric surfaces. This source is designed to be long, and to operate under high density uniform plasma with sub-milli-torr pressures. The above features are accomplished by a slot-excited long racetrack resonator with a toroidal geometry of magnetic field ECR configuration, and reinforced microwave electric distributions along the central region of plasma chamber. Also, a new feature has been added to the source. This is to employ a tail plunger, which allows the microwave electric field and the uniformity of the plasma profile to be easily adjustable. We have successfully generated Ar plasmas operating with the microwave power of 0.53 kW in the pressure range of 0.210 mTorr. The plasma is uniform (<10%) in the direction of the straight track and has a Gaussian profile in the roll-to-roll (scanning) direction. In addition, it is shown that the tail plunger could adjust the plasma profile in order to obtain plasma uniformity. Furthermore, based on the results, we suggest a newly designed up-scaled racetrack-SLAN source.

  1. Flexible indium zinc oxide/Ag/indium zinc oxide multilayer electrode grown on polyethersulfone substrate by cost-efficient roll-to-roll sputtering for flexible organic photovoltaics

    SciTech Connect

    Park, Yong-Seok; Kim, Han-Ki

    2010-01-15

    The authors describe the preparation and characteristics of flexible indium zinc oxide (IZO)-Ag-IZO multilayer electrodes grown on flexible polyethersulfone (PES) substrates using a roll-to-roll sputtering system for use in flexible organic photovoltaics. By the continuous roll-to-roll sputtering of the bottom IZO, Ag, and top IZO layers at room temperature, they were able to fabricate a high quality IZO-Ag-IZO multilayer electrode with a sheet resistance of 6.15 {epsilon}/square, optical transmittance of 87.4%, and figure of merit value of 42.03x10{sup -3} {Omega}{sup -1} on the PES substrate. In addition, the IZO-Ag-IZO multilayer electrode exhibited superior flexibility to the roll-to-roll sputter grown single ITO electrode due to the existence of a ductile Ag layer between the IZO layers and stable amorphous structure of the IZO film. Furthermore, the flexible organic solar cells (OSCs) fabricated on the roll-to-roll sputter grown IZO-Ag-IZO electrode showed higher power efficiency (3.51%) than the OSCs fabricated on the roll-to-roll sputter grown single ITO electrode (2.67%).

  2. In situ monitoring of structure formation in the active layer of polymer solar cells during roll-to-roll coating

    SciTech Connect

    Rossander, Lea H.; Zawacka, Natalia K.; Dam, Henrik F.; Krebs, Frederik C.; Andreasen, Jens W.

    2014-08-15

    The active layer crystallization during roll-to-roll coating of organic solar cells is studied in situ. We developed an X-ray setup where the coater unit is an integrated part of the small angle X-ray scattering instrument, making it possible to control the coating process while recording scattering measurements in situ, enabling us to follow the crystal formation during drying. By varying the distance between the coating head and the point where the X-ray beam hits the film, we obtained measurements of 4 different stages of drying. For each of those stages, the scattering from as long a foil as possible is summed together, with the distance from coating head to scattering point kept constant. The results are average crystallographic properties for the active layer coated on a 30 m long foil. With this insight into the dynamics of crystallization in a roll-coated polymer film, we find that the formation of textured and untextured crystallites seems uncorrelated, and happens at widely different rates. Untextured P3HT crystallites form later in the drying process than expected which may explain previous studies speculating that untextured crystallization depends on concentration. Textured crystallites, however, begin forming much earlier and steadily increases as the film dries, showing a development similar to other in situ studies of these materials.

  3. Develop Roll-to-Roll Manufacturing Process of ZrO2 Nanocrystals/Acrylic Nanocomposites for High Refractive Index Applications

    SciTech Connect

    Joshi, Pooran C.; Compton, Brett G.; Li, Jianlin; Jellison, Jr, Gerald Earle; Duty, Chad E; Chen, Zhiyun

    2015-04-01

    The purpose of this Cooperative Research and Development Agreement (CRADA) was to develop and evaluate ZrO2/acrylic nanocomposite coatings for integrated optoelectronic applications. The formulations engineered to be compatible with roll-to-roll process were evaluated in terms of optical and dielectric properties. The uniform distribution of the ZrO2 nanocrystals in the polymer matrix resulted in highly tunable refractive index and dielectric response suitable for advanced photonic and electronic device applications.

  4. CX-001153: Categorical Exclusion Determination

    Energy.gov [DOE]

    Roll-to-Roll Solution-Processable Small-Molecule Organic Light-Emitting Diodes (Wilmington) Date: 03/11/2010Location(s): Wilmington, DelawareOffice(s): Energy Efficiency and Renewable Energy, National Energy Technology Laboratory

  5. Inverted, semitransparent small molecule photovoltaic cells ...

    Office of Scientific and Technical Information (OSTI)

    small molecule photovoltaic cells Authors: Xiao, Xin 1 ; Lee, Kyusang 1 ; Forrest, Stephen R. 2 + Show Author Affiliations Department of Electrical Engineering and Computer...

  6. Protein Scaffolding for Small Molecule Catalysts

    SciTech Connect

    Baker, David

    2014-09-14

    We aim to design hybrid catalysts for energy production and storage that combine the high specificity, affinity, and tunability of proteins with the potent chemical reactivities of small organometallic molecules. The widely used Rosetta and RosettaDesign methodologies will be extended to model novel protein / small molecule catalysts in which one or many small molecule active centers are supported and coordinated by protein scaffolding. The promise of such hybrid molecular systems will be demonstrated with the nickel-phosphine hydrogenase of DuBois et. al.We will enhance the hydrogenase activity of the catalyst by designing protein scaffolds that incorporate proton relays and systematically modulate the local environment of the catalyticcenter. In collaboration with DuBois and Shaw, the designs will be experimentally synthesized and characterized.

  7. A Supramolecular Complex in Small-Molecule Solar Cells based...

    Office of Scientific and Technical Information (OSTI)

    in Small-Molecule Solar Cells based on Contorted Aromatic Molecules Citation Details In-Document Search Title: A Supramolecular Complex in Small-Molecule Solar Cells based on ...

  8. Understanding Small-Molecule Interactions in Metal-Organic Frameworks...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Understanding Small-Molecule Interactions in Metal-Organic Frameworks: Coupling Experiment ... guest molecules and the internal surface of the framework must first be understood. ...

  9. X-ray characterization of solid small molecule organic materials

    DOEpatents

    Billinge, Simon; Shankland, Kenneth; Shankland, Norman; Florence, Alastair

    2014-06-10

    The present invention provides, inter alia, methods of characterizing a small molecule organic material, e.g., a drug or a drug product. This method includes subjecting the solid small molecule organic material to x-ray total scattering analysis at a short wavelength, collecting data generated thereby, and mathematically transforming the data to provide a refined set of data.

  10. Comparison of light out-coupling enhancements in single-layer blue-phosphorescent organic light emitting diodes using small-molecule or polymer hosts

    SciTech Connect

    Chang, Yung-Ting; Liu, Shun-Wei; Yuan, Chih-Hsien; Lee, Chih-Chien; Ho, Yu-Hsuan; Wei, Pei-Kuen; Chen, Kuan-Yu; Lee, Yi-Ting; Wu, Min-Fei; Chen, Chin-Ti E-mail: chihiwu@cc.ee.ntu.edu.tw; Wu, Chih-I E-mail: chihiwu@cc.ee.ntu.edu.tw

    2013-11-07

    Single-layer blue phosphorescence organic light emitting diodes (OLEDs) with either small-molecule or polymer hosts are fabricated using solution process and the performances of devices with different hosts are investigated. The small-molecule device exhibits luminous efficiency of 14.7?cd/A and maximum power efficiency of 8.39?lm/W, which is the highest among blue phosphorescence OLEDs with single-layer solution process and small molecular hosts. Using the same solution process for all devices, comparison of light out-coupling enhancement, with brightness enhancement film (BEF), between small-molecule and polymer based OLEDs is realized. Due to different dipole orientation and anisotropic refractive index, polymer-based OLEDs would trap less light than small molecule-based OLEDs internally, about 37% better based simulation results. In spite of better electrical and spectroscopic characteristics, including ambipolar characteristics, higher carrier mobility, higher photoluminescence quantum yield, and larger triplet state energy, the overall light out-coupling efficiency of small molecule-based devices is worse than that of polymer-based devices without BEF. However, with BEF for light out-coupling enhancement, the improved ratio in luminous flux and luminous efficiency for small molecule based device is 1.64 and 1.57, respectively, which are significantly better than those of PVK (poly-9-vinylcarbazole) devices. In addition to the theoretical optical simulation, the experimental data also confirm the origins of differential light-outcoupling enhancement. The maximum luminous efficiency and power efficiency are enhanced from 14.7?cd/A and 8.39?lm/W to 23?cd/A and 13.2?lm/W, respectively, with laminated BEF, which are both the highest so far for single-layer solution-process blue phosphorescence OLEDs with small molecule hosts.

  11. CX-001152: Categorical Exclusion Determination

    Energy.gov [DOE]

    Roll-to-Roll Solution-Processable Small-Molecule Organic Light-Emitting Diodes (Niskayuna)CX(s) Applied: B3.6Date: 03/11/2010Location(s): Niskayuna, New YorkOffice(s): Energy Efficiency and Renewable Energy, National Energy Technology Laboratory

  12. Solution-Procesed Small-Molecule OLED Luminaire for Interior Illumination

    SciTech Connect

    Parker, Ian

    2012-02-29

    Prototype lighting panels and luminaires were fabricated using DuPont Displays solution-processed small-molecule OLED technology. These lighting panels were based on a spatially-patterned, 3-color design, similar in concept to an OLED display panel, with materials chosen to maximize device efficacy. The majority of the processing steps take place in air (rather than high vacuum). Optimization of device architecture, processing and construction was undertaken, with a final prototype design of 50 cm{sup 2} being fabricated and tested. Performance of these panels reached 35 lm/W at illuminant-A. A unique feature of this technology is the ability to color tune the emission, and color temperatures ranging from 2700 to > 6,500K were attained in the final build. Significant attention was paid to low-cost fabrication techniques.

  13. Small-Molecule Inhibition of TNF-alpha

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Small-Molecule Inhibition of TNF-alpha Tumour necrosis factor is a polypeptide cytokine involved in inflammation and the acute phase response. TNF-alpha is present in larger quantities in persons with rheumatoid arthritis or Crohn's disease. Direct inhibition of TNF-a by the commercial biological agents etanercept (Enbrel), infliximab (Remicade), adalimumab (Humira), has produced significant advances in rheumatoid arthritis treatment and validated the extra-cellular inhibition of this

  14. Polymer and small molecule based hybrid light source

    DOEpatents

    Choong, Vi-En; Choulis, Stelios; Krummacher, Benjamin Claus; Mathai, Mathew; So, Franky

    2010-03-16

    An organic electroluminescent device, includes: a substrate; a hole-injecting electrode (anode) coated over the substrate; a hole injection layer coated over the anode; a hole transporting layer coated over the hole injection layer; a polymer based light emitting layer, coated over the hole transporting layer; a small molecule based light emitting layer, thermally evaporated over the polymer based light emitting layer; and an electron-injecting electrode (cathode) deposited over the electroluminescent polymer layer.

  15. A general strategy to construct small molecule biosensors in eukaryotes

    DOE PAGES [OSTI]

    Feng, Justin; Jester, Benjamin W.; Tinberg, Christine E.; Mandell, Daniel J.; Antunes, Mauricio S.; Chari, Raj; Morey, Kevin J.; Rios, Xavier; Medford, June I.; Church, George M.; et al

    2015-12-29

    Biosensors for small molecules can be used in applications that range from metabolic engineering to orthogonal control of transcription. Here, we produce biosensors based on a ligand-binding domain (LBD) by using a method that, in principle, can be applied to any target molecule. The LBD is fused to either a fluorescent protein or a transcriptional activator and is destabilized by mutation such that the fusion accumulates only in cells containing the target ligand. We illustrate the power of this method by developing biosensors for digoxin and progesterone. Addition of ligand to yeast, mammalian, or plant cells expressing a biosensor activatesmore » transcription with a dynamic range of up to ~100-fold. We use the biosensors to improve the biotransformation of pregnenolone to progesterone in yeast and to regulate CRISPR activity in mammalian cells. This work provides a general methodology to develop biosensors for a broad range of molecules in eukaryotes.« less

  16. WORKSHOP: HIGH VALUE ROLL TO ROLL MANUFACTURING INNOVATION, DECEMBER...

    Energy.gov [DOE] (indexed site)

    December 2, 2015 8:00AM EST to December 3, 2015 3:30PM EST The Advanced Manufacturing Office (AMO) is planning to host a workshop at the Westin Alexandria on 2-3 December, 2015. ...

  17. Manufacturing Demonstration Facility: Roll-to-Roll Processing...

    Office of Scientific and Technical Information (OSTI)

    effort described in this report provided an excellent opportunity to investigate a number of advanced manufacturing approaches to achieve a path for low cost devices and sensors. ...

  18. Roll to Roll Processing Projects ITN Energy Systems

    Energy.gov [DOE] (indexed site)

    Integrated into Structure: BIPV, Defense & Space (Power on wing of MAV), etc. * Next Generation SolarEnergy Harvesting - Rectenna Based Energy Harvesting of Waste Heat 3 ...

  19. Small Molecule Adsorption in Open-Site Metal-Organic Frameworks...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Small Molecule Adsorption in Open-Site Metal-Organic Frameworks: A Systematic Density Functional Theory Study for Rational Design Previous Next List Kyuho Lee, Joshua D. Howe,...

  20. A Small Molecule That Switches a Ubiquitin Ligase From a Processive...

    Office of Scientific and Technical Information (OSTI)

    Title: A Small Molecule That Switches a Ubiquitin Ligase From a Processive to a Distributive Enzymatic Mechanism Authors: Kathman, Stefan G. ; Span, Ingrid ; Smith, Aaron T. ; Xu, ...

  1. Group specific internal standard technology (GSIST) for simultaneous identification and quantification of small molecules

    DOEpatents

    Adamec, Jiri; Yang, Wen-Chu; Regnier, Fred E

    2014-01-14

    Reagents and methods are provided that permit simultaneous analysis of multiple diverse small molecule analytes present in a complex mixture. Samples are labeled with chemically identical but isotopically distince forms of the labeling reagent, and analyzed using mass spectrometry. A single reagent simultaneously derivatizes multiple small molecule analytes having different reactive functional groups.

  2. Studies of solution-processed organic light-emitting diodes and their materials

    SciTech Connect

    Hellerich, Emily

    2013-01-01

    A hitherto unexplored approach is presented in which a small molecule is used as a host to polymer guests in solution-processed OLEDs. We find that the small molecule host results in much more efficient devices than the often-used alternative polymer host when used for the guests presented. It is likely that nano- and microstructural differences between the hosts contribute to the improvements, which highlights some interesting characteristics that can help to better understand the nature of these mixtures. A number of the guests used in this study were newly synthesized benzobisoxazole-based copolymers. New organic copolymers are presented that are based on the chemical structure of benzobisoxazoles, which have been shown in the past to have good electron transporting properties. The novel concept in this publication pertains to a change in the direction of polymerization, also known as the conjugation pathway, which we show increases the emission efficiency. This work highlights a unique and useful property of organic semiconducting materials in that they can be synthesized to create the desired characteristics. Earlier work is described that kick-started in our research group the use of small molecules in solution-processed OLEDs. Originally these devices were to be used in magnetoresistance studies, but the project took a different path when the devices were more efficient than expected. The efficient use of small molecules in solution-processed OLEDs is highlighted, which at the time was not often the case. Also, the important observation of the effect of solvent choice on the resultant film is emphasized, with discussion of the likely cause of these effects. Microcavity OLEDs are introduced in which the transparent anode ITO is replaced with semi-transparent thin silver, which creates an optical cavity within the devices. The goal was to expand a previous work that created an on-chip spectrometer covering wavelengths 493 to 639 nm. In this case, a spin

  3. Solution-Processed Squaraine Bulk Heterojunction Photovoltaic Cells

    SciTech Connect

    Wei, Guodan; Wang, Siyi; Renshaw, Kyle; Thompson, Mark E.; Forrest, Stephen R.

    2010-04-01

    The donor, 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (SQ) is used with the acceptor, [6,6]-phenyl C70 butyric acid methyl ester (PC70 BM) to result in efficient, solution-processed, small-molecule bulk heterojunction photovoltaic cells. The distribution of the donor nanoparticles in the acceptor matrix as a function of relative concentrations results in a trade-off between exciton dissociation and hole mobility (and hence, cell series resistance). A bulk heterojunction solar cell consisting of an active region with a component ratio of SQ to PC70 BM of 1:6 has a power conversion efficiency of 2.7 ± 0.1% with a 8.85 ± 0.22 mA/cm2 short-circuit current density and an open-circuit voltage of 0.89 ± 0.01 V obtained under simulated 1 sun (100 mW/cm2) air mass 1.5 global (AM1.5 G) solar illumination. This is a decrease from 3.3 ± 0.3% at 0.2 sun intensity, and is less than that of a control planar heterojunction SQ/C60 cell with 4.1 ± 0.2% at 1 sun, suggesting that the nanoparticle morphology introduces internal resistance into the solution-based thin film. The nanomorphology and hole mobility in the films is strongly dependent on the SQ-to-PC{sub 70}BM ratio, increasing by greater than 2 orders of magnitude as the ratio increases from 28% to 100% SQ.

  4. Solution-Processed Squaraine Bulk Heterojunction Photovoltaic Cells

    SciTech Connect

    Wei, Guodan; Wang, Siyi; Renshaw, Kyle; Thompson, Mark E.; Forrest, Stephen R.

    2010-04-01

    The donor, 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (SQ) is used with the acceptor, [6,6]-phenyl C70 butyric acid methyl ester (PC70 BM) to result in efficient, solution-processed, small-molecule bulk heterojunction photovoltaic cells. The distribution of the donor nanoparticles in the acceptor matrix as a function of relative concentrations results in a trade-off between exciton dissociation and hole mobility (and hence, cell series resistance). A bulk heterojunction solar cell consisting of an active region with a component ratio of SQ to PC70 BM of 1:6 has a power conversion efficiency of 2.7 ± 0.1% with a 8.85 ± 0.22 mA/cm2 short-circuit current density and an open-circuit voltage of 0.89 ± 0.01 V obtained under simulated 1 sun (100 mW/cm2) air mass 1.5 global (AM1.5 G) solar illumination. This is a decrease from 3.3 ± 0.3% at 0.2 sun intensity, and is less than that of a control planar heterojunction SQ/C60 cell with 4.1 ± 0.2% at 1 sun, suggesting that the nanoparticle morphology introduces internal resistance into the solution-based thin film. The nanomorphology and hole mobility in the films is strongly dependent on the SQ-to-PC70 BM ratio, increasing by greater than 2 orders of magnitude as the ratio increases from 28% to 100% SQ.

  5. Discovery of Small Molecules that Inhibit the Disordered Protein, p27Kip1

    SciTech Connect

    Iconaru, Luigi I.; Ban, David; Bharatham, Kavitha; Ramanathan, Arvind; Zhang, Weixing; Shelat, Anang A.; Zuo, Jian; Kriwacki, Richard W.

    2015-10-28

    In disordered proteins we see that they are highly prevalent in biological systems. They control myriad signaling and regulatory processes, and their levels and/or cellular localization are often altered in human disease. In contrast to folded proteins, disordered proteins, due to conformational heterogeneity and dynamics, are not considered viable drug targets. We challenged this paradigm by identifying through NMR-based screening small molecules that bound specifically, albeit weakly, to the disordered cell cycle regulator, p27Kip1 (p27). Moreover, two groups of molecules bound to sites created by transient clusters of aromatic residues within p27. Conserved chemical features within these two groups of small molecules exhibited complementarity to their binding sites within p27, establishing structure-activity relationships for small molecule: disordered protein interactions. Finally, one compound counteracted the Cdk2/cyclin A inhibitory function of p27 in vitro, providing proof-of- principle that small molecules can inhibit the function of a disordered protein (p27) through sequestration in a conformation incapable of folding and binding to a natural regulatory target (Cdk2/cyclin A).

  6. Discovery of Small Molecules that Inhibit the Disordered Protein, p27Kip1

    DOE PAGES [OSTI]

    Iconaru, Luigi I.; Ban, David; Bharatham, Kavitha; Ramanathan, Arvind; Zhang, Weixing; Shelat, Anang A.; Zuo, Jian; Kriwacki, Richard W.

    2015-10-28

    In disordered proteins we see that they are highly prevalent in biological systems. They control myriad signaling and regulatory processes, and their levels and/or cellular localization are often altered in human disease. In contrast to folded proteins, disordered proteins, due to conformational heterogeneity and dynamics, are not considered viable drug targets. We challenged this paradigm by identifying through NMR-based screening small molecules that bound specifically, albeit weakly, to the disordered cell cycle regulator, p27Kip1 (p27). Moreover, two groups of molecules bound to sites created by transient clusters of aromatic residues within p27. Conserved chemical features within these two groups ofmore » small molecules exhibited complementarity to their binding sites within p27, establishing structure-activity relationships for small molecule: disordered protein interactions. Finally, one compound counteracted the Cdk2/cyclin A inhibitory function of p27 in vitro, providing proof-of- principle that small molecules can inhibit the function of a disordered protein (p27) through sequestration in a conformation incapable of folding and binding to a natural regulatory target (Cdk2/cyclin A).« less

  7. Mathematical modeling of the aptamers and its effect on small molecule

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    transport into the cell | The Ames Laboratory Mathematical modeling of the aptamers and its effect on small molecule transport into the cell In this proposed research, we expect to explore the hypothesis that the levels of accumulation of chemicals by cells can be mediated by mobile intracellular receptors1. As initial evidence of this hypothesis, we have recently determined experimentally that bacterial uptake of a toxin can be increased by aptamer receptors expressed by the cells. We

  8. Early-Late Heterobimetallic Complexes Linked by Phosphinoamide Ligands. Tuning Redox Potentials and Small Molecule Activation

    SciTech Connect

    Thomas, Christine M.

    2015-08-01

    Recent attention in the chemical community has been focused on the energy efficient and environmentally benign conversion of abundant small molecules (CO2, H2O, etc.) to useful liquid fuels. This project addresses these goals by examining fundamental aspects of catalyst design to ultimately access small molecule activation processes under mild conditions. Specifically, Thomas and coworkers have targetted heterobimetallic complexes that feature metal centers with vastly different electronic properties, dictated both by their respective positions on the periodic table and their coordination environment. Unlike homobimetallic complexes featuring identical or similar metals, the bonds between metals in early/late heterobimetallics are more polarized, with the more electron-rich late metal center donating electron density to the more electron-deficient early metal center. While metal-metal bonds pose an interesting strategy for storing redox equivalents and stabilizing reactive metal fragments, the polar character of metal-metal bonds in heterobimetallic complexes renders these molecules ideally poised to react with small molecule substrates via cleavage of energy-rich single and double bonds. In addition, metal-metal interactions have been shown to dramatically affect redox potentials and promote multielectron redox activity, suggesting that metal-metal interactions may provide a mechanism to tune redox potentials and access substrate reduction/activation at mild overpotentials. This research project has provided a better fundamental understanding of how interactions between transition metals can be used as a strategy to promote and/or control chemical transformations related to the clean production of fuels. While this project focused on the study of homogeneous systems, it is anticipated that the broad conclusions drawn from these investigations will be applicable to heterogeneous catalysis as well, particularly on heterogeneous processes that occur at interfaces in

  9. A "roller-wheel" Pt-containing small molecule that outperforms its polymer analogs in organic solar cells

    DOE PAGES [OSTI]

    He, Wenhan; Wu, Qin; Livshits, Maksim Y.; Dickie, Diane A.; Yang, Jianzhong; Quinnett, Rachel; Rack, Jeffrey R.; Qin, Yang

    2016-05-23

    A novel Pt-bisacetylide small molecule (Pt-SM) featuring “roller-wheel” geometry was synthesized and characterized. When compared with conventional Pt-containing polymers and small molecules having “dumbbell” shaped structures, Pt-SM displays enhanced crystallinity and intermolecular π–π interactions, as well as favorable panchromatic absorption behaviors. Furthermore, organic solar cells (OSCs) employing Pt-SM achieve power conversion efficiencies (PCEs) up to 5.9%, the highest reported so far for Pt-containing polymers and small molecules.

  10. Reprogramming Bacteria to Seek and Destroy Small Molecules (JGI Seventh Annual User Meeting 2012: Genomics of Energy and Environment)

    ScienceCinema

    Gallivan, Justin [Emory University

    2016-07-12

    Justin Gallivan, of Emory University presents a talk titled "Reprogramming Bacteria to Seek and Destroy Small Molecules" at the JGI User 7th Annual Genomics of Energy & Environment Meeting on March 21, 2012 in Walnut Creek, Calif

  11. Reprogramming Bacteria to Seek and Destroy Small Molecules (JGI Seventh Annual User Meeting 2012: Genomics of Energy and Environment)

    SciTech Connect

    Gallivan, Justin [Emory University] [Emory University

    2012-03-21

    Justin Gallivan, of Emory University presents a talk titled "Reprogramming Bacteria to Seek and Destroy Small Molecules" at the JGI User 7th Annual Genomics of Energy & Environment Meeting on March 21, 2012 in Walnut Creek, Calif

  12. XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

    DOE PAGES [OSTI]

    Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; Veith, Gabriel M.; Dai, Sheng; Lin, Wenbin; Abney, C. W.; Bryantsev, V. S.

    2015-11-12

    In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η2 motifs proposed by small molecule and computationalmore » studies. Samples exposed to environmental seawater also display a feature consistent with a μ2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.« less

  13. XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

    SciTech Connect

    Mayes, Richard T.; Piechowicz, Marek; Lin, Zekai; Veith, Gabriel M.; Dai, Sheng; Lin, Wenbin; Abney, C. W.; Bryantsev, V. S.

    2015-11-12

    In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η2 motifs proposed by small molecule and computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.

  14. Link between hopping models and percolation scaling laws for charge transport in mixtures of small molecules

    DOE PAGES [OSTI]

    Ha, Dong -Gwang; Kim, Jang -Joo; Baldo, Marc A.

    2016-04-29

    Mixed host compositions that combine charge transport materials with luminescent dyes offer superior control over exciton formation and charge transport in organic light emitting devices (OLEDs). Two approaches are typically used to optimize the fraction of charge transport materials in a mixed host composition: either an empirical percolative model, or a hopping transport model. We show that these two commonly-employed models are linked by an analytic expression which relates the localization length to the percolation threshold and critical exponent. The relation is confirmed both numerically and experimentally through measurements of the relative conductivity of Tris(4-carbazoyl-9-ylphenyl) amine (TCTA) :1,3-bis(3,5-dipyrid-3-yl-phenyl) benzene (BmPyPb)more » mixtures with different concentrations, where the TCTA plays a role as hole conductor and the BmPyPb as hole insulator. Furthermore, the analytic relation may allow the rational design of mixed layers of small molecules for high-performance OLEDs.« less

  15. WORKSHOP: HIGH VALUE ROLL TO ROLL MANUFACTURING INNOVATION, DECEMBER 2-3

    Energy.gov [DOE]

    The Advanced Manufacturing Office (AMO) is planning to host a workshop at the Westin Alexandria on 2-3 December, 2015. This 2-day workshop will focus on the on the advanced manufacturing technology...

  16. Solution-Processed Solar Cells using Colloidal Quantum Dots ...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Solution-Processed Solar Cells using Colloidal Quantum Dots September 27, 2012 at 3pm36-428 Ted Sargent Department of Electrical and Computer Engineering - Canada Research Chair ...

  17. Oxidation-resistant, solution-processed plasmonic Ni nanochain...

    Office of Scientific and Technical Information (OSTI)

    Oxidation-resistant, solution-processed plasmonic Ni nanochain-SiOsub x (x < 2) selective solar thermal absorbers Citation Details In-Document Search Title: Oxidation-resistant, ...

  18. High open-circuit voltage small-molecule p-DTS(FBTTh 2 )2.ICBA bulk heterojunction solar cells – morphology, excited-state dynamics, and photovoltaic performance

    DOE PAGES [OSTI]

    Ko Kyaw, Aung Ko; Gehrig, Dominik; Zhang, Jie; Huang, Ye; Bazan, Guillermo C.; Laquai, Frédéric; Nguyen, Thuc -Quyen

    2014-11-27

    The photovoltaic performance of bulk heterojunction solar cells using the solution-processable small molecule donor 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole) (p-DTS(FBTTh2)2 in combination with indene-C60 bis-adduct (ICBA) as an acceptor is systematically optimized by altering the processing conditions. A high open-circuit voltage of 1 V, more than 0.2 V higher than that of a p-DTS(FBTTh2)2:PC70BM blend, is achieved. However, the power conversion efficiency remains around 5% and thus is lower than ~8% previously reported for p-DTS(FBTTh2)2:PC70BM. Transient absorption (TA) pump–probe spectroscopy over a wide spectral (Vis-NIR) and dynamic (fs to μs) range in combination with multivariate curve resolution analysis of the TA data reveals thatmore » generation of free charges is more efficient in the blend with PC70BM as an acceptor. In contrast, blends with ICBA create more coulombically bound interfacial charge transfer (CT) states, which recombine on the sub-nanosecond timescale by geminate recombination. Furthermore, the ns to μs charge carrier dynamics in p-DTS(FBTTh2)2:ICBA blends are only weakly intensity dependent implying a significant contribution of recombination from long-lived CT states and trapped charges, while those in p-DTS(FBTTh2)2:PC70BM decay via an intensity-dependent recombination mechanism indicating that spatially separated (free) charge carriers are observed, which can be extracted as photocurrent from the device.« less

  19. Solution-grown small-molecule organic semiconductor with enhanced crystal alignment and areal coverage for organic thin film transistors

    DOE PAGES [OSTI]

    Bi, Sheng; He, Zhengran; Chen, Jihua; Li, Dawen

    2015-07-24

    Drop casting of small-molecule organic semiconductors typically forms crystals with random orientation and poor areal coverage, which leads to significant performance variations of organic thin-film transistors (OTFTs). In this study, we utilize the controlled evaporative self-assembly (CESA) method combined with binary solvent system to control the crystal growth. A small-molecule organic semiconductor,2,5-Di-(2-ethylhexyl)-3,6-bis(5"-n-hexyl-2,2',5',2"]terthiophen-5-yl)-pyrrolo[3,4-c]pyrrole-1,4-dione (SMDPPEH), is used as an example to demonstrate the effectiveness of our approach. By optimizing the double solvent ratios, well-aligned SMDPPEH crystals with significantly improved areal coverage were achieved. As a result, the SMDPPEH based OTFTs exhibit a mobility of 1.6 × 10-2 cm2/V s, which is themore » highest mobility from SMDPPEH ever reported.« less

  20. Solution-grown small-molecule organic semiconductor with enhanced crystal alignment and areal coverage for organic thin film transistors

    SciTech Connect

    Bi, Sheng; He, Zhengran; Chen, Jihua; Li, Dawen

    2015-07-24

    Drop casting of small-molecule organic semiconductors typically forms crystals with random orientation and poor areal coverage, which leads to significant performance variations of organic thin-film transistors (OTFTs). In this study, we utilize the controlled evaporative self-assembly (CESA) method combined with binary solvent system to control the crystal growth. A small-molecule organic semiconductor,2,5-Di-(2-ethylhexyl)-3,6-bis(5"-n-hexyl-2,2',5',2"]terthiophen-5-yl)-pyrrolo[3,4-c]pyrrole-1,4-dione (SMDPPEH), is used as an example to demonstrate the effectiveness of our approach. By optimizing the double solvent ratios, well-aligned SMDPPEH crystals with significantly improved areal coverage were achieved. As a result, the SMDPPEH based OTFTs exhibit a mobility of 1.6 × 10-2 cm2/V s, which is the highest mobility from SMDPPEH ever reported.

  1. Low-cost copper complexes as p-dopants in solution processable hole transport layers

    SciTech Connect

    Kellermann, Renate; Taroata, Dan; Maltenberger, Anna; Hartmann, David; Schmid, Guenter; Brabec, Christoph J.

    2015-09-07

    We demonstrate the usage of the Lewis-acidic copper(II)hexafluoroacetylacetonate (Cu(hfac){sub 2}) and copper(II)trifluoroacetylacetonate (Cu(tfac){sub 2}) as low-cost p-dopants for conductivity enhancement of solution processable hole transport layers based on small molecules in organic light emitting diodes (OLEDs). The materials were clearly soluble in mixtures of environmentally friendly anisole and xylene and spin-coated under ambient atmosphere. Enhancements of two and four orders of magnitude, reaching 4.0 × 10{sup −11} S/cm with a dopant concentration of only 2 mol% Cu(hfac){sub 2} and 1.5 × 10{sup −9} S/cm with 5 mol% Cu(tfac){sub 2} in 2,2′,7,7′-tetra(N,N-ditolyl)amino-9,9-spiro-bifluorene (spiro-TTB), respectively, were achieved. Red light emitting diodes were fabricated with reduced driving voltages and enhanced current and power efficiencies (8.6 lm/W with Cu(hfac){sub 2} and 5.6 lm/W with Cu(tfac){sub 2}) compared to the OLED with undoped spiro-TTB (3.9 lm/W). The OLED with Cu(hfac){sub 2} doped spiro-TTB showed an over 8 times improved LT{sub 50} lifetime of 70 h at a starting luminance of 5000 cd/m{sup 2}. The LT{sub 50} lifetime of the reference OLED with PEDOT:PSS was only 8 h. Both non-optimized OLEDs were operated at similar driving voltage and power efficiency.

  2. Organic electronic devices with multiple solution-processed layers

    DOEpatents

    Forrest, Stephen R.; Lassiter, Brian E.; Zimmerman, Jeramy D.

    2015-08-04

    A method of fabricating a tandem organic photosensitive device involves depositing a first layer of an organic electron donor type material film by solution-processing of the organic electron donor type material dissolved in a first solvent; depositing a first layer of an organic electron acceptor type material over the first layer of the organic electron donor type material film by a dry deposition process; depositing a conductive layer over the interim stack by a dry deposition process; depositing a second layer of the organic electron donor type material over the conductive layer by solution-processing of the organic electron donor type material dissolved in a second solvent, wherein the organic electron acceptor type material and the conductive layer are insoluble in the second solvent; depositing a second layer of an organic electron acceptor type material over the second layer of the organic electron donor type material film by a dry deposition process, resulting in a stack.

  3. Molecular and Hybrid Solution Processable Thermoelectrics | MIT-Harvard

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Center for Excitonics and Hybrid Solution Processable Thermoelectrics February 15, 2011 at 3pm/36-428 Rachel Segalman University of California, Berkeley segalman_001 abstract: Thermoelectric materials for energy generation have several advantages over conventional power cycles including lack of moving parts, silent operation, miniaturizability, and CO2 free conversion of heat to electricity. Excellent thermoelectric efficiency requires a combination of high thermopower (S, V/K), high

  4. Evidence for small-molecule-mediated loop stabilization in the structure of the isolated Pin1 WW domain

    SciTech Connect

    Mortenson, David E.; Kreitler, Dale F.; Yun, Hyun Gi; Gellman, Samuel H., E-mail: gellman@chem.wisc.edu; Forest, Katrina T., E-mail: gellman@chem.wisc.edu [University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2013-12-01

    Two structures of a small protein with a defined tertiary fold, the isolated Pin1 WW domain, have been determined via racemic crystallization with small-molecule additives. These additives, which are either racemic or achiral, appear to stabilize a dynamic loop region of the structure. The human Pin1 WW domain is a small autonomously folding protein that has been useful as a model system for biophysical studies of ?-sheet folding. This domain has resisted previous attempts at crystallization for X-ray diffraction studies, perhaps because of intrinsic conformational flexibility that interferes with the formation of a crystal lattice. Here, the crystal structure of the human Pin1 WW domain has been obtained via racemic crystallization in the presence of small-molecule additives. Both enantiomers of a 36-residue variant of the Pin1 WW domain were synthesized chemically, and the l- and d-polypeptides were combined to afford diffracting crystals. The structural data revealed packing interactions of small carboxylic acids, either achiral citrate or a d,l mixture of malic acid, with a mobile loop region of the WW-domain fold. These interactions with solution additives may explain our success in crystallization of this protein racemate. Molecular-dynamics simulations starting from the structure of the Pin1 WW domain suggest that the crystal structure closely resembles the conformation of this domain in solution. The structural data presented here should provide a basis for further studies of this important model system.

  5. Surface-supported Ag islands stabilized by a quantum size effect: Their interaction with small molecules relevant to ethylene epoxidation

    SciTech Connect

    Shao, Dahai

    2013-05-15

    This dissertation focuses on how QSE-stabilized, surface-supported Ag nanoclusters will interact with ethylene or oxygen. Experiments are performed to determine whether the QSE-mediated Ag islands react differently toward adsorption of ethylene or oxygen, or whether the adsorption of these small molecules will affect the QSE-mediated stability of Ag islands. Studies of the interaction of oxygen with Ag/Si(111)-77 were previously reported, but these studies were performed at a low Ag coverage where 3D Ag islands were not formed. So the study of such a system at a higher Ag coverage will be a subject of this work. The interaction of ethylene with Ag/Si(111)-77, as well as the interaction of oxygen with Ag/NiAl(110) are also important parts of this study.

  6. White top-emitting organic light-emitting diodes with solution-processed nano-particle scattering layers

    SciTech Connect

    Schaefer, Tim; Schwab, Tobias; Lenk, Simone; Gather, Malte C.

    2015-12-07

    A random scattering approach to enhance light extraction in white top-emitting organic light-emitting diodes (OLEDs) is reported. Through solution processing from fluorinated solvents, a nano-particle scattering layer (NPSL) can be deposited directly on top of small molecule OLEDs without affecting their electrical performance. The scattering length for light inside the NPSL is determined from transmission measurements and found to be in agreement with Mie scattering theory. Furthermore, the dependence of the light outcoupling enhancement on electron transport layer thickness is studied. Depending on the electron transport layer thickness, the NPSL enhances the external quantum efficiency of the investigated white OLEDs by between 1.5 and 2.3-fold. For a device structure that has been optimized prior to application of the NPSL, the maximum external quantum efficiency is improved from 4.7% to 7.4% (1.6-fold improvement). In addition, the scattering layer strongly reduces the undesired shift in emission color with viewing angle.

  7. Actinide solution processing at the Rocky Flats Environmental Technology Site

    SciTech Connect

    1995-04-01

    The Department of Energy (DOE) has prepared an Environmental Assessment (EA), DOE/EA-1039, for radioactive solution removal and processing at Rocky Flats Environmental Technology Site, Golden, Colorado. The proposal for solution removal and processing is in response to independent safety assessments and an agreement with the State of Colorado to remove mixed residues at Rocky Flats and reduce the risk of future accidents. Monthly public meetings were held during the scoping and preparation of the EA. The scope of the EA included evaluations of alternative methods and locations of solution processing. A comment period from February 20, 1995 through March 21, 1995 was provided to the public and the State of Colorado to offer written comment on the EA. Comments were received from the State of Colorado and the U.S. Environmental Protection Agency. A response to the agency comments is included in the Final EA.

  8. Peculiarity of two thermodynamically-stable morphologies and their impact on the efficiency of small molecule bulk heterojunction solar cells

    DOE PAGES [OSTI]

    Herath, Nuradhika; Das, Sanjib; Keum, Jong K.; Zhu, Jiahua; Kumar, Rajeev; Ivanov, Ilia N.; Sumpter, Bobby G.; Browning, James F.; Xiao, Kai; Gu, Gong; et al

    2015-08-28

    Structural characteristics of the active layers in organic photovoltaic (OPV) devices play a critical role in charge generation, separation and transport. Here we report on morphology and structural control of p-DTS(FBTTh2)2:PC71BM films by means of thermal annealing and 1,8-diiodooctane (DIO) solvent additive processing, and correlate it to the device performance. By combining surface imaging with nanoscale depth-sensitive neutron reflectometry (NR) and X-ray diffraction, three-dimensional morphologies of the films are reconstituted with information extending length scales from nanometers to microns. DIO promotes the formation of a well-mixed donor-acceptor vertical phase morphology with a large population of small p-DTS(FBTTh2)2 nanocrystals arranged inmore » an elongated domain network of the film, thereby enhancing the device performance. In contrast, films without DIO exhibit three-sublayer vertical phase morphology with phase separation in agglomerated domains. Our findings are supported by thermodynamic description based on the Flory-Huggins theory with quantitative evaluation of pairwise interaction parameters that explain the morphological changes resulting from thermal and solvent treatments. Our study reveals that vertical phase morphology of small-molecule based OPVs is significantly different from polymer-based systems. Lastly, the significant enhancement of morphology and information obtained from theoretical modeling may aid in developing an optimized morphology to enhance device performance for OPVs.« less

  9. Peculiarity of two thermodynamically-stable morphologies and their impact on the efficiency of small molecule bulk heterojunction solar cells

    SciTech Connect

    Herath, Nuradhika; Das, Sanjib; Keum, Jong K.; Zhu, Jiahua; Kumar, Rajeev; Ivanov, Ilia N.; Sumpter, Bobby G.; Browning, James F.; Xiao, Kai; Gu, Gong; Joshi, Pooran; Smith, Sean; Lauter, Valeria

    2015-08-28

    Structural characteristics of the active layers in organic photovoltaic (OPV) devices play a critical role in charge generation, separation and transport. Here we report on morphology and structural control of p-DTS(FBTTh2)2:PC71BM films by means of thermal annealing and 1,8-diiodooctane (DIO) solvent additive processing, and correlate it to the device performance. By combining surface imaging with nanoscale depth-sensitive neutron reflectometry (NR) and X-ray diffraction, three-dimensional morphologies of the films are reconstituted with information extending length scales from nanometers to microns. DIO promotes the formation of a well-mixed donor-acceptor vertical phase morphology with a large population of small p-DTS(FBTTh2)2 nanocrystals arranged in an elongated domain network of the film, thereby enhancing the device performance. In contrast, films without DIO exhibit three-sublayer vertical phase morphology with phase separation in agglomerated domains. Our findings are supported by thermodynamic description based on the Flory-Huggins theory with quantitative evaluation of pairwise interaction parameters that explain the morphological changes resulting from thermal and solvent treatments. Our study reveals that vertical phase morphology of small-molecule based OPVs is significantly different from polymer-based systems. Lastly, the significant enhancement of morphology and information obtained from theoretical modeling may aid in developing an optimized morphology to enhance device performance for OPVs.

  10. Investigation of solution-processed bismuth-niobium-oxide films

    SciTech Connect

    Inoue, Satoshi; Ariga, Tomoki; Matsumoto, Shin; Onoue, Masatoshi; Miyasako, Takaaki; Tokumitsu, Eisuke; Shimoda, Tatsuya; Chinone, Norimichi; Cho, Yasuo

    2014-10-21

    The characteristics of bismuth-niobium-oxide (BNO) films prepared using a solution process were investigated. The BNO film annealed at 550C involving three phases: an amorphous phase, Bi?NbO? fluorite microcrystals, and Nb-rich cubic pyrochlore microcrystals. The cubic pyrochlore structure, which was the main phase in this film, has not previously been reported in BNO films. The relative dielectric constant of the BNO film was approximately 140, which is much higher than that of a corresponding film prepared using a conventional vacuum sputtering process. Notably, the cubic pyrochlore microcrystals disappeared with increasing annealing temperature and were replaced with triclinic ?-BiNbO? crystals at 590C. The relative dielectric constant also decreased with increasing annealing temperature. Therefore, the high relative dielectric constant of the BNO film annealed at 550C is thought to result from the BNO cubic pyrochlore structure. In addition, the BNO films annealed at 500C contained approximately 6.5 atm.% carbon, which was lost at approximately 550C. This result suggests that the carbon in the BNO film played an important role in the formation of the cubic pyrochlore structure.

  11. Structural and optoelectronic properties of hybrid bulk-heterojunction materials based on conjugated small molecules and mesostructured TiO{sub 2}

    SciTech Connect

    Phan, Hung [Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106 (United States); Jahnke, Justin P.; Chmelka, Bradley F. [Department of Chemical Engineering, University of California, Santa Barbara, California 93106 (United States); Nguyen, Thuc-Quyen, E-mail: quyen@chem.ucsb.edu [Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106 (United States); Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah (Saudi Arabia)

    2014-06-09

    Improved hybrid bulk-heterojunction materials was fabricated by spin-casting a benchmark conjugated small molecule, namely, 3,6-bis(5-(benzofuran-2-yl)thiophen-2-yl)-2,5-bis(2-ethylhexyl) pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DPP(TBFu){sub 2}), into mesostructured TiO{sub 2}. Due to both a reduced molecular size and less hydrophobic nature of the conjugated molecules (relative to conjugated polymers), homogeneous and improved infiltration into the mesoporous TiO{sub 2} are achieved without the need for pre-treatment of the TiO{sub 2}. Remarkably, this small molecule can realize loadings of up to 25% of the total pore volume2.5 the typical loadings achieved for conjugated polymers. The small molecule loading was determined using dynamic secondary ion mass spectroscopy and absorption spectroscopy. Further characterization such as charge transfer and nanoscale conducting atomic force microscopy helps to demonstrate the promise and viability of small molecule donors for hybrid optoelectronic devices.

  12. Photochemically enhanced binding of small molecules to the tumor necrosis factor receptor-1 inhibits the binding of TNF-[alpha

    SciTech Connect

    Carter, Percy H.; Scherle, Peggy A.; Muckelbauer, Jodi K.; Voss, Matthew E.; Liu, Rui-qin; Thompson III, Lorin A.; Xu, Meizhong; Lo, Yvonne C.; Li, Zhong; Strzemienski, Paul; Yang, Gengjie; Falahatpishen, Nikoo; Farrow, Neil A.; Tebben, Andrew J.; Underwood, Denis; Trzaskos, James M.; Friedman, Steven M.; Newton, Robert C.; Decicco, Carl P.

    2010-03-05

    The binding of tumor necrosis factor alpha (TNF-{alpha}) to the type-1 TNF receptor (TNFRc1) plays an important role in inflammation. Despite the clinical success of biologics (antibodies, soluble receptors) for treating TNF-based autoimmune conditions, no potent small molecule antagonists have been developed. Our screening of chemical libraries revealed that N-alkyl 5-arylidene-2-thioxo-1,3-thiazolidin-4-ones were antagonists of this protein-protein interaction. After chemical optimization, we discovered IW927, which potently disrupted the binding of TNF-{alpha} to TNFRc1 (IC{sub 50} = 50 nM) and also blocked TNF-stimulated phosphorylation of I{kappa}-B in Ramos cells (IC{sub 50} = 600 nM). This compound did not bind detectably to the related cytokine receptors TNFRc2 or CD40, and did not display any cytotoxicity at concentrations as high as 100 {micro}M. Detailed evaluation of this and related molecules revealed that compounds in this class are 'photochemically enhanced' inhibitors, in that they bind reversibly to the TNFRc1 with weak affinity (ca. 40-100 mM) and then covalently modify the receptor via a photochemical reaction. We obtained a crystal structure of IV703 (a close analog of IW927) bound to the TNFRc1. This structure clearly revealed that one of the aromatic rings of the inhibitor was covalently linked to the receptor through the main-chain nitrogen of Ala-62, a residue that has already been implicated in the binding of TNF-{alpha} to the TNFRc1. When combined with the fact that our inhibitors are reversible binders in light-excluded conditions, the results of the crystallography provide the basis for the rational design of nonphotoreactive inhibitors of the TNF-{alpha}-TNFRc1 interaction.

  13. Discovery and Characterization of a Cell-Permeable, Small-Molecule c-Abl Kinase Activator that Binds to the Myristoyl Binding Site

    SciTech Connect

    Yang, Jingsong; Campobasso, Nino; Biju, Mangatt P.; Fisher, Kelly; Pan, Xiao-Qing; Cottom, Josh; Galbraith, Sarah; Ho, Thau; Zhang, Hong; Hong, Xuan; Ward, Paris; Hofmann, Glenn; Siegfried, Brett; Zappacosta, Francesca; Washio, Yoshiaki; Cao, Ping; Qu, Junya; Bertrand, Sophie; Wang, Da-Yuan; Head, Martha S.; Li, Hu; Moores, Sheri; Lai, Zhihong; Johanson, Kyung; Burton, George; Erickson-Miller, Connie; Simpson, Graham; Tummino, Peter; Copeland, Robert A.; Oliff, Allen

    2014-10-02

    c-Abl kinase activity is regulated by a unique mechanism involving the formation of an autoinhibited conformation in which the N-terminal myristoyl group binds intramolecularly to the myristoyl binding site on the kinase domain and induces the bending of the {alpha}I helix that creates a docking surface for the SH2 domain. Here, we report a small-molecule c-Abl activator, DPH, that displays potent enzymatic and cellular activity in stimulating c-Abl activation. Structural analyses indicate that DPH binds to the myristoyl binding site and prevents the formation of the bent conformation of the {alpha}I helix through steric hindrance, a mode of action distinct from the previously identified allosteric c-Abl inhibitor, GNF-2, that also binds to the myristoyl binding site. DPH represents the first cell-permeable, small-molecule tool compound for c-Abl activation.

  14. Interfacial engineering of solution-processed Ni nanochain-SiOx...

    Office of Scientific and Technical Information (OSTI)

    Title: Interfacial engineering of solution-processed Ni ... 03755, USA Department of Chemical and Materials ... Type: Publisher's Accepted Manuscript Journal Name: Journal ...

  15. A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

    DOE PAGES [OSTI]

    Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; Shi, Si -Qi; Zhou, Yong -Ning; Chen, Guo -Ying; Yang, Xiao -Qing; Weng, Lin -Hong; Zhao, Jing -Tai; Fu, Zheng -Wen

    2016-06-16

    A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN)2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g–1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

  16. Solution-Processed Solar Cells using Colloidal Quantum Dots | MIT-Harvard

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Center for Excitonics Solution-Processed Solar Cells using Colloidal Quantum Dots September 27, 2012 at 3pm/36-428 Ted Sargent Department of Electrical and Computer Engineering - Canada Research Chair in Nanotechnology, University of Toronto, Canada sargent001_000 Abstract: Solution-processed photovoltaics offer a cost-effective path to harvesting the abundant resource that is solar energy. The organic and polymer semiconductors at the heart of these devices generally absorb visible light;

  17. High open-circuit voltage small-molecule p-DTS(FBTTh 2 )2.ICBA bulk heterojunction solar cells – morphology, excited-state dynamics, and photovoltaic performance

    SciTech Connect

    Ko Kyaw, Aung Ko; Gehrig, Dominik; Zhang, Jie; Huang, Ye; Bazan, Guillermo C.; Laquai, Frédéric; Nguyen, Thuc -Quyen

    2014-11-27

    The photovoltaic performance of bulk heterojunction solar cells using the solution-processable small molecule donor 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole) (p-DTS(FBTTh2)2 in combination with indene-C60 bis-adduct (ICBA) as an acceptor is systematically optimized by altering the processing conditions. A high open-circuit voltage of 1 V, more than 0.2 V higher than that of a p-DTS(FBTTh2)2:PC70BM blend, is achieved. However, the power conversion efficiency remains around 5% and thus is lower than ~8% previously reported for p-DTS(FBTTh2)2:PC70BM. Transient absorption (TA) pump–probe spectroscopy over a wide spectral (Vis-NIR) and dynamic (fs to μs) range in combination with multivariate curve resolution analysis of the TA data reveals that generation of free charges is more efficient in the blend with PC70BM as an acceptor. In contrast, blends with ICBA create more coulombically bound interfacial charge transfer (CT) states, which recombine on the sub-nanosecond timescale by geminate recombination. Furthermore, the ns to μs charge carrier dynamics in p-DTS(FBTTh2)2:ICBA blends are only weakly intensity dependent implying a significant contribution of recombination from long-lived CT states and trapped charges, while those in p-DTS(FBTTh2)2:PC70BM decay via an intensity-dependent recombination mechanism indicating that spatially separated (free) charge carriers are observed, which can be extracted as photocurrent from the device.

  18. Shift in the Equilibrium between On and Off States of the Allosteric Switch in Ras-GppNHp Affected by Small Molecules and Bulk Solvent Composition

    SciTech Connect

    Holzapfel, Genevieve; Buhrman, Greg; Mattos, Carla

    2012-08-31

    Ras GTPase cycles between its active GTP-bound form promoted by GEFs and its inactive GDP-bound form promoted by GAPs to affect the control of various cellular functions. It is becoming increasingly apparent that subtle regulation of the GTP-bound active state may occur through promotion of substates mediated by an allosteric switch mechanism that induces a disorder to order transition in switch II upon ligand binding at an allosteric site. We show with high-resolution structures that calcium acetate and either dithioerythritol (DTE) or dithiothreitol (DTT) soaked into H-Ras-GppNHp crystals in the presence of a moderate amount of poly(ethylene glycol) (PEG) can selectively shift the equilibrium to the 'on' state, where the active site appears to be poised for catalysis (calcium acetate), or to what we call the 'ordered off' state, which is associated with an anticatalytic conformation (DTE or DTT). We also show that the equilibrium is reversible in our crystals and dependent on the nature of the small molecule present. Calcium acetate binding in the allosteric site stabilizes the conformation observed in the H-Ras-GppNHp/NOR1A complex, and PEG, DTE, and DTT stabilize the anticatalytic conformation observed in the complex between the Ras homologue Ran and Importin-{beta}. The small molecules are therefore selecting biologically relevant conformations in the crystal that are sampled by the disordered switch II in the uncomplexed GTP-bound form of H-Ras. In the presence of a large amount of PEG, the ordered off conformation predominates, whereas in solution, in the absence of PEG, switch regions appear to remain disordered in what we call the off state, unable to bind DTE.

  19. Pharmacokinetic drivers of toxicity for basic molecules: Strategy to lower pKa results in decreased tissue exposure and toxicity for a small molecule Met inhibitor

    SciTech Connect

    Diaz, Dolores; Ford, Kevin A.; Hartley, Dylan P.; Harstad, Eric B.; Cain, Gary R.; Achilles-Poon, Kirsten; Nguyen, Trung; Peng, Jing; Zheng, Zhong; Merchant, Mark; Sutherlin, Daniel P.; Gaudino, John J.; Kaus, Robert; Lewin-Koh, Sock C.; Choo, Edna F.; Liederer, Bianca M.; Dambach, Donna M.

    2013-01-01

    Several toxicities are clearly driven by free drug concentrations in plasma, such as toxicities related to on-target exaggerated pharmacology or off-target pharmacological activity associated with receptors, enzymes or ion channels. However, there are examples in which organ toxicities appear to correlate better with total drug concentrations in the target tissues, rather than with free drug concentrations in plasma. Here we present a case study in which a small molecule Met inhibitor, GEN-203, with significant liver and bone marrow toxicity in preclinical species was modified with the intention of increasing the safety margin. GEN-203 is a lipophilic weak base as demonstrated by its physicochemical and structural properties: high LogD (distribution coefficient) (4.3) and high measured pKa (7.45) due to the basic amine (N-ethyl-3-fluoro-4-aminopiperidine). The physicochemical properties of GEN-203 were hypothesized to drive the high distribution of this compound to tissues as evidenced by a moderately-high volume of distribution (Vd > 3 l/kg) in mouse and subsequent toxicities of the compound. Specifically, the basicity of GEN-203 was decreased through addition of a second fluorine in the 3-position of the aminopiperidine to yield GEN-890 (N-ethyl-3,3-difluoro-4-aminopiperidine), which decreased the volume of distribution of the compound in mouse (Vd = 1.0 l/kg), decreased its tissue drug concentrations and led to decreased toxicity in mice. This strategy suggests that when toxicity is driven by tissue drug concentrations, optimization of the physicochemical parameters that drive tissue distribution can result in decreased drug concentrations in tissues, resulting in lower toxicity and improved safety margins. -- Highlights: ? Lower pKa for a small molecule: reduced tissue drug levels and toxicity. ? New analysis tools to assess electrostatic effects and ionization are presented. ? Chemical and PK drivers of toxicity can be leveraged to improve safety.

  20. HIV-1 entry inhibition by small-molecule CCR5 antagonists: A combined molecular modeling and mutant study using a high-throughput assay

    SciTech Connect

    Labrecque, Jean; Metz, Markus; Lau, Gloria; Darkes, Marilyn C.; Wong, Rebecca S.Y.; Bogucki, David; Carpenter, Bryon; Chen Gang; Li Tongshuang; Nan, Susan; Schols, Dominique; Bridger, Gary J.; Fricker, Simon P.; Skerlj, Renato T.

    2011-05-10

    Based on the attrition rate of CCR5 small molecule antagonists in the clinic the discovery and development of next generation antagonists with an improved pharmacology and safety profile is necessary. Herein, we describe a combined molecular modeling, CCR5-mediated cell fusion, and receptor site-directed mutagenesis approach to study the molecular interactions of six structurally diverse compounds (aplaviroc, maraviroc, vicriviroc, TAK-779, SCH-C and a benzyloxycarbonyl-aminopiperidin-1-yl-butane derivative) with CCR5, a coreceptor for CCR5-tropic HIV-1 strains. This is the first study using an antifusogenic assay, a model of the interaction of the gp120 envelope protein with CCR5. This assay avoids the use of radioactivity and HIV infection assays, and can be used in a high throughput mode. The assay was validated by comparison with other established CCR5 assays. Given the hydrophobic nature of the binding pocket several binding models are suggested which could prove useful in the rational drug design of new lead compounds.

  1. Computational Ranking of Yerba Mate Small Molecules Based on Their Predicted Contribution to Antibacterial Activity against Methicillin-Resistant Staphylococcus aureus

    SciTech Connect

    Rempe, Caroline S.; Burris, Kellie P.; Woo, Hannah L.; Goodrich, Benjamin; Gosnell, Denise Koessler; Tschaplinski, Timothy J.; Stewart, C. Neal

    2015-05-08

    We report that the aqueous extract of yerba mate, a South American tea beverage made from Ilex paraguariensis leaves, has demonstrated bactericidal and inhibitory activity against bacterial pathogens, including methicillin-resistant Staphylococcus aureus (MRSA). The gas chromatography-mass spectrometry (GC-MS) analysis of two unique fractions of yerba mate aqueous extract revealed 8 identifiable small molecules in those fractions with antimicrobial activity. For a more comprehensive analysis, a data analysis pipeline was assembled to prioritize compounds for antimicrobial testing against both MRSA and methicillin-sensitive S. aureus using forty-two unique fractions of the tea extract that were generated in duplicate, assayed for activity, and analyzed with GC-MS. As validation of our automated analysis, we checked our predicted active compounds for activity in literature references and used authentic standards to test for antimicrobial activity. 3,4-dihydroxybenzaldehyde showed the most antibacterial activity against MRSA at low concentrations in our bioassays. In addition, quinic acid and quercetin were identified using random forests analysis and 5-hydroxy pipecolic acid was identified using linear discriminant analysis. We also generated a ranked list of unidentified compounds that may contribute to the antimicrobial activity of yerba mate against MRSA. Here we utilized GC-MS data to implement an automated analysis that resulted in a ranked list of compounds that likely contribute to the antimicrobial activity of aqueous yerba mate extract against MRSA.

  2. Computational Ranking of Yerba Mate Small Molecules Based on Their Predicted Contribution to Antibacterial Activity against Methicillin-Resistant Staphylococcus aureus

    DOE PAGES [OSTI]

    Rempe, Caroline S.; Burris, Kellie P.; Woo, Hannah L.; Goodrich, Benjamin; Gosnell, Denise Koessler; Tschaplinski, Timothy J.; Stewart, C. Neal

    2015-05-08

    We report that the aqueous extract of yerba mate, a South American tea beverage made from Ilex paraguariensis leaves, has demonstrated bactericidal and inhibitory activity against bacterial pathogens, including methicillin-resistant Staphylococcus aureus (MRSA). The gas chromatography-mass spectrometry (GC-MS) analysis of two unique fractions of yerba mate aqueous extract revealed 8 identifiable small molecules in those fractions with antimicrobial activity. For a more comprehensive analysis, a data analysis pipeline was assembled to prioritize compounds for antimicrobial testing against both MRSA and methicillin-sensitive S. aureus using forty-two unique fractions of the tea extract that were generated in duplicate, assayed for activity, andmore » analyzed with GC-MS. As validation of our automated analysis, we checked our predicted active compounds for activity in literature references and used authentic standards to test for antimicrobial activity. 3,4-dihydroxybenzaldehyde showed the most antibacterial activity against MRSA at low concentrations in our bioassays. In addition, quinic acid and quercetin were identified using random forests analysis and 5-hydroxy pipecolic acid was identified using linear discriminant analysis. We also generated a ranked list of unidentified compounds that may contribute to the antimicrobial activity of yerba mate against MRSA. Here we utilized GC-MS data to implement an automated analysis that resulted in a ranked list of compounds that likely contribute to the antimicrobial activity of aqueous yerba mate extract against MRSA.« less

  3. Including screening in van der Waals corrected density functional theory calculations: The case of atoms and small molecules physisorbed on graphene

    SciTech Connect

    Silvestrelli, Pier Luigi; Ambrosetti, Alberto

    2014-03-28

    The Density Functional Theory (DFT)/van der Waals-Quantum Harmonic Oscillator-Wannier function (vdW-QHO-WF) method, recently developed to include the vdW interactions in approximated DFT by combining the quantum harmonic oscillator model with the maximally localized Wannier function technique, is applied to the cases of atoms and small molecules (X=Ar, CO, H{sub 2}, H{sub 2}O) weakly interacting with benzene and with the ideal planar graphene surface. Comparison is also presented with the results obtained by other DFT vdW-corrected schemes, including PBE+D, vdW-DF, vdW-DF2, rVV10, and by the simpler Local Density Approximation (LDA) and semilocal generalized gradient approximation approaches. While for the X-benzene systems all the considered vdW-corrected schemes perform reasonably well, it turns out that an accurate description of the X-graphene interaction requires a proper treatment of many-body contributions and of short-range screening effects, as demonstrated by adopting an improved version of the DFT/vdW-QHO-WF method. We also comment on the widespread attitude of relying on LDA to get a rough description of weakly interacting systems.

  4. Highly efficient electroluminescence from a solution-processable thermally activated delayed fluorescence emitter

    SciTech Connect

    Wada, Yoshimasa; Kubo, Shosei; Suzuki, Katsuaki; Kaji, Hironori; Shizu, Katsuyuki; Tanaka, Hiroyuki; Adachi, Chihaya

    2015-11-02

    We developed a thermally activated delayed fluorescence (TADF) emitter, 2,4,6-tris(4-(9,9-dimethylacridan-10-yl)phenyl)-1,3,5-triazine (3ACR-TRZ), suitable for use in solution-processed organic light-emitting diodes (OLEDs). When doped into 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host at 16 wt. %, 3ACR-TRZ showed a high photoluminescence quantum yield of 98%. Transient photoluminescence decay measurements of the 16 wt. % 3ACR-TRZ:CBP film confirmed that 3ACR-TRZ exhibits efficient TADF with a triplet-to-light conversion efficiency of 96%. This high conversion efficiency makes 3ACR-TRZ attractive as an emitting dopant in OLEDs. Using 3ACR-TRZ as an emitter, we fabricated a solution-processed OLED exhibiting a maximum external quantum efficiency of 18.6%.

  5. Multi-functional ultrathin PdxCu1-x and Pt~PdxCu1-x one-dimensional nanowire motifs for various small molecule oxidation reactions

    DOE PAGES [OSTI]

    Liu, Haiqing; Wong, Stanislaus S.; Adzic, Radoslav R.

    2015-11-18

    Developing novel electrocatalysts for small molecule oxidation processes, including formic acid oxidation (FAOR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR), denoting the key anodic reactions for their respective fuel cell configurations, is a significant and relevant theme of recent efforts in the field. Herein, in this report, we demonstrated a concerted effort to couple and combine the benefits of small size, anisotropic morphology, and tunable chemical composition in order to devise a novel “family” of functional architectures. In particular, we have fabricated not only ultrathin 1-D Pd1–xCux alloys but also Pt-coated Pd1–xCux (i.e., Pt~Pd1–xCux; herein the ~ indicatesmore » an intimate association, but not necessarily actual bond formation, between the inner bimetallic core and the Pt outer shell) core–shell hierarchical nanostructures with readily tunable chemical compositions by utilizing a facile, surfactant-based, wet chemical synthesis coupled with a Cu underpotential deposition technique. Our main finding is that our series of as-prepared nanowires are functionally flexible. More precisely, we demonstrate that various examples within this “family” of structural motifs can be tailored for exceptional activity with all 3 of these important electrocatalytic reactions. In particular, we note that our series of Pd1–xCux nanowires all exhibit enhanced FAOR activities as compared with not only analogous Pd ultrathin nanowires but also commercial Pt and Pd standards, with Pd9Cu representing the “optimal” composition. Moreover, our group of Pt~Pd1–xCux nanowires consistently outperformed not only commercial Pt NPs but also ultrathin Pt nanowires by several fold orders of magnitude for both the MOR and EOR reactions in alkaline media. As a result, the variation of the MOR and EOR performance with the chemical composition of our ultrathin Pt~Pd1–xCux nanowires was also discussed.« less

  6. Tolerance of Three-Stage CIGS Deposition to Variations Imposed by Roll-to-Roll Processing: Final Technical Report, May 2003 - September 2005

    SciTech Connect

    Beck, M. E.; Britt, J. S.

    2006-01-01

    Three-stage co-evaporation of CIGS imposes stringent limits on the parameter space if high-efficient devices are to result. Substrate temperatures during the 1st stage (as well as during the 2nd and 3rd stage), Se partial pressure, and amount of Na supplied are critical for good nucleation, proper In-Ga-selenide precursor phase, and diffusion of Cu into the precursor, as well as diffusion of Ga through the film. In addition, the degree of Cu-rich excursion impacts maximum performance and process tolerance. Enveloping the above is the basic time-temperature profile inextricably linked to the metals delivery rates. Although high-efficiency, three-stage deposited CIGS devices on the R&D scale are grown at about 20-45 minutes to thicknesses of 2 to 2.5 m, the latter is not a viable approach for an economic manufacturing process. At Global Solar Energy, Inc., CIGS films are typically grown in about 6 minutes to thicknesses of less than 2 m. At the same time, the emissivity and thermal conductivity of stainless steel is vastly different from that of glass, and the reduced growth time poses restrictions on the substrate temperature ramp rates and diffusion of species (reaction kinetics). Material compatibility in the highly corrosive Se environment places limitations on the substrate heaters; i.e., substrate temperatures. Finally, one key advantage of a RTR deposition approach (compact equipment) restricts post CIGS Se exposure and cool-down rates to be vastly different than those practiced in the laboratory.

  7. Efficiency and throughput advances in continuous roll-to-roll a-Si alloy PV manufacturing technology: Annual technical progress report: 22 June 1998--21 June 1999

    SciTech Connect

    Izu, M.

    1999-11-09

    This document reports on work performed by Energy Conversion Devices, Inc. (ECD) during Phase 1 of this subcontract. During this period, ECD researchers: (1) Completed design and construction of new, improved substrate heater; (2) Tested and verified improved performance of the new substrate heater in the pilot machine; (3) Verified improved performance of the new substrate heater in the production machine; (4) Designed and bench-tested a new infrared temperature sensor; (5) Installed a prototype new infrared temperature sensor in the production machine for evaluation; (6) Designed a new rolling thermocouple temperature sensor; (7) Designed and bench-tested a reflectometer for the backreflector deposition machine; (8) Designed and bench-tested in-line non-contacting cell diagnostic sensor and PV capacitive diagnostic system; (9) Installed the in-line cell diagnostic sensor in the 5-MW a-Si deposition machine for evaluation; (10) Demonstrated a new low-cost zinc metal process in the pilot back reflector machine; and (11) Fully tested a new cathode design for improved uniformity.

  8. Horizontal molecular orientation in solution-processed organic light-emitting diodes

    SciTech Connect

    Zhao, L.; Inoue, M.; Komino, T.; Kim, J.-H.; Ribierre, J. C. E-mail: adachi@cstf.kyushu-u.ac.jp [Center for Organic Photonics and Electronics Research , Kyushu University, 744 Motooka, Nishi, Fukuoka 819-0395; Japan Science and Technology Agency , ERATO, Adachi Molecular Exciton Engineering Project, c and others

    2015-02-09

    Horizontal orientation of the emission transition dipole moments achieved in glassy vapor-deposited organic thin films leads to an enhancement of the light out-coupling efficiency in organic light-emitting diodes (OLEDs). Here, our combined study of variable angle spectroscopic ellipsometry and angle dependent photoluminescence demonstrates that such a horizontal orientation can be achieved in glassy spin-coated organic films based on a composite blend of a heptafluorene derivative as a dopant and a 4,4′-bis(N-carbazolyl)-1,1′-biphenyl as a host. Solution-processed fluorescent OLEDs with horizontally oriented heptafluorene emitters were then fabricated and emitted deep blue electroluminescence with an external quantum efficiency as high as 5.3%.

  9. Modifying the organic/electrode interface in Organic Solar Cells (OSCs) and improving the efficiency of solution-processed phosphorescent Organic Light-Emitting Diodes (OLEDs)

    SciTech Connect

    Xiao, Teng

    2012-04-27

    thin LiF layer serves typically as the electron injection layer in OLEDs and electron collection interlayer in the OSCs. However, several reports showed that it can also assist in holeinjection in OLEDs. Here we first demonstrate that it assists hole-collection in OSCs, which is more obvious after air-plasma treatment, and explore this intriguing dual role. For OLEDs, we focus on solution processing methods to fabricate highly efficient phosphorescent OLEDs. First, we investigated OLEDs with a polymer host matrix, and enhanced charge injection by adding hole- and electron-transport materials into the system. We also applied a hole-blocking and electron-transport material to prevent luminescence quenching by the cathode. Finally, we substituted the polymer host by a small molecule, to achieve more efficient solution processed small molecular OLEDs (SMOLEDs); this approach is cost-effective in comparison to the more common vacuum thermal evaporation. All these studies help us to better understand the underlying relationship between the organic semiconductor materials and the OSCs and OLEDs’ performance and will subsequently assist in further enhancing the efficiencies of OSCs and OLEDs. With better efficiency and longer lifetime, the OSCs and OLEDs will be competitive with their inorganic counterparts.

  10. Solution processed lanthanum aluminate gate dielectrics for use in metal oxide-based thin film transistors

    SciTech Connect

    Esro, M.; Adamopoulos, G.; Mazzocco, R.; Kolosov, O.; Krier, A.; Vourlias, G.; Milne, W. I.

    2015-05-18

    We report on ZnO-based thin-film transistors (TFTs) employing lanthanum aluminate gate dielectrics (La{sub x}Al{sub 1−x}O{sub y}) grown by spray pyrolysis in ambient atmosphere at 440 °C. The structural, electronic, optical, morphological, and electrical properties of the La{sub x}Al{sub 1−x}O{sub y} films and devices as a function of the lanthanum to aluminium atomic ratio were investigated using a wide range of characterization techniques such as UV-visible absorption spectroscopy, impedance spectroscopy, spectroscopic ellipsometry, atomic force microscopy, x-ray diffraction, and field-effect measurements. As-deposited LaAlO{sub y} dielectrics exhibit a wide band gap (∼6.18 eV), high dielectric constant (k ∼ 16), low roughness (∼1.9 nm), and very low leakage currents (<3 nA/cm{sup 2}). TFTs employing solution processed LaAlO{sub y} gate dielectrics and ZnO semiconducting channels exhibit excellent electron transport characteristics with hysteresis-free operation, low operation voltages (∼10 V), high on/off current modulation ratio of >10{sup 6}, subthreshold swing of ∼650 mV dec{sup −1}, and electron mobility of ∼12 cm{sup 2} V{sup −1} s{sup −1}.

  11. Solution Processable n-Type Perylene Diimide Copolymers for Organic Photovoltaics

    SciTech Connect

    Liang, Z.; Cormier, R. A.; Nardes, A. M.; Gregg, B. A.

    2011-01-01

    Perylene diimides are known as promising n-type semiconductor building blocks. Here we report the synthesis and characterization of a set of three soluble poly(perylene diimide)s and their preliminary characterization in organic photovoltaic cells. These polymers are made through the polycondensation of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) with a variety of poly(ethylene glycol) (PEG)- or poly(propylene glycol) (PPG)-based diamine comonomers. The flexible spacer offers increased solubility in organic solvents and allows the perylene core to assume a conformation that promotes favorable cofacial {pi}-{pi} interactions. Mixtures of these polymers with the hole-transporting polymer, poly(3-hexylthiophene) (P3HT) result in significant fluorescence quenching. However, the phase separation occurs on a scale too large for a bulk heterojunction solar cell. The PPGylated poly(perylene diimide) shows an unusually low free electron concentration ({approx}1.0 x 10{sup 12} cm{sup -3}) and therefore makes an excellent model system for future doping studies. These new polymers may have promise as stable electron-conductive layers with large light-absorptivities in solution-processable applications of organic electronics.

  12. Luminescence and electrical properties of solution-processed ZnO thin films by adding fluorides and annealing atmosphere

    SciTech Connect

    Choi, Sungho; Park, Byung-Yoon; Jung, Ha-Kyun

    2011-06-15

    Highlights: {yields} Systematic study of the fluorides doped solution-processed ZnO thin films via the luminescence and electrical behaviors. {yields} Defect-related visible emission bands are affected by annealing ambient and fluoride addition. {yields} Adding lithium fluoride followed by annealing in oxygen ambient leads to a controlled defect density with proper TFT performance. -- Abstract: To develop an efficient channel layer for thin film transistors (TFTs), understanding the defect-related luminescence and electrical property is crucial for solution-processed ZnO thin films. Film growth with the fluorides addition, especially using LiF, followed by the oxygen ambient post-annealing leads to decreased defect-related emission as well as enhanced switching property. The saturation mobility and current on/off ratio are 0.31 cm{sup 2} V{sup -1} s{sup -1} and 1.04 x 10{sup 3}. Consequently, we can visualize an optimized process condition and characterization method for solution-processed TFT based on the fluorine-doped ZnO film channel layer by considering the overall emission behavior.

  13. [Transition metal mediated transformations of small molecules

    SciTech Connect

    Sen, A.

    1992-01-01

    Work on organotransition metal chemistry, homogeneous and heterogeneous catalysis is summarized. Several cationic palladium(II) complexes with bulky phosphine or pyridine ligands were discovered that are highly selective catalysts for linear dimerization of vinyl monomers and linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. Our studies were continued on alternating olefin-carbon monoxide copolymers. The copolymerization reaction and reactivity of copolymers were examined. New catalytic systems for alternating copolymerization of [alpha]-olefins with CO were discovered. In the case of styrene derivatives, tactic copolymers were obtained. Poly(ethylenepyrrolediyl) derivatives were synthesized from alternating ethylene-carbon monoxide copolymer and become electronic conductors when doped with iodine. A catalytic system for direct synthesis of polyureas and polyoxamides from and diamines was also discovered. Pt metal catalyzed the oxidation of ethers, esters, and amines to carboxylic acids and the oxidation of olefins to 1,2-diols. Anaerobic and aerobic decomposition of molybdenum(VI)-oxoalkyl compounds were studied for heterogeneous oxidation of alkanes and olefins on Mo(VI)-oxide surfaces. Synthesis of polymer-trapped metal, metal oxide, and metal sulfide nanoclusters (size <1--10 nm) was studied.

  14. Multimodality Plant Imaging of Small Molecules

    SciTech Connect

    DeJesus, Onofre T.

    2015-03-12

    Positron emission tomography (PET) is a non-invasive imaging technique used to diagnose disease and monitor therapy. PET imaging has had tremendous impact in healthcare delivery resulting in improved outcomes and reduced costs. The discovery and development of PET is one of the achievements of the Department of Energy’s (DOE) support of the peaceful uses of the atom. This project is a logical extension of the use of the PET technique to live plant imaging to advance DOE’s biological and environmental initiatives.

  15. Allosteric Modulation of DNA by Small Molecules

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    converge at transcription factors, which in turn regulate the transcription of sets of genes that result in the gene expression. Many human diseases are caused by dysregulated...

  16. Interfacial Engineering for Highly Efficient-Conjugated Polymer-Based Bulk Heterojunction Photovoltaic Devices

    SciTech Connect

    Alex Jen; David Ginger; Christine Luscombe; Hong Ma

    2012-04-02

    The aim of our proposal is to apply interface engineering approach to improve charge extraction, guide active layer morphology, improve materials compatibility, and ultimately allow the fabrication of high efficiency tandem cells. Specifically, we aim at developing: i. Interfacial engineering using small molecule self-assembled monolayers ii. Nanostructure engineering in OPVs using polymer brushes iii. Development of efficient light harvesting and high mobility materials for OPVs iv. Physical characterization of the nanostructured systems using electrostatic force microscopy, and conducting atomic force microscopy v. All-solution processed organic-based tandem cells using interfacial engineering to optimize the recombination layer currents vi. Theoretical modeling of charge transport in the active semiconducting layer The material development effort is guided by advanced computer modeling and surface/ interface engineering tools to allow us to obtain better understanding of the effect of electrode modifications on OPV performance for the investigation of more elaborate device structures. The materials and devices developed within this program represent a major conceptual advancement using an integrated approach combining rational molecular design, material, interface, process, and device engineering to achieve solar cells with high efficiency, stability, and the potential to be used for large-area roll-to-roll printing. This may create significant impact in lowering manufacturing cost of polymer solar cells for promoting clean renewable energy use and preventing the side effects from using fossil fuels to impact environment.

  17. Suppression of dark current through barrier engineer for solution-processed colloidal quantum-dots infrared photodetectors

    SciTech Connect

    Jiang, Zhenyu E-mail: jianxu@engr.psu.edu; Liu, Yan; Mo, Chen; Wang, Li; Atalla, Mahmoud R. M.; Liu, Jie; Kurhade, Kandhar K.; Xu, Jian E-mail: jianxu@engr.psu.edu; Hu, Wenjia; Zhang, Wenjun; You, Guanjun; Zhang, Yu

    2015-08-31

    In an attempt to suppress the dark current, the barrier layer engineer for solution-processed PbSe colloidal quantum-dot (CQD) photodetectors has been investigated in the present study. It was found that the dark current can be significantly suppressed by implementing two types of carrier blocking layers, namely, hole blocking layer and electron blocking layer, sandwiched in between two active PbSe CQD layers. Meanwhile no adverse impact has been observed for the photo current. Our study suggests that this improvement resides on the transport pathway created via carrier recombination at intermediate layer, which provides wide implications for the suppression of dark current for infrared photodetectors.

  18. Final Closeout report for grant FG36-08GO18018, titled: Functional Multi-Layer Solution Processable Polymer Solar Cells

    SciTech Connect

    Adam J. Moule

    2012-05-01

    The original objectives were: (1) Develop a method to deposit multiple conjugated polymer film layers and avoid the problem of dissolution from mutually solubility; (2) Use this deposition method to develop multi-layer polymer based solar cells with layers that are function specific; (3) characterize these layers and devices; (4) develop electrical and optical models that describe and predict the properties of the multi-layers; and (5) Ultimate efficiency goals are {approx}6.75% with J{sub sc} = 12 mA/cm{sup 2}, FF = 0.75, and V{sub oc} = 0.75. The question of whether photovoltaic (PV) cells will ever be able to replace fossil fuels as the main provider of electrical power is not just a question of device efficiency; it is a question of how much power can be provided for what price. It has been well documented that PV devices at 10% power efficiency can provide for all of the world's power needs without covering too much of the earth's surface. Assuming desert like cloud coverage, an area equivalent to the land area of Texas would have to be covered. However, it has also been shown that using the current state-of-the-art silicon devices, the price-per-Watt will never be low enough to be economically feasible for large-scale development. Solution-processable PV devices based on polymers are a very attractive alternative to traditional Silicon PV because this technology is much lower in materials cost and in environmentally toxic waste production. Solution-based polymers can be rapidly deposited using printing technologies and are compatible with light-weight flexible substrates that can increase the range of available PV applications. In the past ten years, the efficiency of polymer based PV devices has increased from {approx}1% to over 10%. The highest efficiency organic solar cells are based upon a single layer than consists of a mixture of donor and acceptor moieties. This one layer has multiple optical and electrical functions, so the design of a single

  19. Light-induced hysteresis and recovery behaviors in photochemically activated solution-processed metal-oxide thin-film transistors

    SciTech Connect

    Jo, Jeong-Wan; Park, Sung Kyu E-mail: skpark@cau.ac.kr; Kim, Yong-Hoon E-mail: skpark@cau.ac.kr

    2014-07-28

    In this report, photo-induced hysteresis, threshold voltage (V{sub T}) shift, and recovery behaviors in photochemically activated solution-processed indium-gallium-zinc oxide (IGZO) thin-film transistors (TFTs) are investigated. It was observed that a white light illumination caused negative V{sub T} shift along with creation of clockwise hysteresis in electrical characteristics which can be attributed to photo-generated doubly ionized oxygen vacancies at the semiconductor/gate dielectric interface. More importantly, the photochemically activated IGZO TFTs showed much reduced overall V{sub T} shift compared to thermally annealed TFTs. Reduced number of donor-like interface states creation under light illumination and more facile neutralization of ionized oxygen vacancies by electron capture under positive gate potential are claimed to be the origin of the less V{sub T} shift in photochemically activated TFTs.

  20. SKLB70326, a novel small-molecule inhibitor of cell-cycle progression, induces G{sub 0}/G{sub 1} phase arrest and apoptosis in human hepatic carcinoma cells

    SciTech Connect

    Han, Yuanyuan; He, Haiyun; Peng, Feng; Liu, Jiyan; Dai, Xiaoyun; Lin, Hongjun; Xu, Youzhi; Zhou, Tian; Mao, Yongqiu; Xie, Gang; Yang, Shengyong; Yu, Luoting; Yang, Li; Zhao, Yinglan

    2012-05-18

    Highlights: Black-Right-Pointing-Pointer SKLB70326 is a novel compound and has activity of anti-HCC. Black-Right-Pointing-Pointer SKLB70326 induces cell cycle arrest and apoptosis in HepG2 cells. Black-Right-Pointing-Pointer SKLB70326 induces G{sub 0}/G{sub 1} phase arrest via inhibiting the activity of CDK2, CDK4 and CDK6. Black-Right-Pointing-Pointer SKLB70326 induces apoptosis through the intrinsic pathway. -- Abstract: We previously reported the potential of a novel small molecule 3-amino-6-(3-methoxyphenyl)thieno[2.3-b]pyridine-2-carboxamide (SKLB70326) as an anticancer agent. In the present study, we investigated the anticancer effects and possible mechanisms of SKLB70326 in vitro. We found that SKLB70326 treatment significantly inhibited human hepatic carcinoma cell proliferation in vitro, and the HepG2 cell line was the most sensitive to its treatment. The inhibition of cell proliferation correlated with G{sub 0}/G{sub 1} phase arrest, which was followed by apoptotic cell death. The SKLB70326-mediated cell-cycle arrest was associated with the downregulation of cyclin-dependent kinase (CDK) 2, CDK4 and CDK6 but not cyclin D1 or cyclin E. The phosphorylation of the retinoblastoma protein (Rb) was also observed. SKLB70326 treatment induced apoptotic cell death via the activation of PARP, caspase-3, caspase-9 and Bax as well as the downregulation of Bcl-2. The expression levels of p53 and p21 were also induced by SKLB70326 treatment. Moreover, SKLB70326 treatment was well tolerated. In conclusion, SKLB70326, a novel cell-cycle inhibitor, notably inhibits HepG2 cell proliferation through the induction of G{sub 0}/G{sub 1} phase arrest and subsequent apoptosis. Its potential as a candidate anticancer agent warrants further investigation.

  1. Multi-functional ultrathin PdxCu1-x and Pt~PdxCu1-x one-dimensional nanowire motifs for various small molecule oxidation reactions

    SciTech Connect

    Liu, Haiqing; Wong, Stanislaus S.; Adzic, Radoslav R.

    2015-11-18

    Developing novel electrocatalysts for small molecule oxidation processes, including formic acid oxidation (FAOR), methanol oxidation reaction (MOR), and ethanol oxidation reaction (EOR), denoting the key anodic reactions for their respective fuel cell configurations, is a significant and relevant theme of recent efforts in the field. Herein, in this report, we demonstrated a concerted effort to couple and combine the benefits of small size, anisotropic morphology, and tunable chemical composition in order to devise a novel “family” of functional architectures. In particular, we have fabricated not only ultrathin 1-D Pd1–xCux alloys but also Pt-coated Pd1–xCux (i.e., Pt~Pd1–xCux; herein the ~ indicates an intimate association, but not necessarily actual bond formation, between the inner bimetallic core and the Pt outer shell) core–shell hierarchical nanostructures with readily tunable chemical compositions by utilizing a facile, surfactant-based, wet chemical synthesis coupled with a Cu underpotential deposition technique. Our main finding is that our series of as-prepared nanowires are functionally flexible. More precisely, we demonstrate that various examples within this “family” of structural motifs can be tailored for exceptional activity with all 3 of these important electrocatalytic reactions. In particular, we note that our series of Pd1–xCux nanowires all exhibit enhanced FAOR activities as compared with not only analogous Pd ultrathin nanowires but also commercial Pt and Pd standards, with Pd9Cu representing the “optimal” composition. Moreover, our group of Pt~Pd1–xCux nanowires consistently outperformed not only commercial Pt NPs but also ultrathin Pt nanowires by several fold orders of magnitude for both the MOR and EOR reactions in alkaline media. As a result, the variation of the MOR and EOR performance with

  2. Modulation of physical and photocatalytic properties of (Cr, N) codoped TiO{sub 2} nanorods using soft solution processing

    SciTech Connect

    Lu, Wen-Chung; Nguyen, Hoang-Diem; Wu, Chun-Yi; Chang, Kao-Shuo Yoshimura, Masahiro

    2014-04-14

    Facile polymerized complex reactions together with a hydrothermal reaction were implemented to make single crystalline TiO{sub 2} nanorods for the first time. Chromium (Cr) and nitrogen (N{sub 2}) co-doping was performed to tailor the physical properties. Transmission electron microscopy and x-ray diffraction study illustrated that highly reactive facets of (101), (111), and (001) dominated rutile TiO{sub 2} nanorods. A growth model, based on formation of complex species, was proposed to elucidate effectiveness of the soft solution processing in making TiO{sub 2} nanorods. X-ray photoelectron spectroscopy analysis and consideration of fundamentals of charge neutrality showed N{sub 2} doping could inhibit formation of Cr{sup 6+} and oxygen vacancies (V{sub O}{sup 2+}). An investigation of the photocatalytic properties exhibited high efficiency of photodegradation of methylene blue in 15 min under pH = 10, using a nanocomposite of (7% Cr, 0.0021% N) codoped and 3% Cr doped TiO{sub 2} nanorods.

  3. A water-processable organic electron-selective layer for solution-processed inverted organic solar cells

    SciTech Connect

    Chen, Dongcheng; Zhou, Hu; Cai, Ping; Sun, Shi; Ye, Hua; Su, Shi-Jian Cao, Yong

    2014-02-03

    A triazine- and pyridinium-containing water-soluble material of 1,1?,1?-(4,4?,4?-(1,3,5-triazine-2,4,6-triyl)tris(benzene-4,1-diyl)) tris(methylene)tripyridinium bromide (TzPyBr) was developed as an organic electron-selective layer in solution-processed inverted organic solar cells due to its strong anti-erosion capacity against non-polar organic solvents commonly used for the active layer. Ohmic-like contact with the adjacent active materials like fullerene derivatives is speculated to be formed, as confirmed by the work-function measurements with scanning Kelvin probe and ultraviolet photoelectron spectroscopy techniques. Besides, considering the deep highest occupied molecular orbital energy level of TzPyBr, excellent hole-blocking property of the electron-selective layer is also anticipated. The inverted organic photovoltaic devices based on the TzPyBr/ITO (indium tin oxide) bilayer cathode exhibit dramatically enhanced performance compared to the control devices with bare ITO as the cathode and even higher efficiency than the conventional type devices with ITO and Al as the electrodes.

  4. CRADA final report: Technical assessment of roll-to-roll operation of lamination process, thermal treatment, and alternative carbon fiber precursors for low-cost, high-efficiency manufacturing of flow battery stacks and other energy devices

    SciTech Connect

    Daniel, Claus; Madden, Thomas; Wood, III, David L; Muth, Thomas R.; Warrington, Curtis; Ozcan, Soydan; Manson, Hunter; Tekinalp, Halil L.; Smith, Mark A.; Lu, Yuan; Loretz, Jeremy

    2015-09-23

    Among the various stationary-storage technologies under development, redox flow batteries (RFBs) offer the greatest potential to deliver inexpensive, scalable, and efficient grid-scale electrical-energy storage. Unlike traditional sealed batteries, in a flow battery power and energy are decoupled. Cell area and cell count in the stack determine the device power, and the chemical storage volume determines the total energy. Grid-scale energy-storage applications require megawatt-scale devices, which require the assembly of hundreds of large-area, bipolar cells per power plant. The cell-stack is the single system component with the largest impact on capital cost (due to the large number of highly engineered components) and operating costs (determined by overall round-trip efficiency).

  5. Morphology Development of Polymer-Fullerene and Polymer-Polymer Solar

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Cells during Solution-Shearing Blade Coating | Stanford Synchrotron Radiation Lightsource Morphology Development of Polymer-Fullerene and Polymer-Polymer Solar Cells during Solution-Shearing Blade Coating Monday, October 31, 2016 Polymer solar cells represent a promising technology that enables solution processing of low-cost, flexible photovoltaic devices for clean energy applications through typical industrial mass production techniques, such as roll-to-roll printing. When fabricating

  6. Solution-processable glass LiI-Li4SnS4 superionic conductors for all-solid-state Li-ion batteries

    DOE PAGES [OSTI]

    Kern Ho Park; Oh, Dae Yang; Choi, Young Eun; Nam, Young Jin; Han, Lili; Kim, Ju -Young; Xin, Huolin; Lin, Feng; Oh, Seung M.; Jung, Yoon Seok

    2015-12-22

    The new, highly conductive (4.1 × 10–4 S cm–1 at 30 °C), highly deformable, and dry-air-stable glass 0.4LiI-0.6Li4SnS4 is prepared using a homogeneous methanol solution. Furthermore, the solution process enables the wetting of any exposed surface of the active materials with highly conductive solidified electrolytes (0.4LiI-0.6Li4SnS4), resulting in considerable improvements in electrochemical performances of these electrodes over conventional mixture electrodes.

  7. Solution-processable glass LiI-Li4SnS4 superionic conductors for all-solid-state Li-ion batteries

    SciTech Connect

    Kern Ho Park; Oh, Dae Yang; Choi, Young Eun; Nam, Young Jin; Han, Lili; Kim, Ju -Young; Xin, Huolin; Lin, Feng; Oh, Seung M.; Jung, Yoon Seok

    2015-12-22

    The new, highly conductive (4.1 × 10–4 S cm–1 at 30 °C), highly deformable, and dry-air-stable glass 0.4LiI-0.6Li4SnS4 is prepared using a homogeneous methanol solution. Furthermore, the solution process enables the wetting of any exposed surface of the active materials with highly conductive solidified electrolytes (0.4LiI-0.6Li4SnS4), resulting in considerable improvements in electrochemical performances of these electrodes over conventional mixture electrodes.

  8. SEP Benefits to Program Administrators

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    High Value Roll-to-Roll Manufacturing Workshop Alexandria, VA 22314 December 2-3

  9. [Transition metal mediated transformations of small molecules]. Progress report

    SciTech Connect

    Sen, A.

    1992-10-01

    Work on organotransition metal chemistry, homogeneous and heterogeneous catalysis is summarized. Several cationic palladium(II) complexes with bulky phosphine or pyridine ligands were discovered that are highly selective catalysts for linear dimerization of vinyl monomers and linear polymerization of p-divinylbenzene, the reactions proceeding through a carbocationic mechanism. Our studies were continued on alternating olefin-carbon monoxide copolymers. The copolymerization reaction and reactivity of copolymers were examined. New catalytic systems for alternating copolymerization of {alpha}-olefins with CO were discovered. In the case of styrene derivatives, tactic copolymers were obtained. Poly(ethylenepyrrolediyl) derivatives were synthesized from alternating ethylene-carbon monoxide copolymer and become electronic conductors when doped with iodine. A catalytic system for direct synthesis of polyureas and polyoxamides from and diamines was also discovered. Pt metal catalyzed the oxidation of ethers, esters, and amines to carboxylic acids and the oxidation of olefins to 1,2-diols. Anaerobic and aerobic decomposition of molybdenum(VI)-oxoalkyl compounds were studied for heterogeneous oxidation of alkanes and olefins on Mo(VI)-oxide surfaces. Synthesis of polymer-trapped metal, metal oxide, and metal sulfide nanoclusters (size <1--10 nm) was studied.

  10. Preface for small-molecule activation: Carbon-containing fuels

    SciTech Connect

    Fujita, Etsuko; Goldman, Alan S.

    2015-06-01

    For millennia, human transportation was fueled largely through the consumption of biomass (by humans or domestic animals) and to a lesser extent by wind. The 19th century saw a major shift to coal-fueled transportation, with trains and ships powered by steam engines. A second major shift in the fueling of transportation occurred in the 20th century, this time to petroleum. Thus, this transition was not driven by the cost or ease of obtaining energy from oil wells vs. coal mines indeed, the cost of petroleum has always been higher than coal on a per-unit-energy basis but rather by the tremendous technical advantages of powering engines with liquids, specifically liquid hydrocarbons.

  11. A general strategy to construct small molecule biosensors in...

    Office of Scientific and Technical Information (OSTI)

    Authors: Feng, Justin ; Jester, Benjamin W. ; Tinberg, Christine E. ; Mandell, Daniel J. ; Antunes, Mauricio S. ; Chari, Raj ; Morey, Kevin J. ; Rios, Xavier ; Medford, June I. ; ...

  12. Preface for small-molecule activation: Carbon-containing fuels

    DOE PAGES [OSTI]

    Fujita, Etsuko; Goldman, Alan S.

    2015-06-01

    For millennia, human transportation was fueled largely through the consumption of biomass (by humans or domestic animals) and to a lesser extent by wind. The 19th century saw a major shift to coal-fueled transportation, with trains and ships powered by steam engines. A second major shift in the fueling of transportation occurred in the 20th century, this time to petroleum. Thus, this transition was not driven by the cost or ease of obtaining energy from oil wells vs. coal mines – indeed, the cost of petroleum has always been higher than coal on a per-unit-energy basis – but rather bymore » the tremendous technical advantages of powering engines with liquids, specifically liquid hydrocarbons.« less

  13. Preface for small-molecule activation: Carbon-containing fuels

    SciTech Connect

    Fujita, Etsuko; Goldman, Alan S.

    2015-06-01

    For millennia, human transportation was fueled largely through the consumption of biomass (by humans or domestic animals) and to a lesser extent by wind. The 19th century saw a major shift to coal-fueled transportation, with trains and ships powered by steam engines. A second major shift in the fueling of transportation occurred in the 20th century, this time to petroleum. Thus, this transition was not driven by the cost or ease of obtaining energy from oil wells vs. coal mines – indeed, the cost of petroleum has always been higher than coal on a per-unit-energy basis – but rather by the tremendous technical advantages of powering engines with liquids, specifically liquid hydrocarbons.

  14. Oxidation-resistant, solution-processed plasmonic Ni nanochain-SiO{sub x} (x < 2) selective solar thermal absorbers

    SciTech Connect

    Yu, Xiaobai; Wang, Xiaoxin; Liu, Jifeng; Zhang, Qinglin; Li, Juchuan

    2014-08-21

    Metal oxidation at high temperatures has long been a challenge in cermet solar thermal absorbers, which impedes the development of atmospherically stable, high-temperature, high-performance concentrated solar power (CSP) systems. In this work, we demonstrate solution-processed Ni nanochain-SiO{sub x} (x < 2) and Ni nanochain-SiO{sub 2} selective solar thermal absorbers that exhibit a strong anti-oxidation behavior up to 600 °C in air. The thermal stability is far superior to previously reported Ni nanoparticle-Al{sub 2}O{sub 3} selective solar thermal absorbers, which readily oxidize at 450 °C. The SiO{sub x} (x < 2) and SiO{sub 2} matrices are derived from hydrogen silsesquioxane and tetraethyl orthosilicate precursors, respectively, which comprise Si-O cage-like structures and Si-O networks. Fourier transform infrared spectroscopy shows that the dissociation of Si-O cage-like structures and Si-O networks at high temperatures have enabled the formation of new bonds at the Ni/SiO{sub x} interface to passivate the surface of Ni nanoparticles and prevent oxidation. X-ray photoelectron spectroscopy and Raman spectroscopy demonstrate that the excess Si in the SiO{sub x} (x < 2) matrices reacts with Ni nanostructures to form silicides at the interfaces, which further improves the anti-oxidation properties. As a result, Ni-SiO{sub x} (x < 2) systems demonstrate better anti-oxidation performance than Ni-SiO{sub 2} systems. This oxidation-resistant Ni nanochain-SiO{sub x} (x < 2) cermet coating also exhibits excellent high-temperature optical performance, with a high solar absorptance of ∼90% and a low emittance ∼18% measured at 300 °C. These results open the door towards atmospheric stable, high temperature, high-performance solar selective absorber coatings processed by low-cost solution-chemical methods for future generations of CSP systems.

  15. Efficient indium-tin-oxide free inverted organic solar cells based on aluminum-doped zinc oxide cathode and low-temperature aqueous solution processed zinc oxide electron extraction layer

    SciTech Connect

    Chen, Dazheng; Zhang, Chunfu Wang, Zhizhe; Zhang, Jincheng; Tang, Shi; Wei, Wei; Sun, Li; Hao, Yue

    2014-06-16

    Indium-tin-oxide (ITO) free inverted organic solar cells (IOSCs) based on aluminum-doped zinc oxide (AZO) cathode, low-temperature aqueous solution processed zinc oxide (ZnO) electron extraction layer, and poly(3-hexylthiophene-2, 5-diyl):[6, 6]-phenyl C{sub 61} butyric acid methyl ester blend were realized in this work. The resulted IOSC with ZnO annealed at 150 °C shows the superior power conversion efficiency (PCE) of 3.01%, if decreasing the ZnO annealing temperature to 100 °C, the obtained IOSC also shows a PCE of 2.76%, and no light soaking issue is observed. It is found that this ZnO film not only acts as an effective buffer layer but also slightly improves the optical transmittance of AZO substrates. Further, despite the relatively inferior air-stability, these un-encapsulated AZO/ZnO IOSCs show comparable PCEs to the referenced ITO/ZnO IOSCs, which demonstrates that the AZO cathode is a potential alternative to ITO in IOSCs. Meanwhile, this simple ZnO process is compatible with large area deposition and plastic substrates, and is promising to be widely used in IOSCs and other relative fields.

  16. An easy-to-fabricate low-temperature TiO{sub 2} electron collection layer for high efficiency planar heterojunction perovskite solar cells

    SciTech Connect

    Conings, B.; Baeten, L.; Jacobs, T.; Dera, R.; D’Haen, J.; Manca, J.; Boyen, H.-G.

    2014-08-01

    Organometal trihalide perovskite solar cells arguably represent the most auspicious new photovoltaic technology so far, as they possess an astonishing combination of properties. The impressive and brisk advances achieved so far bring forth highly efficient and solution processable solar cells, holding great promise to grow into a mature technology that is ready to be embedded on a large scale. However, the vast majority of state-of-the-art perovskite solar cells contains a dense TiO{sub 2} electron collection layer that requires a high temperature treatment (>450 °C), which obstructs the road towards roll-to-roll processing on flexible foils that can withstand no more than ∼150 °C. Furthermore, this high temperature treatment leads to an overall increased energy payback time and cumulative energy demand for this emerging photovoltaic technology. Here we present the implementation of an alternative TiO{sub 2} layer formed from an easily prepared nanoparticle dispersion, with annealing needs well within reach of roll-to-roll processing, making this technology also appealing from the energy payback aspect. Chemical and morphological analysis allows to understand and optimize the processing conditions of the TiO{sub 2} layer, finally resulting in a maximum obtained efficiency of 13.6% for a planar heterojunction solar cell within an ITO/TiO{sub 2}/CH{sub 3}NH{sub 3}PbI{sub 3-x}Cl{sub x}poly(3-hexylthiophene)/Ag architecture.

  17. Evidence for near-Surface NiOOH Species in Solution-Processed NiOx Selective Interlayer Materials: Impact on Energetics and the Performance of Polymer Bulk Heterojunction Photovoltaics

    SciTech Connect

    Ratcliff, Erin L.; Meyer, Jens; Steirer, K. Xerxes; Garcia, Andres; Berry, Joseph J.; Ginley, David S.; Olson, Dana C.; Kahn, Antoine; Armstrong, Neal R.

    2011-11-22

    The characterization and implementation of solution-processed, wide bandgap nickel oxide (NiO{sub x}) hole-selective interlayer materials used in bulk-heterojunction (BHJ) organic photovoltaics (OPVs) are discussed. The surface electrical properties and charge selectivity of these thin films are strongly dependent upon the surface chemistry, band edge energies, and midgap state concentrations, as dictated by the ambient conditions and film pretreatments. Surface states were correlated with standards for nickel oxide, hydroxide, and oxyhydroxide components, as determined using monochromatic X-ray photoelectron spectroscopy. Ultraviolet and inverse photoemission spectroscopy measurements show changes in the surface chemistries directly impact the valence band energies. O?-plasma treatment of the as-deposited NiO{sub x} films was found to introduce the dipolar surface species nickel oxyhydroxide (NiOOH), rather than the p-dopant Ni?O?, resulting in an increase of the electrical band gap energy for the near-surface region from 3.1 to 3.6 eV via a vacuum level shift. Electron blocking properties of the as-deposited and O?-plasma treated NiO{sub x} films are compared using both electron-only and BHJ devices. O?-plasma-treated NiO{sub x} interlayers produce electron-only devices with lower leakage current and increased turn on voltages. The differences in behavior of the different pretreated interlayers appears to arise from differences in local density of states that comprise the valence band of the NiO{sub x} interlayers and changes to the band gap energy, which influence their hole-selectivity. The presence of NiOOH states in these NiO{sub x} films and the resultant chemical reactions at the oxide/organic interfaces in OPVs is predicted to play a significant role in controlling OPV device efficiency and lifetime.

  18. Structural influences on charge carrier dynamics for small-molecule organic photovoltaics

    SciTech Connect

    Wang, Zhiping Shibata, Yosei; Yamanari, Toshihiro; Matsubara, Koji; Yoshida, Yuji; Miyadera, Tetsuhiko; Saeki, Akinori; Seki, Shu; Zhou, Ying

    2014-07-07

    We investigated the structural influences on the charge carrier dynamics in zinc phthalocyanine/fullerene (ZnPc/C{sub 60}) photovoltaic cells by introducing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and 2,5-bis(4-biphenylyl)-bithiophene (BP2T) between indium tin oxide and ZnPc layers. ZnPc films can be tuned to be round, long fiber-like, and short fiber-like structure, respectively. Time-resolved microwave conductivity measurements reveal that charge carrier lifetime in ZnPc/C{sub 60} bilayer films is considerably affected by the intra-grain properties. Transient photocurrent of ZnPc single films indicated that the charge carriers can transport for a longer distance in the long fiber-like grains than that in the round grains, due to the greatly lessened grain boundaries. By carefully controlling the structure of ZnPc films, the short-circuit current and fill factor of a ZnPc/C{sub 60} heterojunction solar cell with BP2T are significantly improved and the power conversion efficiency is increased to 2.6%, which is 120% larger than the conventional cell without BP2T.

  19. Development of chiral LC-MS methods for small molecules and their...

    Office of Scientific and Technical Information (OSTI)

    ... Reverse phase methods containifig high water were found to decrease ionization efficiency ... all mobile phase components such as water, solvents, and buffers; c) ensure ...

  20. Proceedings of the workshop on some aspects of autoionization in atoms and small molecules

    SciTech Connect

    Berkowitz, J.; Berry, H.G.; Berry, R.S.

    1985-11-01

    Do we really understand the phenomenon of autoionization in atoms sufficiently well to consider it a ''mature'' topic. Can we generalize our understanding to predict behavior in systems not yet studied. Can we extract physical understanding from the encouraging results of the ''many-body calculations''. Or must we still try to understand one atom at a time. Molecular autoionization is clearly more difficult. Not only must we content with ''vibrational autoionization'' as well as ''electronic autoionization'', but the competing process of predissociation must also be taken into account. In this molecular domain, we have many experiments and many phenomena. The extant theories only deal with some cases, and are not yet able to explain some prominent observations. A group consisting of theorists and experimentalists active in the field of autoionization assembled at Argonne National Laboratory for a two-day Workshop on May 2-3, 1985, to try to provide some consensus of our present understanding and to point out the most promising direction for progress in the near future. Abstracts of individual items from the workshop were prepared separately for the data base.

  1. High-Affinity, Small-Molecule Peptidomimetic Inhibitors of MLL1...

    Office of Scientific and Technical Information (OSTI)

    Authors: Karatas, Hacer ; Townsend, Elizabeth C ; Cao, Fang ; Chen, Yong ; Bernard, Denzil ; Liu, Liu ; Lei, Ming ; Dou, Yali ; Wang, Shaomeng 1 ; HHMI) 2 + Show Author ...

  2. Antiandrogenic properties of parabens and other phenolic containing small molecules in personal care products

    SciTech Connect

    Chen Jiangang; Ahn, Ki Chang; Gee, Nancy A.; Gee, Shirley J.; Hammock, Bruce D.; Lasley, Bill L. . E-mail: bllasley@ucdavis.edu

    2007-06-15

    To identify the androgenic potency of commonly used antimicrobials, an in vitro androgen receptor-mediated transcriptional activity assay was employed to evaluate the androgenic/antiandrogenic activity of parabens and selected other antimicrobials containing a phenolic moiety. This cell-based assay utilizes a stably transfected cell line that lacks critical steroid metabolizing enzymes and is formatted in a 96-well format. At a concentration of 10 {mu}M, methyl-, propyl- and butyl-4-hydroxybenzoate (parabens) inhibited testosterone (T)-induced transcriptional activity by 40%, 33% and 19%, respectively (P < 0.05), while 4-hydroxybenzoic acid, the major metabolite of parabens, had no effect on T-induced transcriptional activity. Triclosan inhibited transcriptional activity induced by T by more than 92% at a concentration of 10 {mu}M, and 38.8% at a concentration of 1.0 {mu}M (P < 0.05). Thirty-four percent of T-induced transcriptional activity was inhibited by thymol at 10 {mu}M (P < 0.05). Cell proliferation and/or cytotoxicity were not observed in any of the treatments. None of the compounds appeared to be androgenic when tested individually without T. The data presented in this report demonstrate that some widely used antimicrobial compounds have antiandrogenic properties and warrant further investigation to fully understand their potential impact on human reproductive health.

  3. A Small-Molecule Inhibitor of BCL6 Kills DLBCL Cells In Vitro and In Vivo

    SciTech Connect

    Cerchietti, L.C.; Ghetu, A.F.; Zhu, X.; Da Silva, G.F.; Zhong, S.; Matthews, M.; Bunting, K.L.; Polo, J.M.; Fares, C.; Arrowsmith, C.H.; Yang, S.N.; Garcia, M.; Coop, A.; Mackerell, A.D.; Prive, G.G.; Melnick, A.

    2010-09-22

    The BCL6 transcriptional repressor is the most frequently involved oncogene in diffuse large B cell lymphoma (DLBCL). We combined computer-aided drug design with functional assays to identify low-molecular-weight compounds that bind to the corepressor binding groove of the BCL6 BTB domain. One such compound disrupted BCL6/corepressor complexes in vitro and in vivo, and was observed by X-ray crystallography and NMR to bind the critical site within the BTB groove. This compound could induce expression of BCL6 target genes and kill BCL6-positive DLBCL cell lines. In xenotransplantation experiments, the compound was nontoxic and potently suppressed DLBCL tumors in vivo. The compound also killed primary DLBCLs from human patients.

  4. Structural basis for specificity of TGF[beta] family receptor small molecule inhibitors

    SciTech Connect

    Ogunjimi, Abiodun A.; Zeqiraj, Elton; Ceccarelli, Derek F.; Sicheri, Frank; Wrana, Jeffrey L.; David, Laurent

    2012-07-24

    Transforming growth factor-{beta} (TGF{beta}) receptor kinase inhibitors have a great therapeutic potential. SB431542 is one of the mainly used kinase inhibitors of the TGF{beta}/Activin pathway receptors, but needs improvement of its EC{sub 50} (EC{sub 50} = 1 {mu}M) to be translated to clinical use. A key feature of SB431542 is that it specifically targets receptors from the TGF{beta}/Activin pathway but not the closely related receptors from the bone morphogenic proteins (BMP) pathway. To understand the mechanisms of this selectivity, we solved the crystal structure of the TGF{beta} type I receptor (T{beta}RI) kinase domain in complex with SB431542. We mutated T{beta}RI residues coordinating SB431542 to their counterparts in activin-receptor like kinase 2 (ALK2), a BMP receptor kinase, and tested the kinase activity of mutated T{beta}RI. We discovered that a Ser280Thr mutation yielded a T{beta}RI variant that was resistant to SB431542 inhibition. Furthermore, the corresponding Thr283Ser mutation in ALK2 yielded a BMP receptor sensitive to SB431542. This demonstrated that Ser280 is the key determinant of selectivity for SB431542. This work provides a framework for optimising the SB431542 scaffold to more potent and selective inhibitors of the TGF{beta}/Activin pathway.

  5. Preface: Forum on small molecules related to carbon-containing fuels

    DOE PAGES [OSTI]

    Fujita, Etsuko; Goldman, Alan S.

    2015-06-01

    For millennia, human transportation was fueled largely through the consumption of biomass (by humans or domestic animals) and to a lesser extent by wind. The 19th century saw a major shift to coal-fueled transportation, with trains and ships powered by steam engines. A second major shift in the fueling of transportation occurred in the 20th century, this time to petroleum. This transition was not driven by the cost or ease of obtaining energy from oil wells vs. coal mines indeed, the cost of petroleum has always been higher than coal on a per-unit-energy basis but rather by themoretremendous technical advantages of powering engines with liquids, specifically liquid hydrocarbons.less

  6. Small-Molecule CD4-Mimics: Structure-Based Optimization of HIV...

    Office of Scientific and Technical Information (OSTI)

    S. ; Freire, Ernesto ; Sodroski, Joseph ; Madani, Navid ; Hendrickson, Wayne A. ; Smith, III, Amos B. 1 ; DFCI) 2 ; UPENN) 2 ; JHU) 2 ; Bryn Mawr) 2 ; Harvard-Med) ...

  7. Sensors and Controls Subprogram Overview - 2016 BTO Peer Review...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Self-Powering Wireless Sensors and Sensor Networks ORNL researchers are experimenting with additive roll-to-roll manufacturing techniques to develop low-cost wireless sensors. ...

  8. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... optical curing appears very promising for roll-to-roll manufacturing of high-efficiency, flexible perovskite solar cells. less Full Text Available January 2015 High-Performance ...

  9. In-situ characterization of colloidal soft solution processes...

    Office of Scientific and Technical Information (OSTI)

    growth process with characterization of stability ... Acoustic methods require a significant particle ... Full Text preview image File size NAView Full Text View ...

  10. In-situ characterization of colloidal soft solution processes...

    Office of Scientific and Technical Information (OSTI)

    Authors: Tallant, David Robert ; Rodriguez, Mark Andrew ; Bell, Nelson Simmons Publication Date: 2003-11-01 OSTI Identifier: 918371 Report Number(s): SAND2003-3868 TRN: ...

  11. Solution-processed amorphous silicon surface passivation layers

    SciTech Connect

    Mews, Mathias Sontheimer, Tobias; Korte, Lars; Rech, Bernd; Mader, Christoph; Traut, Stephan; Wunnicke, Odo

    2014-09-22

    Amorphous silicon thin films, fabricated by thermal conversion of neopentasilane, were used to passivate crystalline silicon surfaces. The conversion is investigated using X-ray and constant-final-state-yield photoelectron spectroscopy, and minority charge carrier lifetime spectroscopy. Liquid processed amorphous silicon exhibits high Urbach energies from 90 to 120?meV and 200?meV lower optical band gaps than material prepared by plasma enhanced chemical vapor deposition. Applying a hydrogen plasma treatment, a minority charge carrier lifetime of 1.37?ms at an injection level of 10{sup 15}/cm{sup 3} enabling an implied open circuit voltage of 724?mV was achieved, demonstrating excellent silicon surface passivation.

  12. Solution processed nickel oxide anodes for organic photovoltaic devices

    SciTech Connect

    Mustafa, Bestoon; Griffin, Jonathan; Alsulami, Abdullah S.; Lidzey, David G.; Buckley, Alastair R.

    2014-02-10

    Nickel oxide thin films have been prepared from a nickel acetylacetonate (Ni(acac)) precursor for use in bulk heterojunction organic photovoltaic devices. The conversion of Ni(acac) to NiO{sub x} has been investigated. Oxygen plasma treatment of the NiO layer after annealing at 400 °C affords solar cell efficiencies of 5.2%. Photoelectron spectroscopy shows that high temperature annealing converts the Ni(acac) to a reduced form of nickel oxide. Additional oxygen plasma treatment further oxidizes the surface layers and deepens the NiO work function from 4.7 eV for the annealed film, to 5.0 eV allowing for efficient hole extraction at the organic interface.

  13. Catalytic site inhibition of insulin-degrading enzyme by a small molecule induces glucose intolerance in mice

    DOE PAGES [OSTI]

    Deprez-Poulain, Rebecca; Hennuyer, Nathalie; Bosc, Damien; Liang, Wenguang G.; Enée, Emmanuelle; Marechal, Xavier; Charton, Julie; Totobenazara, Jane; Berte, Gonzague; Jahklal, Jouda; et al

    2015-09-23

    Insulin-degrading enzyme (IDE) is a protease that cleaves insulin and other bioactive peptides such as amyloid-β. Knockout and genetic studies have linked IDE to Alzheimer’s disease and type-2 diabetes. As the major insulin-degrading protease, IDE is a candidate drug target in diabetes. Here we have used kinetic target-guided synthesis to design the first catalytic site inhibitor of IDE suitable for in vivo studies (BDM44768). Crystallographic and small angle X-ray scattering analyses show that it locks IDE in a closed conformation. Among a panel of metalloproteases, BDM44768 selectively inhibits IDE. Acute treatment of mice with BDM44768 increases insulin signalling and surprisinglymore » impairs glucose tolerance in an IDE-dependent manner. These results confirm that IDE is involved in pathways that modulate short-term glucose homeostasis, but casts doubt on the general usefulness of the inhibition of IDE catalytic activity to treat diabetes.« less

  14. Discovery of Small Molecule Isozyme Non-specific Inhibitors of Mammalian Acetyl-CoA Carboxylase 1 and 2

    SciTech Connect

    Corbett, J.; Freeman-Cook, K; Elliott, R; Vajdos, F; Rajamohan, F; Kohls, D; Marr, E; Harwood Jr., H; Esler, W; et al.

    2010-01-01

    Screening Pfizer's compound library resulted in the identification of weak acetyl-CoA carboxylase inhibitors, from which were obtained rACC1 CT-domain co-crystal structures. Utilizing HTS hits and structure-based drug discovery, a more rigid inhibitor was designed and led to the discovery of sub-micromolar, spirochromanone non-specific ACC inhibitors. Low nanomolar, non-specific ACC-isozyme inhibitors that exhibited good rat pharmacokinetics were obtained from this chemotype.

  15. Catalytic site inhibition of insulin-degrading enzyme by a small molecule induces glucose intolerance in mice

    SciTech Connect

    Deprez-Poulain, Rebecca; Hennuyer, Nathalie; Bosc, Damien; Liang, Wenguang G.; Enée, Emmanuelle; Marechal, Xavier; Charton, Julie; Totobenazara, Jane; Berte, Gonzague; Jahklal, Jouda; Verdelet, Tristan; Dumont, Julie; Dassonneville, Sandrine; Woitrain, Eloise; Gauriot, Marion; Paquet, Charlotte; Duplan, Isabelle; Hermant, Paul; Cantrelle, François- Xavier; Sevin, Emmanuel; Culot, Maxime; Landry, Valerie; Herledan, Adrien; Piveteau, Catherine; Lippens, Guy; Leroux, Florence; Tang, Wei-Jen; van Endert, Peter; Staels, Bart; Deprez, Benoit

    2015-09-23

    Insulin-degrading enzyme (IDE) is a protease that cleaves insulin and other bioactive peptides such as amyloid-β. Knockout and genetic studies have linked IDE to Alzheimer’s disease and type-2 diabetes. As the major insulin-degrading protease, IDE is a candidate drug target in diabetes. Here we have used kinetic target-guided synthesis to design the first catalytic site inhibitor of IDE suitable for in vivo studies (BDM44768). Crystallographic and small angle X-ray scattering analyses show that it locks IDE in a closed conformation. Among a panel of metalloproteases, BDM44768 selectively inhibits IDE. Acute treatment of mice with BDM44768 increases insulin signalling and surprisingly impairs glucose tolerance in an IDE-dependent manner. These results confirm that IDE is involved in pathways that modulate short-term glucose homeostasis, but casts doubt on the general usefulness of the inhibition of IDE catalytic activity to treat diabetes.

  16. Surface structures from low energy electron diffraction: Atoms, small molecules and an ordered ice film on metal surfaces

    SciTech Connect

    Materer, N.F.

    1995-09-01

    We investigated the surface bonding of various adsorbates (0, S, C{sub 2}H{sub 3} and NO) along with the resulting relaxation of the Pt(111) surface using low energy electron diffiraction (LEED). LEED experiments have been performed on these ordered overlayers along with theoretical structural analysis using automated tensor LEED (ATLEED). The resulting surface structures of these ordered overlayers exhibit similar adsorbate-induced relaxations. In all cases the adsorbate occupies the fcc hollow site and induces an approximately 0.1 A buckling of the metal surface. The three metal atoms directly bonded to the adsorbate are ``pulled`` out of the surface and the metal atom that is not bound to the adsorbate is `pushed`` inward. In order to understand the reliability of such details, we have carried out a comprehensive study of various non-structural parameters used in a LEED computation. We also studied the adsorption of water on the Pt(lll) surface. We ordered an ultra thin ice film on this surface. The film`s surface is found to be the (0001) face of hexagonal ice. This surface is apparently terminated by a full-bilayer, in which the uppermost water molecules have large vibrational amplitudes even at temperatures as low as 90 K. We examined two other metal surfaces besides Pt(111): Ni(111) and Fe(lll). On Ni(111), we have studied the surface under a high coverage of NO. On both Ni(111) and Pt(111) NO molecules occupy the hollow sites and the N-0 bond distances are practically identical. The challenging sample preparation of an Fe(111) surface has been investigated and a successful procedure has been obtained. The small interlayer spacing found on Fe(111) required special treatment in the LEED calculations. A new ATLEED program has been developed to handle this surface.

  17. Innovative, Lower Cost Sensors and Controls Yield Better Energy...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Energy Efficiency March 23, 2015 - 1:05pm Addthis ORNL researchers are experimenting with additive roll-to-roll manufacturing techniques to develop low-cost wireless sensors. ...

  18. Helianthos | Open Energy Information

    OpenEI (Open Energy Information) [EERE & EIA]

    Developer of patented technology for the roll-to-roll manufacture of flexible solar cell laminates. References: Helianthos1 This article is a stub. You can help OpenEI by...

  19. Smart Manufacturing Institute Industry Day Workshop | Department...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Process Intensification Workshop - September 29-30, 2015 WORKSHOP: HIGH VALUE ROLL TO ROLL (HV R2R) MANUFACTURING INNOVATION, DECEMBER 2-3, 2015 Fiber Reinforced Polymer Composite ...

  20. CX-009536: Categorical Exclusion Determination

    Energy.gov [DOE]

    In-situ Roll-to-Roll Printing of Highly Efficient Organic Solar Cells CX(s) Applied: A9, B3.6 Date: 11/21/2012 Location(s): California Offices(s): Golden Field Office

  1. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... roll-to-roll manufacturing processes of thin film deposition on low-cost flexible ... Changes in film resistance and mass were measured in situ. In the dark, resistance of metallic ...

  2. QTR Webinar: Chapter 8 - Industry and Manufacturing | Department...

    Office of Environmental Management (EM)

    ... - Process Intensification (1.81 MB) R2R - Roll-to-Roll Processing (1.47 MB) TE - Thermoelectric Materials, Devices, and Systems (1003.12 KB) WHR - Waste Heat Recovery (861.04 KB) ...

  3. Utilizing Bacteria for Sustainable Manufacturing of Low-Cost...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Bacteria for Sustainable Manufacturing of Low-Cost Nanoparticles Chad Duty, Ph.D. Technical Lead Additive Manufacturing Roll-to-Roll Processing June 26, 2012 2 Managed by ...

  4. Pulsed Thermal Processing of Self-Assembled Quantum Dot Structures

    SciTech Connect

    2009-04-01

    This factsheet describes a study that will develop the quantum dot manufacturing system for roll-to-roll thin film processing for use in applications such as solid state lighting.

  5. Low-Cost, Third Generation Solar Cells on Solid Ground | U.S. DOE Office of

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Wireless Sensors for Building Applications Low-Cost Wireless Sensors for Building Applications ORNL researchers are experimenting with additive roll-to-roll manufacturing techniques to develop low-cost wireless sensors. ORNL's Pooran Joshi shows how the process enables electronics components to be printed on flexible plastic substrates. Credit: Oak Ridge National Lab ORNL researchers are experimenting with additive roll-to-roll manufacturing techniques to develop low-cost wireless sensors.

  6. Scalable fabrication of efficient organolead trihalide perovskite solar cells with doctor-bladed active layers

    SciTech Connect

    Deng, Yehao; Peng, Edwin; Shao, Yuchuan; Xiao, Zhengguo; Dong, Qingfeng; Huang, Jinsong

    2015-03-25

    Organolead trihalide perovskites (OTPs) are nature abundant materials with prospects as future low-cost renewable energy sources boosted by the solution process capability of these materials. Here we report the fabrication of efficient OTP devices by a simple, high throughput and low-cost doctor-blade coating process which can be compatible with the roll-to-roll fabrication process for the large scale production of perovskite solar cell panels. The formulation of appropriate precursor inks by removing impurities is shown to be critical in the formation of continuous, pin-hole free and phase-pure perovskite films on large area substrates, which is assisted by a high deposition temperature to guide the nucleation and grain growth process. The domain size reached 80250 ?m in 1.52 ?m thick bladed films. By controlling the stoichiometry and thickness of the OTP films, highest device efficiencies of 12.8% and 15.1% are achieved in the devices fabricated on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate and cross-linked N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)N4,N4'-diphenylbiphenyl-4,4'-diamine covered ITO substrates. Furthermore, the carrier diffusion length in doctor-bladed OTP films is beyond 3.5 ?m which is significantly larger than in the spin-coated films, due to the formation of crystalline grains with a very large size by the doctor-blade coating method.

  7. Synthesis and Exploratory Catalysis of 3d Metals: Group-Transfer Reactions, and the Activation and Functionalization of Small Molecules Including Greenhouse Gases

    SciTech Connect

    Mindiola, Daniel J.

    2014-05-07

    Our work over the past three years has resulted in the development of electron rich and low-coordinate vanadium fragments, molecular nitrides of vanadium and parent imide systems of titanium, and the synthesis of phosphorus containing molecules of the 3d transition metal series. Likewise, with financial support from BES Division in DOE (DE-FG02-07ER15893), we now completed the full characterization of the first single molecular magnet (SMM) of Fe(III). We demonstrated that this monomeric form of Fe(III) has an unusual slow relaxation of the magnetization under zero applied field. To make matters more interesting, this system also undergoes a rare example of an intermediate to high-spin transition (an S = 3/2 to S = 5/2 transition). In 2010 we reported the synthesis of the first neutral and low-coordinate vanadium complexes having the terminal nitride functionality. We have now completed a full study to understand formation of the nitride ligand from the metastable azide precursor, and have also explored the reactivity of the nitride ligand in the context of incomplete and complete N-atom transfer. During the 2010-2013 period we also discovered a facile approach to assemble low-coordinate and low-valent vanadium(II) complexes and exploit their multielectron chemistry ranging from 1-3 electrons. Consequently, we can now access 3d ligand frameworks such as cyclo-P3 (and its corresponding radical anion), nitride radical anions and cations, low-coordinate vanadium oxo’s, and the first example of a vanadium thionitrosyl complex. A cis-divacant iron(IV) imido having some ligand centered radical has been also discovered, and we are in the process of elucidating its electronic structure (in particular the sign of zero field splitting and the origin of its magnitude), bonding and reactivity. We have also revisited some paramagnetic and classic metallocene compounds with S >1/2 ground states in order to understand their reactivity patterns and electronic structure. Lastly, we are completing the synthesis and characterization of a titanium nitride anion and formation of the first example of boryl and aluminyl imido titanium complexes.

  8. Mechanisms of Operation and Degradation in Solution-Processable Organic Photovoltaics

    SciTech Connect

    Shaheen, S. E.

    2007-01-01

    Organic photovoltaic devices are being intensely researched as a low-cost solar power conversion technology. In general, reliability and degradation mechanisms for these devices have not been examined by researchers in detail, however recent efficiency gains justify more concerted efforts toward achieving commercially viable device lifetimes. The molecular nature of these materials and the atmospheric processing techniques used for their fabrication provide for potentially low cost production. These aspects also bring with them unique challenges in achieving stable device performance. In this paper, I provide a brief description of the operational mechanisms of these devices, and I outline what is known about the mechanisms of degradation and the device lifetimes.

  9. Self-Assembly, Molecular Ordering, and Charge Mobility in Solution-Processed Ultrathin Oligothiophene Films

    SciTech Connect

    Murphy,A.; Chang, P.; VanDyke, P.; Liu, J.; Frechet, J.; Subramanian, V.; Delongchamp, D.; Sambasivan, S.; Fischer, D.; Lin, E.

    2005-01-01

    Symmetrical {alpha}, {omega}-substituted quarter-(T4), penta-(T5), sexi-(T6), and heptathiophene (T7) oligomers containing thermally removable aliphatic ester solubilizing groups were synthesized, and their UV-vis and thermal characteristics were compared. Spun-cast thin films of each oligomer were examined with atomic force microscopy and near-edge X-ray absorption fine structure spectroscopy to evaluate the ability of the material to self-assemble from a solution-based process while maintaining complete surface coverage. Films of the T5-T7 oligomers self-assemble into crystalline terraces after thermal annealing with higher temperatures required to affect this transformation as the size of the oligomers increases. A symmetrical {alpha}, {omega}-substituted sexithiophene (T6-acid) that reveals carboxylic acids after thermolysis was also prepared to evaluate the effect of the presence of hydrogen-bonding moieties. The charge transport properties for these materials evaluated in top-contact thin film transistor devices were found to correlate with the observed morphology of the films. Therefore, the T4 and the T6-acid performed poorly because of incomplete surface coverage after thermolysis, while T5-T7 exhibited much higher performance as a result of molecular ordering. Increases in charge mobility correlated to increasing conjugation length with measured mobilities ranging from 0.02 to 0.06 cm2/(V{center_dot}s). The highest mobilities were measured when films of each oligomer had an average thickness between one and two monolayers, indicating that the molecules become exceptionally well-ordered during the thermolysis process. This unprecedented ordering of the solution-cast molecules results in efficient charge mobility rarely seen in such ultrathin films.

  10. Enhancing performing characteristics of organic semiconducting films by improved solution processing

    DOEpatents

    Bazan, Guillermo C; Moses, Daniel; Peet, Jeffrey; Heeger, Alan J

    2014-05-13

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  11. Enhancing performance characteristics of organic semiconducting films by improved solution processing

    DOEpatents

    Bazan, Guillermo C; Mikhailovsky, Alexander; Moses, Daniel; Nguyen, Thuc-Quyen; Peet, Jeffrey; Soci, Cesare

    2012-11-27

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  12. Enhancing performance characteristics of organic semiconducting films by improved solution processing

    DOEpatents

    Bazan, Guillermo C.; Heeger, Alan J.; Moses, Daniel; Peet, Jeffrey

    2013-09-25

    Improved processing methods for enhanced properties of conjugated polymer films are disclosed, as well as the enhanced conjugated polymer films produced thereby. Addition of low molecular weight alkyl-containing molecules to solutions used to form conjugated polymer films leads to improved photoconductivity and improvements in other electronic properties. The enhanced conjugated polymer films can be used in a variety of electronic devices, such as solar cells and photodiodes.

  13. Scalable fabrication of efficient organolead trihalide perovskite solar cells with doctor-bladed active layers

    DOE PAGES [OSTI]

    Deng, Yehao; Peng, Edwin; Shao, Yuchuan; Xiao, Zhengguo; Dong, Qingfeng; Huang, Jinsong

    2015-03-25

    Organolead trihalide perovskites (OTPs) are nature abundant materials with prospects as future low-cost renewable energy sources boosted by the solution process capability of these materials. Here we report the fabrication of efficient OTP devices by a simple, high throughput and low-cost doctor-blade coating process which can be compatible with the roll-to-roll fabrication process for the large scale production of perovskite solar cell panels. The formulation of appropriate precursor inks by removing impurities is shown to be critical in the formation of continuous, pin-hole free and phase-pure perovskite films on large area substrates, which is assisted by a high deposition temperaturemore » to guide the nucleation and grain growth process. The domain size reached 80–250 μm in 1.5–2 μm thick bladed films. By controlling the stoichiometry and thickness of the OTP films, highest device efficiencies of 12.8% and 15.1% are achieved in the devices fabricated on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate and cross-linked N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)–N4,N4'-diphenylbiphenyl-4,4'-diamine covered ITO substrates. Furthermore, the carrier diffusion length in doctor-bladed OTP films is beyond 3.5 μm which is significantly larger than in the spin-coated films, due to the formation of crystalline grains with a very large size by the doctor-blade coating method.« less

  14. Scalable fabrication of efficient organolead trihalide perovskite solar cells with doctor-bladed active layers

    SciTech Connect

    Deng, Yehao; Peng, Edwin; Shao, Yuchuan; Xiao, Zhengguo; Dong, Qingfeng; Huang, Jinsong

    2015-03-25

    Organolead trihalide perovskites (OTPs) are nature abundant materials with prospects as future low-cost renewable energy sources boosted by the solution process capability of these materials. Here we report the fabrication of efficient OTP devices by a simple, high throughput and low-cost doctor-blade coating process which can be compatible with the roll-to-roll fabrication process for the large scale production of perovskite solar cell panels. The formulation of appropriate precursor inks by removing impurities is shown to be critical in the formation of continuous, pin-hole free and phase-pure perovskite films on large area substrates, which is assisted by a high deposition temperature to guide the nucleation and grain growth process. The domain size reached 80–250 μm in 1.5–2 μm thick bladed films. By controlling the stoichiometry and thickness of the OTP films, highest device efficiencies of 12.8% and 15.1% are achieved in the devices fabricated on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate and cross-linked N4,N4'-bis(4-(6-((3-ethyloxetan-3-yl)methoxy)hexyl)phenyl)–N4,N4'-diphenylbiphenyl-4,4'-diamine covered ITO substrates. Furthermore, the carrier diffusion length in doctor-bladed OTP films is beyond 3.5 μm which is significantly larger than in the spin-coated films, due to the formation of crystalline grains with a very large size by the doctor-blade coating method.

  15. AMO Weekly Announcements 11/16/15 | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    16/15 AMO Weekly Announcements 11/16/15 November 16, 2015 - 10:00am Addthis WORKSHOP: High Value Roll to Roll Manufacturing Innovation The Advanced Manufacturing Office (AMO) will host a workshop at the Westin Alexandria on December 2-3, 2015. This 2-day workshop will focus on the topic of High Value Roll to Roll (HV R2R) Manufacturing Innovation. Categories for discussion include Advanced Deposition Processing and Printing, Unique Metrology and Quality Systems, and Continuous Processing/Process

  16. Air-stable solution-processed n-channel organic thin film transistors with polymer-enhanced morphology

    SciTech Connect

    He, Zhengran; Shaik, Shoieb; Bi, Sheng; Li, Dawen; Chen, Jihua

    2015-05-04

    N,N′-1H,1H-perfluorobutyl dicyanoperylenecarboxydiimide (PDIF-CN{sub 2}) is an n-type semiconductor exhibiting high electron mobility and excellent air stability. However, the reported electron mobility based on spin-coated PDIF-CN{sub 2} film is much lower than the value of PDIF-CN{sub 2} single crystals made from vapor phase deposition, indicating significant room for mobility enhancement. In this study, various insulating polymers, including poly(vinyl alcohol), poly(methyl methacrylate) (PMMA), and poly(alpha-methylstyrene) (PαMS), are pre-coated on silicon substrate aiming to enhance the morphology of the PDIF-CN{sub 2} thin film, thereby improving the charge transport and air stability. Atomic force microscopy images reveal that with the pre-deposition of PαMS or PMMA polymers, the morphology of the PDIF-CN{sub 2} polycrystalline films is optimized in semiconducting crystal connectivity, domain size, and surface roughness, which leads to significant improvement of organic thin-film transistor (OTFT) performance. Particularly, an electron mobility of up to 0.55 cm{sup 2}/V s has been achieved from OTFTs based on the PDIF-CN{sub 2} film with the pre-deposition of PαMS polymer.

  17. Organic solution-processible electroluminescent molecular glasses for non-doped standard red OLEDs with electrically stable chromaticity

    SciTech Connect

    Bi, Xiaoman; Zuo, Weiwei; Liu, Yingliang Zhang, Zhenru; Zeng, Cen; Xu, Shengang; Cao, Shaokui

    2015-10-15

    Highlights: • The D–A–D electroluminescent molecular glasses are synthesized. • Non-doped red electroluminescent film is fabricated by spin-coating. • Red OLED shows stable wavelength, luminous efficiency and chromaticity. • CIE1931 coordinate is in accord with standard red light in PAL system. - Abstract: Organic light-emitting molecular glasses (OEMGs) are synthesized through the introduction of nonplanar donor and branched aliphatic chain into electroluminescent emitters. The target OEMGs are characterized by {sup 1}H NMR, {sup 13}C NMR, IR, UV–vis and fluorescent spectra as well as elemental analysis, TG and DSC. The results indicated that the optical, electrochemical and electroluminescent properties of OEMGs are adjusted successfully by the replacement of electron-donating group. The non-doped OLED device with a standard red electroluminescent emission is achieved by spin-coating the THF solution of OEMG with a triphenylamine moiety. This non-doped red OLED device takes on an electrically stable electroluminescent performance, including the stable maximum electroluminescent wavelength of 640 nm, the stable luminous efficiency of 2.4 cd/A and the stable CIE1931 coordinate of (x, y) = (0.64, 0.35), which is basically in accord with the CIE1931 coordinate (x, y) = (0.64, 0.33) of standard red light in PAL system.

  18. Development of Inorganic Precursors for Manufacturing of Photovoltaic Devices: Cooperative Research and Development Final Report, CRADA Number CRD-08-308

    SciTech Connect

    van Hest, M.; Ginley, D.

    2013-06-01

    Both NREL and Rohm and Haas Electronic Materials are interested in the development of solution phase metal and semiconductive precursors for the manufacturing of photovoltaic devices. In particular, we intend to develop material sets for atmospheric deposition processes. The cooperation between these two parties will enable high value materials and processing solutions for the manufacturing of low cost, roll-to-roll photovoltaics.

  19. Air-stable ink for scalable, high-throughput layer deposition

    DOEpatents

    Weil, Benjamin D; Connor, Stephen T; Cui, Yi

    2014-02-11

    A method for producing and depositing air-stable, easily decomposable, vulcanized ink on any of a wide range of substrates is disclosed. The ink enables high-volume production of optoelectronic and/or electronic devices using scalable production methods, such as roll-to-roll transfer, fast rolling processes, and the like.

  20. SEP Benefits to Program Administrators

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Sustainability Workshop Portland, OR January 6-7, 2016 ADVANCED MANUFACTURING OFFICE Broad Topical Areas  Platform Materials and Technologies for Energy Applications - Advanced Materials Manufacturing (Mat'l Genome, Nanomaterials, etc.) - Critical Materials - Advanced Composites & Lightweight Materials - 3D Printing / Additive Manufacturing - 2D Manufacturing / Roll-to-Roll Processes - Wide Bandgap Power Electronics - Next Generation Electric Machines  Efficiency in Manufacturing

  1. Technology Assessment

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Roll to Roll (R2R) Processing 1 Technology Assessment 2 3 Contents 4 1. Introduction to the Technology/System ............................................................................................... 2 5 1.1. Introduction to R2R Processing..................................................................................................... 2 6 1.2. R2R Processing Mechanisms ......................................................................................................... 3 7 2.

  2. Interplay of Metalloligand and Organic Ligand to Tune Micropores within Isostructural Mixed-Metal Organic Frameworks (M MOFs) for Their Highly Selective Separation of Chiral and Achiral Small Molecules

    SciTech Connect

    Madhab, Das; He, Yabing; Kim, Jaheon; Guo, Qunsheng; Zhao, Cong-Gui; Hong, Kunlun; Xiang, Sheng-Chang; Zhang, Zhangjing; Thomas, K Mark; Krishna, Rajamani; Chen, Banglin

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M'MOFs) have been synthesized and structurally characterized. The pores within these M'MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selective separation of chiral alcohols 1-phenylethanol (PEA), 2-butanol (BUT), and 2-pentanol (2-PEN) with the highest ee up to 82.4% but also to lead highly selective separation of achiral C{sub 2}H{sub 2}/C{sub 2}H{sub 4} separation. The potential application of these M'MOFs for the fixed bed pressure swing adsorption (PSA) separation of C{sub 2}H{sub 2}/C{sub 2}H{sub 4} has been further examined and compared by the transient breakthrough simulations in which the purity requirement of 40 ppm in the outlet gas can be readily fulfilled by the fixed bed M'MOF-4a adsorber at ambient conditions.

  3. Charge Recombination, Transport Dynamics, and Interfacial Effects in Organic Solar Cells

    SciTech Connect

    Heeger, Alan; Bazan, Guillermo; Nguyen, Thuc-Quyen; Wudl, Fred

    2015-02-27

    are the following: • Photo-excitation of the donor (or the acceptor). • Charge transfer with holes in the donor domain and electrons in the acceptor domain. • Sweep-out to electrodes prior to recombination by the internal electric field. • Energy delivered to the external circuit. Each of these four steps was studied in detail using a wide variety of organic semiconductors with different molecular structures. This UC Santa Barbara group was the first to clarify the origin and the mechanism involved in the ultrafast charge transfer process. The ultrafast charge transfer (time scale approximately 100 times faster than the first step in the photo-synthesis of green plants) is the fundamental reason for the potential for high power conversion efficiency of sunlight to electricity from plastic solar cells. The UCSB group was the first to emphasize, clarify and demonstrate the need for sweep-out to electrodes prior to recombination by the internal electric field. The UCSB group was the first to synthesize small molecule organic semiconductors capable of high power conversion efficiencies. The results of this research were published in high impact peer-reviewed journals. Our published papers (40 in number) provide answers to fundamental questions that have been heavily discussed and debated in the field of Bulk Heterojunction Solar Cells; scientific questions that must be resolved before this technology can be ready for commercialization in large scale for production of renewable energy. Of the forty publications listed, nineteen were co-authored by two or more of the PIs, consistent with the multi-investigator approach described in the original proposal. The specific advantages of this “plastic” solar cell technology are the following: a. Manufacturing by low-cost printing technology using soluble organic semiconductors; this approach can be implemented in large scale by roll-to-roll printing on plastic substrates. b. Low energy cost in manufacturing; all steps

  4. High-Performance Organic Field-Effect Transistors with Dielectric and Active Layers Printed Sequentially by Ultrasonic Spraying

    SciTech Connect

    Shao, Ming [ORNL; Sanjib, Das [University of Tennessee, Knoxville (UTK); Chen, Jihua [ORNL; Keum, Jong Kahk [ORNL; Ivanov, Ilia N [ORNL; Gu, Gong [University of Tennessee, Knoxville (UTK); Geohegan, David B [ORNL; Xiao, Kai [ORNL

    2013-01-01

    High-performance, flexible organic field-effect transistors (OFETs) are reported with PVP dielectric and TIPS-PEN active layers sequentially deposited by ultrasonic spray-coating on plastic substrate. OFETs fabricated in ambient air with a bottom-gate/top-contact geometry are shown to achieve on/off ratios of >104 and mobilities as high as 0.35 cm2/Vs. These rival the characteristics of the best solution-processible small molecule FETs fabricated by other fabrication methods such as drop casting and ink-jet printing.

  5. Lithium Ion Electrode Production NDE and QC Considerations | Department of

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Energy Lithium Ion Electrode Production NDE and QC Considerations Lithium Ion Electrode Production NDE and QC Considerations Review of Oak Ridge process and QC activities by David Wood, Oak Ridge National Laboratory, at the EERE QC Workshop held December 9-10, 2013, at the National Renewable Energy Laboratory in Golden, Colorado. Lithium Ion Electrode Production NDE and QC Considerations (1.1 MB) More Documents & Publications Vehicle Technologies Office Merit Review 2014: Roll-to-Roll

  6. Low-Cost, Highly Transparent, Flexible, Low-Emission Coating Film to Enable

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Electrochromic Windows with Increased Energy Savings | Department of Energy Highly Transparent, Flexible, Low-Emission Coating Film to Enable Electrochromic Windows with Increased Energy Savings Low-Cost, Highly Transparent, Flexible, Low-Emission Coating Film to Enable Electrochromic Windows with Increased Energy Savings ITN Energy Systems is using low-cost, high volume roll-to-roll coating techniques to develop a new low-e film with high visible transmission and high infrared reflectivity.

  7. Sensors and Controls Overview - 2015 BTO Peer Review | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Overview - 2015 BTO Peer Review Sensors and Controls Overview - 2015 BTO Peer Review Presenter: Marina Sofos, U.S. Department of Energy View the Presentation Sensors and Controls Overview - 2015 BTO Peer Review (1.55 MB) More Documents & Publications Sensors and Controls Subprogram Overview - 2016 BTO Peer Review ORNL researchers are experimenting with additive roll-to-roll manufacturing techniques to develop low-cost wireless sensors. ORNL's Pooran Joshi shows how the process enables

  8. PowerPoint Presentation

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    High Value Roll-to-Roll Manufacturing Workshop December 2, 2015 Mark Johnson Director Advanced Manufacturing Office www.manufacturing.energy.gov 2 Clean Energy Solutions Environment Security * Competitiveness in clean energy * Domestic jobs * Clean air * Climate change * Health * Energy self-reliance * Stable, diverse energy supply Economy Clean Energy and Manufacturing: Nexus of Opportunities Clean Energy Manufacturing Making Products which Reduce Impact on Environment Advanced Manufacturing

  9. PowerPoint Presentation

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    High Value Roll to Roll Workshop December 2 - 3, 2015 David Ventola Director Business Development, EP 2 B&W MEGTEC Overview * Babcock & Wilcox MEGTEC De Pere, Wisconsin - MEGTEC employs approximately 350 people in the US and approximately 600 globally * De Pere Facility includes: - Chemical, Mechanical and Electrical Engineers and Designers - 100+ Service, Technical and Support Personnel - 100+ Manufacturing Personnel - Dedicated R&D and Pilot Laboratory Support Team - Oracle ERP,

  10. Chapter 6: Innovating Clean Energy Technologies in Advanced Manufacturing | Combined Heat and Power Systems Technology Assessment

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Platforms and Modeling for Manufacturing Combined Heat and Power Systems Composite Materials Critical Materials Direct Thermal Energy Conversion Materials, Devices, and Systems Materials for Harsh Service Conditions Process Heating Process Intensification Roll-to-Roll Processing Sustainable Manufacturing - Flow of Materials through Industry Waste Heat Recovery Systems Wide Bandgap Semiconductors for Power Electronics ENERGY U.S. DEPARTMENT OF Quadrennial Technology Review 2015 1 Quadrennial

  11. Chapter 6: Innovating Clean Energy Technologies in Advanced Manufacturing | Direct Thermal Energy Conversion Materials, Devices, and Systems Technology Assessment

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    and Modeling for Manufacturing Combined Heat and Power Systems Composite Materials Critical Materials Direct Thermal Energy Conversion Materials, Devices, and Systems Materials for Harsh Service Conditions Process Heating Process Intensification Roll-to-Roll Processing Sustainable Manufacturing - Flow of Materials through Industry Waste Heat Recovery Systems Wide Bandgap Semiconductors for Power Electronics ENERGY U.S. DEPARTMENT OF Quadrennial Technology Review 2015 1 Quadrennial Technology

  12. Chapter 6: Innovating Clean Energy Technologies in Advanced Manufacturing | Materials for Harsh Service Conditions Technology Assessment

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    and Modeling for Manufacturing Combined Heat and Power Systems Composite Materials Critical Materials Direct Thermal Energy Conversion Materials, Devices, and Systems Materials for Harsh Service Conditions Process Heating Process Intensification Roll-to-Roll Processing Sustainable Manufacturing - Flow of Materials through Industry Waste Heat Recovery Systems Wide Bandgap Semiconductors for Power Electronics ENERGY U.S. DEPARTMENT OF Quadrennial Technology Review 2015 1 Quadrennial Technology

  13. Workshops | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Workshops Workshops Presentations, video and audio files, and other information related to AMO workshops are available for review. Dispatchable Distributed Generation: Manufacturing's Role in Support of Grid Modernization - February 10-11 Sustainability In Manufacturing - January 6-7 High Value Roll to Roll (HV R2R) Manufacturing Innovation - December 2-3, 2015 Materials for Harsh Service Conditions - November 19-20, 2015 Desalination Technology Development Workshop - November 5-6, 2015 Process

  14. Innovative, Lower Cost Sensors and Controls Yield Better Energy Efficiency

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    | Department of Energy Innovative, Lower Cost Sensors and Controls Yield Better Energy Efficiency Innovative, Lower Cost Sensors and Controls Yield Better Energy Efficiency March 23, 2015 - 1:05pm Addthis ORNL researchers are experimenting with additive roll-to-roll manufacturing techniques to develop low-cost wireless sensors. ORNL’s Pooran Joshi shows how the process enables electronics components to be printed on flexible plastic substrates. Credit: Oak Ridge National Lab ORNL

  15. Development of high, stable-efficiency triple-junction a-Si alloy solar cells. Annual technical progress report, October 1995--October 1996

    SciTech Connect

    Deng, X.; Izu, M.; Jones, S.J.; Kopf, R.

    1997-04-01

    The overall objective of this amorphous silicon research program is to develop high efficiency a-Si solar cells and to develop and improve processes for large area deposition of a-Si solar cells and modules. The knowledge obtained and technologies demonstrated in this program will be incorporated into ECD`s continuous roll-to-roll deposition process to further enhance its photovoltaic manufacturing technology.

  16. Reliable solution processed planar perovskite hybrid solar cells with large-area uniformity by chloroform soaking and spin rinsing induced surface precipitation

    SciTech Connect

    Chern, Yann-Cherng; Wu, Hung-Ruei; Chen, Yen-Chu; Horng, Sheng-Fu; Zan, Hsiao-Wen; Meng, Hsin-Fei

    2015-08-15

    A solvent soaking and rinsing method, in which the solvent was allowed to soak all over the surface followed by a spinning for solvent draining, was found to produce perovskite layers with high uniformity on a centimeter scale and with much improved reliability. Besides the enhanced crystallinity and surface morphology due to the rinsing induced surface precipitation that constrains the grain growth underneath in the precursor films, large-area uniformity with film thickness determined exclusively by the rotational speed of rinsing spinning for solvent draining was observed. With chloroform as rinsing solvent, highly uniform and mirror-like perovskite layers of area as large as 8 cm × 8 cm were produced and highly uniform planar perovskite solar cells with power conversion efficiency of 10.6 ± 0.2% as well as much prolonged lifetime were obtained. The high uniformity and reliability observed with this solvent soaking and rinsing method were ascribed to the low viscosity of chloroform as well as its feasibility of mixing with the solvent used in the precursor solution. Moreover, since the surface precipitation forms before the solvent draining, this solvent soaking and rinsing method may be adapted to spinless process and be compatible with large-area and continuous production. With the large-area uniformity and reliability for the resultant perovskite layers, this chloroform soaking and rinsing approach may thus be promising for the mass production and commercialization of large-area perovskite solar cells.

  17. PowerPoint Presentation

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Past R2R Processing Successes at ORNL and Current/Future Opportunities Presented by Dr. David L. Wood, III Roll-to-Roll Manufacturing Team Lead & Fuel Cell Technologies Program Manager Oak Ridge National Laboratory Presented to AMO HV R2R Workshop Alexandria, VA 12/2/15 2 AMO HV R2R Workshop, 12/2/15, David Wood ORNL Is Addressing R2R Processing Issues Relevant to Industry * Annealing of materials on temperature-sensitive substrates (solid-state lithium-ion cathodes for large-scale thin-film

  18. Efficient, air-stable colloidal quantum dot solar cells encapsulated using atomic layer deposition of a nanolaminate barrier

    SciTech Connect

    Ip, Alexander H.; Labelle, Andr J.; Sargent, Edward H.

    2013-12-23

    Atomic layer deposition was used to encapsulate colloidal quantum dot solar cells. A nanolaminate layer consisting of alternating alumina and zirconia films provided a robust gas permeation barrier which prevented device performance degradation over a period of multiple weeks. Unencapsulated cells stored in ambient and nitrogen environments demonstrated significant performance losses over the same period. The encapsulated cell also exhibited stable performance under constant simulated solar illumination without filtration of harsh ultraviolet photons. This monolithically integrated thin film encapsulation method is promising for roll-to-roll processed high efficiency nanocrystal solar cells.

  19. NREL Develops High Speed Scanner to Monitor Fuel Cell Material Defects (Fact Sheet), Highlights in Research & Development, NREL (National Renewable Energy Laboratory)

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    fuel cell scanner could provide effective in-line quality control in a high-volume manufacturing facility. NREL scientists have developed and built a high-throughput, high-resolution, in-line fuel cell scanner to monitor quality and detect critical defects in polymer electrolyte membrane fuel cell (PEMFC) materials. The fuel cell scanner uses a visible light diffuse reflectance imaging technique to gener- ate high-resolution images of PEMFC materials as they are transported along a roll-to-roll

  20. High Quantum Efficiency OLED Lighting Systems

    SciTech Connect

    Shiang, Joseph

    2011-09-30

    The overall goal of the program was to apply improvements in light outcoupling technology to a practical large area plastic luminaire, and thus enable the product vision of an extremely thin form factor high efficiency large area light source. The target substrate was plastic and the baseline device was operating at 35 LPW at the start of the program. The target LPW of the program was a >2x improvement in the LPW efficacy and the overall amount of light to be delivered was relatively high 900 lumens. Despite the extremely difficult challenges associated with scaling up a wet solution process on plastic substrates, the program was able to make substantial progress. A small molecule wet solution process was successfully implemented on plastic substrates with almost no loss in efficiency in transitioning from the laboratory scale glass to large area plastic substrates. By transitioning to a small molecule based process, the LPW entitlement increased from 35 LPW to 60 LPW. A further 10% improvement in outcoupling efficiency was demonstrated via the use of a highly reflecting cathode, which reduced absorptive loss in the OLED device. The calculated potential improvement in some cases is even larger, ~30%, and thus there is considerable room for optimism in improving the net light coupling efficacy, provided absorptive loss mechanisms are eliminated. Further improvements are possible if scattering schemes such as the silver nanowire based hard coat structure are fully developed. The wet coating processes were successfully scaled to large area plastic substrate and resulted in the construction of a 900 lumens luminaire device.

  1. Liquid-phase exfoliation of chemical vapor deposition-grown single layer graphene and its application in solution-processed transparent electrodes for flexible organic light-emitting devices

    SciTech Connect

    Wu, Chaoxing; Li, Fushan E-mail: gtl-fzu@hotmail.com; Wu, Wei; Chen, Wei; Guo, Tailiang E-mail: gtl-fzu@hotmail.com

    2014-12-15

    Efficient and low-cost methods for obtaining high performance flexible transparent electrodes based on chemical vapor deposition (CVD)-grown graphene are highly desirable. In this work, the graphene grown on copper foil was exfoliated into micron-size sheets through controllable ultrasonication. We developed a clean technique by blending the exfoliated single layer graphene sheets with conducting polymer to form graphene-based composite solution, which can be spin-coated on flexible substrate, forming flexible transparent conducting film with high conductivity (?8 ?/?), high transmittance (?81% at 550?nm), and excellent mechanical robustness. In addition, CVD-grown-graphene-based polymer light emitting diodes with excellent bendable performances were demonstrated.

  2. Engineered pinning landscapes for enhanced 2G coil wire

    DOE PAGES [OSTI]

    Rupich, Martin W.; Sathyamurthy, Srivatsan; Fleshler, Steven; Li, Qiang; Solovyov, Vyacheslav; Ozaki, Toshinori; Welp, Ulrich; Kwok, Wai -Kwong; Leroux, Maxime; Koshelev, Alexei E.; et al

    2016-04-01

    We demonstrate a twofold increase in the in-field critical current of AMSC's standard 2G coil wire by irradiation with 18-MeV Au ions. The optimum pinning enhancement is achieved with a dose of 6 × 1011 Au ions/cm2. Although the 77 K, self-field critical current is reduced by about 35%, the in-field critical current (H//c) shows a significant enhancement between 4 and 50 K in fields > 1 T. The process was used for the roll-to-roll irradiation of AMSC's standard 46-mm-wide production coated conductor strips, which were further processed into standard copper laminated coil wire. The long-length wires show the samemore » enhancement as attained with short static irradiated samples. The roll-to-roll irradiation process can be incorporated in the standard 2G wire manufacturing, with no modifications to the current process. In conclusion, the enhanced performance of the wire will benefit rotating machine and magnet applications.« less

  3. FINAL REPORT: Transformational electrode drying process

    SciTech Connect

    Claus Daniel, C.; Wixom, M.

    2013-12-19

    This report includes major findings and outlook from the transformational electrode drying project performance period from January 6, 2012 to August 1, 2012. Electrode drying before cell assembly is an operational bottleneck in battery manufacturing due to long drying times and batch processing. Water taken up during shipment and other manufacturing steps needs to be removed before final battery assembly. Conventional vacuum ovens are limited in drying speed due to a temperature threshold needed to avoid damaging polymer components in the composite electrode. Roll to roll operation and alternative treatments can increase the water desorption and removal rate without overheating and damaging other components in the composite electrode, thus considerably reducing drying time and energy use. The objective of this project was the development of an electrode drying procedure, and the demonstration of processes with no decrease in battery performance. The benchmark for all drying data was an 80°C vacuum furnace treatment with a residence time of 18 – 22 hours. This report demonstrates an alternative roll to roll drying process with a 500-fold improvement in drying time down to 2 minutes and consumption of only 30% of the energy compared to vacuum furnace treatment.

  4. Cool Magnetic Molecules

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    and chemistry of small molecules. An international collaboration of researchers from Spain, Scotland, and the U.S. has utilized ALS Beamline 11.3.1 (small-molecule...

  5. High mobility single-crystalline-like GaAs thin films on inexpensive flexible metal substrates by metal-organic chemical vapor deposition

    SciTech Connect

    Dutta, P. Rathi, M.; Gao, Y.; Yao, Y.; Selvamanickam, V.; Zheng, N.; Ahrenkiel, P.; Martinez, J.

    2014-09-01

    We demonstrate heteroepitaxial growth of single-crystalline-like n and p-type doped GaAs thin films on inexpensive, flexible, and light-weight metal foils by metal-organic chemical vapor deposition. Single-crystalline-like Ge thin film on biaxially textured templates made by ion beam assisted deposition on metal foil served as the epitaxy enabling substrate for GaAs growth. The GaAs films exhibited strong (004) preferred orientation, sharp in-plane texture, low grain misorientation, strong photoluminescence, and a defect density of ?10{sup 7?}cm{sup ?2}. Furthermore, the GaAs films exhibited hole and electron mobilities as high as 66 and 300?cm{sup 2}/V-s, respectively. High mobility single-crystalline-like GaAs thin films on inexpensive metal substrates can pave the path for roll-to-roll manufacturing of flexible III-V solar cells for the mainstream photovoltaics market.

  6. Superhydrophobic anti-ultraviolet films by doctor blade coating

    SciTech Connect

    Cai, Chang-Yun; Yang, Hongta; Lin, Kun-Yi Andrew

    2014-11-17

    This article reports a scalable technology for fabricating polymer films with excellent water-repelling and anti-ultraviolet properties. A roll-to-roll compatible doctor blade coating technology is utilized to prepare silica colloidal crystal-polymer composites. The silica microspheres can then be selectively removed to create flexible self-standing macroporous polymer films with crystalline arrays of pores. The void sizes are controlled by tuning the duration of a reactive ion etching process prior to the removal of the templating silica microspheres. After surface modification, superhydrophobic surface can be achieved. This study further demonstrates that the as-prepared transparent porous films with 200?nm of pores exhibit diffraction of ultraviolet lights originated from the Bragg's diffractive of light from the three-dimensional highly ordered air cavities.

  7. Method for forming a nano-textured substrate

    DOEpatents

    Jeong, Sangmoo; Hu, Liangbing; Cui, Yi

    2015-04-07

    A method for forming a nano-textured surface on a substrate is disclosed. An illustrative embodiment of the present invention comprises dispensing of a nanoparticle ink of nanoparticles and solvent onto the surface of a substrate, distributing the ink to form substantially uniform, liquid nascent layer of the ink, and enabling the solvent to evaporate from the nanoparticle ink thereby inducing the nanoparticles to assemble into an texture layer. Methods in accordance with the present invention enable rapid formation of large-area substrates having a nano-textured surface. Embodiments of the present invention are well suited for texturing substrates using high-speed, large scale, roll-to-roll coating equipment, such as that used in office product, film coating, and flexible packaging applications. Further, embodiments of the present invention are well suited for use with rigid or flexible substrates.

  8. Lithium ion batteries and their manufacturing challenges

    SciTech Connect

    Daniel, Claus

    2015-03-01

    There is no single lithium ion battery. With the variety of materials and electrochemical couples available, it is possible to design battery cells specific to their applications in terms of voltage, state of charge use, lifetime needs, and safety. Selection of specific electrochemical couples also facilitates the design of power and energy ratios and available energy. Integration in a large format cell requires optimized roll-to-roll electrode manufacturing and use of active materials. Electrodes are coated on a metal current collector foil in a composite structure of active material, binders, and conductive additives, requiring careful control of colloidal chemistry, adhesion, and solidification. But the added inactive materials and the cell packaging reduce energy density. Furthermore, degree of porosity and compaction in the electrode can affect battery performance.

  9. Lithium ion batteries and their manufacturing challenges

    DOE PAGES [OSTI]

    Daniel, Claus

    2015-03-01

    There is no single lithium ion battery. With the variety of materials and electrochemical couples available, it is possible to design battery cells specific to their applications in terms of voltage, state of charge use, lifetime needs, and safety. Selection of specific electrochemical couples also facilitates the design of power and energy ratios and available energy. Integration in a large format cell requires optimized roll-to-roll electrode manufacturing and use of active materials. Electrodes are coated on a metal current collector foil in a composite structure of active material, binders, and conductive additives, requiring careful control of colloidal chemistry, adhesion, andmore » solidification. But the added inactive materials and the cell packaging reduce energy density. Furthermore, degree of porosity and compaction in the electrode can affect battery performance.« less

  10. Self-assembled asymmetric membrane containing micron-size germanium for high capacity lithium ion batteries

    SciTech Connect

    Byrd, Ian; Chen, Hao; Webber, Theron; Li, Jianlin; Wu, Ji

    2015-10-23

    We report the formation of novel asymmetric membrane electrode containing micron-size (~5 μm) germanium powders through a self-assembly phase inversion method for high capacity lithium ion battery anode. 850 mA h g-1 capacity (70%) can be retained at a current density of 600 mA g-1 after 100 cycles with excellent rate performance. Such a high retention rate has rarely been seen for pristine micron-size germanium anodes. Moreover, scanning electron microscope studies reveal that germanium powders are uniformly embedded in a networking porous structure consisting of both nanopores and macropores. It is believed that such a unique porous structure can efficiently accommodate the ~260% volume change during germanium alloying and de-alloying process, resulting in an enhanced cycling performance. Finally, these porous membrane electrodes can be manufactured in large scale using a roll-to-roll processing method.

  11. Research Update: Atmospheric pressure spatial atomic layer deposition of ZnO thin films: Reactors, doping, and devices

    SciTech Connect

    Hoye, Robert L. Z. E-mail: jld35@cam.ac.uk; MacManus-Driscoll, Judith L. E-mail: jld35@cam.ac.uk; Muñoz-Rojas, David; Nelson, Shelby F.; Illiberi, Andrea; Poodt, Paul

    2015-04-01

    Atmospheric pressure spatial atomic layer deposition (AP-SALD) has recently emerged as an appealing technique for rapidly producing high quality oxides. Here, we focus on the use of AP-SALD to deposit functional ZnO thin films, particularly on the reactors used, the film properties, and the dopants that have been studied. We highlight how these films are advantageous for the performance of solar cells, organometal halide perovskite light emitting diodes, and thin-film transistors. Future AP-SALD technology will enable the commercial processing of thin films over large areas on a sheet-to-sheet and roll-to-roll basis, with new reactor designs emerging for flexible plastic and paper electronics.

  12. Self-assembled asymmetric membrane containing micron-size germanium for high capacity lithium ion batteries

    DOE PAGES [OSTI]

    Byrd, Ian; Chen, Hao; Webber, Theron; Li, Jianlin; Wu, Ji

    2015-10-23

    We report the formation of novel asymmetric membrane electrode containing micron-size (~5 μm) germanium powders through a self-assembly phase inversion method for high capacity lithium ion battery anode. 850 mA h g-1 capacity (70%) can be retained at a current density of 600 mA g-1 after 100 cycles with excellent rate performance. Such a high retention rate has rarely been seen for pristine micron-size germanium anodes. Moreover, scanning electron microscope studies reveal that germanium powders are uniformly embedded in a networking porous structure consisting of both nanopores and macropores. It is believed that such a unique porous structure can efficientlymore » accommodate the ~260% volume change during germanium alloying and de-alloying process, resulting in an enhanced cycling performance. Finally, these porous membrane electrodes can be manufactured in large scale using a roll-to-roll processing method.« less

  13. Manufacturing Demonstration Facility: Low Temperature Materials Synthesis

    SciTech Connect

    Graham, David E.; Moon, Ji-Won; Armstrong, Beth L.; Datskos, Panos G.; Duty, Chad E.; Gresback, Ryan; Ivanov, Ilia N.; Jacobs, Christopher B.; Jellison, Gerald Earle; Jang, Gyoung Gug; Joshi, Pooran C.; Jung, Hyunsung; Meyer, III, Harry M.; Phelps, Tommy

    2015-06-30

    The Manufacturing Demonstration Facility (MDF) low temperature materials synthesis project was established to demonstrate a scalable and sustainable process to produce nanoparticles (NPs) for advanced manufacturing. Previous methods to chemically synthesize NPs typically required expensive, high-purity inorganic chemical reagents, organic solvents and high temperatures. These processes were typically applied at small laboratory scales at yields sufficient for NP characterization, but insufficient to support roll-to-roll processing efforts or device fabrication. The new NanoFermentation processes described here operated at a low temperature (~60 C) in low-cost, aqueous media using bacteria that produce extracellular NPs with controlled size and elemental stoichiometry. Up-scaling activities successfully demonstrated high NP yields and quality in a 900-L pilot-scale reactor, establishing this NanoFermentation process as a competitive biomanufacturing strategy to produce NPs for advanced manufacturing of power electronics, solid-state lighting and sensors.

  14. High mobility high efficiency organic films based on pure organic materials

    DOEpatents

    Salzman, Rhonda F.; Forrest, Stephen R.

    2009-01-27

    A method of purifying small molecule organic material, performed as a series of operations beginning with a first sample of the organic small molecule material. The first step is to purify the organic small molecule material by thermal gradient sublimation. The second step is to test the purity of at least one sample from the purified organic small molecule material by spectroscopy. The third step is to repeat the first through third steps on the purified small molecule material if the spectroscopic testing reveals any peaks exceeding a threshold percentage of a magnitude of a characteristic peak of a target organic small molecule. The steps are performed at least twice. The threshold percentage is at most 10%. Preferably the threshold percentage is 5% and more preferably 2%. The threshold percentage may be selected based on the spectra of past samples that achieved target performance characteristics in finished devices.

  15. Frederic Laquai Seminar: Photocurrent Generation in Low-Bandgap Polymer and

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Small Molecule Organic Solar Cells | Center for Energy Efficient Materials Frederic Laquai Seminar: Photocurrent Generation in Low-Bandgap Polymer and Small Molecule Organic Solar Cells Apr 18, 2014 | 3:30 PM - 4:30 PM Frederic Laquai Head, Max Planck Research Group for Organic Optoelectronics Max Planck Institute for Polymer Research Photocurrent Generation in Low-Bandgap Polymer and Small Molecule Organic Solar Cells April 18, 2014 | 3:30pm | Elings Hall (CNSI) 1605 Faculty host: Quyen

  16. Marie V. Parkes

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    ... frameworks Using ab initio methods to estimate the binding energy between a metal-organic framework and a small molecule guest Research interests include using metal-organic ...

  17. News Item

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Deep absorbing porphyrin molecules and their applications in organic solar cells Ke Gao, South China University of Technology A new category of conjugated small molecules ...

  18. Martin Karplus Wins Nobel Prize in Chemistry

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    For that purpose, researchers instead had to use quantum physics. But these calculations required so much computing power that researchers could only simulate small molecules. By ...

  19. ALSNews Vol. 320

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    useful. Recently, however, an international collaboration of researchers from Spain, Scotland, and the U.S. has utilized ALS Beamline 11.3.1 (small-molecule...

  20. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Assembly of the Ebola Virus Nucleoprotein from a Chaperoned VP35 Complex Kirchdoerfer, ... Hepatitis B Virus Capsids Have Diverse Structural Responses to Small-Molecule Ligands ...

  1. Peptoid Nanosheets Offer a Diversity of Functionalities

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    up, through the self-assembly of small molecule, protein, or polymer building blocks. Polymer-based two-dimensional nanomaterials, in particular, hold promise as templates for...

  2. Peculiarity of two thermodynamically-stable morphologies and...

    Office of Scientific and Technical Information (OSTI)

    of small molecule bulk heterojunction solar cells You are accessing a document from the Department of Energy's (DOE) Public Access Gateway for Energy & Science (PAGES). ...

  3. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... and superfluidity (4) engineering (4) environmental sciences (4) geologic ... Small-Molecule CD4-Mimics: Structure-Based Optimization of HIV-1 Entry Inhibition Melillo, ...

  4. Summer 2012 Intern Project- Kerim Tshimanga | Center for Energy...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    To that end, our lab has been studying optoelectronic devices, photovoltaic, light-emitting, etc. that employ polymers and organic small molecules instead of inorganic materials ...

  5. Beamline 11.3.1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    1 Print Small-molecule crystallography Beamline 11.3.1 web site Scientific disciplines: Structural chemistry, magnetic materials, microporous materials. GENERAL BEAMLINE...

  6. Beamline 11.3.1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    3.1 Print Small-molecule crystallography Beamline 11.3.1 web site Scientific disciplines: Structural chemistry, magnetic materials, microporous materials. GENERAL BEAMLINE...

  7. Sergey Maximoff | Center for Gas SeparationsRelevant to Clean...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    TX EFRC research: Dr. Maximoff's interest within this EFRC centers on theory of adsorption, desorption, and chemical conversion of small molecules within porous materials. He...

  8. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... S. ; de Pablo, J. J. ; Univ. Chicago) ; Univ. Wisconsin-Madison) September 2013 A Supramolecular Complex in Small-Molecule Solar Cells based on Contorted Aromatic Molecules Kang ...

  9. LANL >> GFP Website >> Home

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    of a protein are soluble Evaluate how a protein interacts with other proteins (protein-protein interaction) Reveal the effect of a small molecule on the protein's folding...

  10. Understanding Metal Directed-Assembly Growth of Single-Crystal...

    Office of Scientific and Technical Information (OSTI)

    The deterministic growth of oriented crystalline organic nanowires (CONs) from the vapor-solid chemical reaction (VSCR) between small-molecule reactants and metal nanoparticles has ...

  11. Airbrushed Nickel Nanoparticles for Large-Area

    SciTech Connect

    Sarac, Mehmet; ANDERSON, BRYAN; Pearce, Ryan; Railsback, Justin; Oni, Adedapo; White, Ryan M.; Hensley, Dale K; Lebeau, James M; Melechko, Anatoli; Tracy, Joseph B

    2013-01-01

    Vertically aligned carbon nanofibers (VACNFs) were grown by plasma-enhanced chemical vapor deposition (PECVD) using Ni nanoparticle (NP) catalysts that were deposited by airbrushing onto Si, Al, Cu, and Ti substrates. Airbrushing is a simple method for depositing catalyst NPs over large areas that is compatible with roll-to-roll processing. The distribution and morphology of VACNFs are affected by the airbrushing parameters and the composition of the metal foil. Highly concentrated Ni NPs in heptane give more uniform distributions than pentane and hexanes, resulting in more uniform coverage of VACNFs. For VACNF growth on metal foils, Si micropowder was added as a precursor for Si-enriched coatings formed in situ on the VACNFs that impart mechanical rigidity. Interactions between the catalyst NPs and the metal substrates impart control over the VACNF morphology. Growth of carbon nanostructures on Cu is particularly noteworthy because the miscibility of Ni with Cu poses challenges for VACNF growth, and carbon nanostructures anchored to Cu substrates are desired as anode materials for Li-ion batteries and for thermal interface materials.

  12. Electrophoretic deposited TiO2 pigment-based back reflectors for thin film solar cells

    SciTech Connect

    Bills, Braden; Morris, Nathan; Dubey, Mukul; Wang, Qi; Fan, Qi Hua

    2015-01-16

    Highly reflective coatings with strong light scattering effect have many applications in optical components and optoelectronic devices. This paper reports titanium dioxide (TiO2) pigment-based reflectors that have 2.5 times higher broadband diffuse reflection than commercially produced aluminum or silver based reflectors and result in efficiency enhancements of a single-junction amorphous Si solar cell. Electrophoretic deposition is used to produce pigment-based back reflectors with high pigment density, controllable film thickness and site-specific deposition. Electrical conductivity of the pigment-based back reflectors is improved by creating electrical vias throughout the pigment-based back reflector by making holes using an electrical discharge / dielectric breakdown approach followed by a second electrophoretic deposition of conductive nanoparticles into the holes. While previous studies have demonstrated the use of pigment-based back reflectors, for example white paint, on glass superstrate configured thin film Si solar cells, this work presents a scheme for producing pigment-based reflectors on complex shape and flexible substrates. Finally, mechanical durability and scalability are demonstrated on a continuous electrophoretic deposition roll-to-roll system which has flexible metal substrate capability of 4 inch wide and 300 feet long.

  13. Cost and Reliability Improvement for CIGS-Based PV on Flexible Substrate: May 24, 2006 -- July 31, 2010

    SciTech Connect

    Wiedeman, S.

    2011-05-01

    Global Solar Energy rapidly advances the cost and performance of commercial thin-film CIGS products using roll-to-roll processing on steel foil substrate in compact, low cost deposition equipment, with in-situ sensors for real-time intelligent process control. Substantial increases in power module efficiency, which now exceed 13%, are evident at GSE factories in two countries with a combined capacity greater than 75 MW. During 2009 the average efficiency of cell strings (3780 cm2) was increased from 7% to over 11%, with champion results exceeding 13% Continued testing of module reliability in rigid product has reaffirmed extended life expectancy for standard glass product, and has qualified additional lower-cost methods and materials. Expected lifetime for PV in flexible packages continues to increase as failure mechanisms are elucidated, and resolved by better methods and materials. Cost reduction has been achieved through better materials utilization, enhanced vendor and material qualification and selection. The largest cost gains have come as a result of higher cell conversion efficiency and yields, higher processing rates, greater automation and improved control in all process steps. These improvements are integral to this thin film PV partnership program, and all realized with the 'Gen2' manufacturing plants, processes and equipment.

  14. High-Efficiency Amorphous Silicon Alloy Based Solar Cells and Modules; Final Technical Progress Report, 30 May 2002--31 May 2005

    SciTech Connect

    Guha, S.; Yang, J.

    2005-10-01

    The principal objective of this R&D program is to expand, enhance, and accelerate knowledge and capabilities for development of high-efficiency hydrogenated amorphous silicon (a-Si:H) and amorphous silicon-germanium alloy (a-SiGe:H) related thin-film multijunction solar cells and modules with low manufacturing cost and high reliability. Our strategy has been to use the spectrum-splitting triple-junction structure, a-Si:H/a-SiGe:H/a-SiGe:H, to improve solar cell and module efficiency, stability, and throughput of production. The methodology used to achieve the objectives included: (1) explore the highest stable efficiency using the triple-junction structure deposited using RF glow discharge at a low rate, (2) fabricate the devices at a high deposition rate for high throughput and low cost, and (3) develop an optimized recipe using the R&D batch large-area reactor to help the design and optimization of the roll-to-roll production machines. For short-term goals, we have worked on the improvement of a-Si:H and a-SiGe:H alloy solar cells. a-Si:H and a-SiGe:H are the foundation of current a-Si:H based thin-film photovoltaic technology. Any improvement in cell efficiency, throughput, and cost reduction will immediately improve operation efficiency of our manufacturing plant, allowing us to further expand our production capacity.

  15. Colloidal quantum dot solar cells on curved and flexible substrates

    SciTech Connect

    Kramer, Illan J.; Moreno-Bautista, Gabriel; Minor, James C.; Kopilovic, Damir; Sargent, Edward H.

    2014-10-20

    Colloidal quantum dots (CQDs) are semiconductor nanocrystals synthesized with, processed in, and deposited from the solution phase, potentially enabling low-cost, facile manufacture of solar cells. Unfortunately, CQD solar cell reports, until now, have only explored batch-processing methods—such as spin-coating—that offer limited capacity for scaling. Spray-coating could offer a means of producing uniform colloidal quantum dot films that yield high-quality devices. Here, we explore the versatility of the spray-coating method by producing CQD solar cells in a variety of previously unexplored substrate arrangements. The potential transferability of the spray-coating method to a roll-to-roll manufacturing process was tested by spray-coating the CQD active layer onto six substrates mounted on a rapidly rotating drum, yielding devices with an average power conversion efficiency of 6.7%. We further tested the manufacturability of the process by endeavoring to spray onto flexible substrates, only to find that spraying while the substrate was flexed was crucial to achieving champion performance of 7.2% without compromise to open-circuit voltage. Having deposited onto a substrate with one axis of curvature, we then built our CQD solar cells onto a spherical lens substrate having two axes of curvature resulting in a 5% efficient device. These results show that CQDs deposited using our spraying method can be integrated to large-area manufacturing processes and can be used to make solar cells on unconventional shapes.

  16. Oxygen Incorporation During Fabrication of Substrate CdTe Photovoltaic Devices: Preprint

    SciTech Connect

    Duenow, J. N.; Dhere, R. G.; Kuciauskas, D.; Li, J. V.; Pankow, J. W.; DeHart, C. M.; Gessert, T. A.

    2012-06-01

    Recently, CdTe photovoltaic (PV) devices fabricated in the nonstandard substrate configuration have attracted increasing interest because of their potential compatibility with flexible substrates such as metal foils and polymer films. This compatibility could lead to the suitability of CdTe for roll-to-roll processing and building-integrated PV. Currently, however, the efficiencies of substrate CdTe devices reported in the literature are significantly lower ({approx}6%-8%) than those of high-performance superstrate devices ({approx}17%) because of significantly lower open-circuit voltage (Voc) and fill factor (FF). In our recent device development efforts, we have found that processing parameters required to fabricate high-efficiency substrate CdTe PV devices differ from those necessary for traditional superstrate CdTe devices. Here, we investigate how oxygen incorporation in the CdTe deposition, CdCl2 heat treatment, CdS deposition, and post-deposition heat treatment affect device characteristics through their effects on the junction. By adjusting whether oxygen is incorporated during these processing steps, we have achieved Voc values greater than 860 mV and efficiencies greater than 10%.

  17. Electrophoretic deposited TiO2 pigment-based back reflectors for thin film solar cells

    DOE PAGES [OSTI]

    Bills, Braden; Morris, Nathan; Dubey, Mukul; Wang, Qi; Fan, Qi Hua

    2015-01-16

    Highly reflective coatings with strong light scattering effect have many applications in optical components and optoelectronic devices. This paper reports titanium dioxide (TiO2) pigment-based reflectors that have 2.5 times higher broadband diffuse reflection than commercially produced aluminum or silver based reflectors and result in efficiency enhancements of a single-junction amorphous Si solar cell. Electrophoretic deposition is used to produce pigment-based back reflectors with high pigment density, controllable film thickness and site-specific deposition. Electrical conductivity of the pigment-based back reflectors is improved by creating electrical vias throughout the pigment-based back reflector by making holes using an electrical discharge / dielectric breakdownmore » approach followed by a second electrophoretic deposition of conductive nanoparticles into the holes. While previous studies have demonstrated the use of pigment-based back reflectors, for example white paint, on glass superstrate configured thin film Si solar cells, this work presents a scheme for producing pigment-based reflectors on complex shape and flexible substrates. Finally, mechanical durability and scalability are demonstrated on a continuous electrophoretic deposition roll-to-roll system which has flexible metal substrate capability of 4 inch wide and 300 feet long.« less

  18. Nanowire CdS-CdTe solar cells with molybdenum oxide as contact

    SciTech Connect

    Dang, Hongmei; Singh, Vijay P.

    2015-10-06

    Using a 10 nm thick molybdenum oxide (MoO3-x) layer as a transparent and low barrier contact to p-CdTe, we demonstrate nanowire CdS-CdTe solar cells with a power conversion efficiency of 11% under front side illumination. Annealing the as-deposited MoO3 film in N2 resulted in a reduction of the cell’s series resistance, from 9.97 Ω/cm2 to 7.69 Ω/cm2, and increase in efficiency from 9.9% to 11%. Under illumination from the back, the MoO3-x/Au side, the nanowire solar cells yielded Jsc of 21 mA/cm2 and efficiency of 8.67%. Our results demonstrate use of a thin layer transition metal oxide as a potential way for a transparent back contact to nanowire CdS-CdTe solar cells. As a result, this work has implications toward enabling a novel superstrate structure nanowire CdS-CdTe solar cell on Al foil substrate by a low cost roll-to roll fabrication process.

  19. Nanowire CdS-CdTe solar cells with molybdenum oxide as contact

    DOE PAGES [OSTI]

    Dang, Hongmei; Singh, Vijay P.

    2015-10-06

    Using a 10 nm thick molybdenum oxide (MoO3-x) layer as a transparent and low barrier contact to p-CdTe, we demonstrate nanowire CdS-CdTe solar cells with a power conversion efficiency of 11% under front side illumination. Annealing the as-deposited MoO3 film in N2 resulted in a reduction of the cell’s series resistance, from 9.97 Ω/cm2 to 7.69 Ω/cm2, and increase in efficiency from 9.9% to 11%. Under illumination from the back, the MoO3-x/Au side, the nanowire solar cells yielded Jsc of 21 mA/cm2 and efficiency of 8.67%. Our results demonstrate use of a thin layer transition metal oxide as a potentialmore » way for a transparent back contact to nanowire CdS-CdTe solar cells. As a result, this work has implications toward enabling a novel superstrate structure nanowire CdS-CdTe solar cell on Al foil substrate by a low cost roll-to roll fabrication process.« less

  20. Nanomanufacturing : nano-structured materials made layer-by-layer.

    SciTech Connect

    Cox, James V.; Cheng, Shengfeng; Grest, Gary Stephen; Tjiptowidjojo, Kristianto; Reedy, Earl David, Jr.; Fan, Hongyou; Schunk, Peter Randall; Chandross, Michael Evan; Roberts, Scott A.

    2011-10-01

    Large-scale, high-throughput production of nano-structured materials (i.e. nanomanufacturing) is a strategic area in manufacturing, with markets projected to exceed $1T by 2015. Nanomanufacturing is still in its infancy; process/product developments are costly and only touch on potential opportunities enabled by growing nanoscience discoveries. The greatest promise for high-volume manufacturing lies in age-old coating and imprinting operations. For materials with tailored nm-scale structure, imprinting/embossing must be achieved at high speeds (roll-to-roll) and/or over large areas (batch operation) with feature sizes less than 100 nm. Dispersion coatings with nanoparticles can also tailor structure through self- or directed-assembly. Layering films structured with these processes have tremendous potential for efficient manufacturing of microelectronics, photovoltaics and other topical nano-structured devices. This project is designed to perform the requisite R and D to bring Sandia's technology base in computational mechanics to bear on this scale-up problem. Project focus is enforced by addressing a promising imprinting process currently being commercialized.

  1. Development and Testing of Abrasion Resistant Hard Coats For Polymer Film Reflectors: Preprint

    SciTech Connect

    Jorgensen, G.; Gee, R.; DiGrazia, M.

    2010-10-01

    Reflective polymer film technology can significantly reduce the cost of solar reflectors and installed Concentrated Solar Power (CSP) plants by both reduced material cost and lower weight. One challenge of polymer reflectors in the CSP environment pertains to contact cleaning methods typically used with glass mirrors. Such contact cleaning methods can scratch the surface of polymer reflectors and thereby reduce specular reflectance. ReflecTech, Inc. (a subsidiary of SkyFuel, Inc.) and the National Renewable Energy Laboratory (NREL) initiated a cooperative research and development agreement (CRADA) to devise and develop an abrasion resistant coating (ARC) suitable for deposition onto polymer based mirror film. A number of candidate ARC products were identified as candidate formulations. Industrial collaborators prepared samples having their ARCs deposited onto ReflecTech Mirror Film pre-laminated to aluminum sheet substrates. Samples were provided for evaluation and subjected to baseline (unweathered) and accelerated exposure conditions and subsequently characterized for abrasion resistance and adhesion. An advanced ARC product has been identified that exhibits outstanding initial abrasion resistance and adhesion to ReflecTech Mirror Film. These properties were also retained after exposure to the various accelerated stress conditions. This material has been successfully manufactured as a 1.5 m wide roll-to-roll construction in a production environment.

  2. Rapid low-temperature processing of metal-oxide thin film transistors with combined far ultraviolet and thermal annealing

    SciTech Connect

    Leppniemi, J. Ojanper, K.; Kololuoma, T.; Huttunen, O.-H.; Majumdar, H.; Alastalo, A.; Dahl, J.; Tuominen, M.; Laukkanen, P.

    2014-09-15

    We propose a combined far ultraviolet (FUV) and thermal annealing method of metal-nitrate-based precursor solutions that allows efficient conversion of the precursor to metal-oxide semiconductor (indium zinc oxide, IZO, and indium oxide, In{sub 2}O{sub 3}) both at low-temperature and in short processing time. The combined annealing method enables a reduction of more than 100?C in annealing temperature when compared to thermally annealed reference thin-film transistor (TFT) devices of similar performance. Amorphous IZO films annealed at 250?C with FUV for 5?min yield enhancement-mode TFTs with saturation mobility of ?1?cm{sup 2}/(Vs). Amorphous In{sub 2}O{sub 3} films annealed for 15?min with FUV at temperatures of 180?C and 200?C yield TFTs with low-hysteresis and saturation mobility of 3.2?cm{sup 2}/(Vs) and 7.5?cm{sup 2}/(Vs), respectively. The precursor condensation process is clarified with x-ray photoelectron spectroscopy measurements. Introducing the FUV irradiation at 160?nm expedites the condensation process via in situ hydroxyl radical generation that results in the rapid formation of a continuous metal-oxygen-metal structure in the film. The results of this paper are relevant in order to upscale printed electronics fabrication to production-scale roll-to-roll environments.

  3. USFOE: Extended Summary - Lithium ion batteries and their manufacturing challenges

    SciTech Connect

    Daniel, Claus

    2014-01-01

    There is no one lithium ion battery. With the variety of materials and electrochemical couples at our disposal as shown in the previous talks, we have the opportunity to design battery cells specific for their applications. Such applications require optimization of voltage, state of charge utilization, lifetime needs, and safety considerations. Electrochemical couples allow for designing power and energy ratios and available energy for the application. Integration in a large format cell requires optimized roll to roll electrode manufacturing and active material utilization. Electrodes are coated on a current collector in a composite structure comprised of active material, binders, and conductive additives which requires careful control of colloidal chemistry, adhesion, and solidification. These added inactive materials and the cell packaging reduce energy density. Degree of porosity and compaction in the electrode can impede or enhance battery performance. Pathways are explored to bring batteries from currently commercially available 100Wh/kg and 200Wh/L at $500/kWh to 250Wh/kg and 400Wh/L at $125/kWh.

  4. High-Performance Flexible Perovskite Solar Cells by Using a Combination of Ultrasonic Spray-Coating and Low Thermal Budget Photonic Curing

    SciTech Connect

    Sanjib, Das; Yang, Bin; Gu, Gong; Joshi, Pooran C; Ivanov, Ilia N; Rouleau, Christopher; Aytug, Tolga; Geohegan, David B; Xiao, Kai

    2015-01-01

    Realizing the commercialization of high-performance and robust perovskite solar cells urgently requires the development of economically scalable processing techniques. Here we report a high-throughput ultrasonic spray-coating (USC) process capable of fabricating perovskite film-based solar cells on glass substrates with power conversion efficiency (PCE) as high as 13.04%. Perovskite films with high uniformity, crystallinity, and surface coverage are obtained in a single step. Moreover, we report USC processing on TiOx/ITO-coated polyethylene terephthalate (PET) substrates to realize flexible perovskite solar cells with PCE as high as 8.02% that are robust under mechanical stress. In this case, an optical curing technique was used to achieve a highly-conductive TiOx layer on flexible PET substrates for the first time. The high device performance and reliability obtained by this combination of USC processing with optical curing appears very promising for roll-to-roll manufacturing of high-efficiency, flexible perovskite solar cells.

  5. Final Technical Report CONDUCTIVE COATINGS FOR SOLAR CELLS USING CARBON NANOTUBES

    SciTech Connect

    Paul J Glatkowski; Jorma Peltola; Christopher Weeks; Mike Trottier; David Britz

    2007-09-30

    US Department of Energy (DOE) awarded a grant for Eikos Inc. to investigate the feasibility of developing and utilizing Transparent Conducting Coatings (TCCs) based on carbon nanotubes (CNT) for solar cell applications. Conventional solar cells today employ metal oxide based TCCs with both Electrical Resistivity (R) and Optical Transparency (T), commonly referred to as optoelectronic (RT) performance significantly higher than with those possible with CNT based TCCs available today. Transparent metal oxide based coatings are also inherently brittle requiring high temperature in vacuum processing and are thus expensive to manufacture. One such material is indium tin oxide (ITO). Global demand for indium has recently increased rapidly while supply has diminished causing substantial spikes in raw material cost and availability. In contrast, the raw material, carbon, needed for CNT fabrication is abundantly available. Transparent Conducting Coatings based on CNTs can overcome not only cost and availability constraints while also offering the ability to be applied by existing, low cost process technologies under ambient conditions. Processes thus can readily be designed both for rigid and flexible PV technology platforms based on mature spray or dip coatings for silicon based solar cells and continuous roll to roll coating processes for polymer solar applications.

  6. Synthesis of Two-Dimensional Materials for Capacitive Energy Storage

    DOE PAGES [OSTI]

    Mendoza-Sánchez, Beatriz; Gogotsi, Yury

    2016-06-02

    The unique properties and great variety of two-dimensional (2D) nanomaterials make them highly attractive for energy storage applications. Here, an insight into the progress made towards the application of 2D nanomaterials for capacitive energy storage is provided. Moreover, synthesis methods, and electrochemical performance of various classes of 2D nanomaterials, particularly based on graphene, transition metal oxides, dichalcogenides, and carbides, are presented. Some factors that directly influence capacitive performance are discussed throughout the text and include nanosheet composition, morphology and texture, electrode architecture, and device configuration. Recent progress in the fabrication of 2D-nanomaterials-based microsupercapacitors and flexible and free-standing supercapacitors is presented.more » The main electrode manufacturing techniques with emphasis on scalability and cost-effectiveness are discussed, and include laser scribing, printing, and roll-to-roll manufacture. Some various issues that prevent the use of the full energy-storage potential of 2D nanomaterials and how they have been tackled are discussed, and include nanosheet aggregation and the low electrical conductivity of some 2D nanomaterials. In particular, the design of hybrid and hierarchical 2D and 3D structures based on 2D nanomaterials is presented. Other challenges and opportunities are discussed and include: control of nanosheets size and thickness, chemical and electrochemical instability, and scale-up of electrode films.« less

  7. DE-FE0010799 | netl.doe.gov

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    ... research is being funded through a DOE ARPA-E project which, if successful, will ... At least three papers related to the ARPA-e funded design of small molecule ...

  8. ALSNews Vol. 320

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    has utilized ALS Beamline 11.3.1 (small-molecule crystallography) to characterize the design of such "molecular coolers." Read more... Contact: This e-mail address is being...

  9. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Unfortunately, less attention has been given to the effect of the core block on the micelle stability, morphology, and the rate of diffusion of small molecules from the core. This ...

  10. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Have feedback or suggestions for a way to improve these results? Small-Molecule CD4-Mimics: Structure-Based Optimization of HIV-1 Entry Inhibition Melillo, Bruno ; Liang, Shuaiyi ...

  11. ALSNews Vol. 320

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    from Spain, Scotland, and the U.S. has utilized ALS Beamline 11.3.1 (small-molecule crystallography) to characterize the design of such "molecular coolers." Read more... ...

  12. Cool Magnetic Molecules

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    of researchers from Spain, Scotland, and the U.S. has utilized ALS Beamline 11.3.1 (small-molecule crystallography) to characterize the design of such "molecular coolers." ...

  13. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Filter Results Filter by Subject aids virus (5) applied life sciences (4) cleavage (2) ... Resistance of a human immunodeficiency virus type 1 isolate to a small molecule CCR5 ...

  14. CX-009472: Categorical Exclusion Determination

    Energy.gov [DOE]

    Small Molecule Associative Carbon Dioxide Thickeners for Improved Mobility Control CX(s) Applied: A1, B3.6 Date: 10/15/2012 Location(s): Pennsylvania Offices(s): National Energy Technology Laboratory

  15. ALSNews Vol. 363

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Read more... Contact: This e-mail address is being protected from spambots. You need JavaScript enabled to view it A Fullerene that Breaks the Rules Scientists used small-molecule...

  16. Development of New Absorber Materials to Achieve Organic Photovoltaic Commercial Modules with 15% Efficiency and 20 Years Lifetime: Cooperative Research and Development Final Report, CRADA Number CRD-12-498

    SciTech Connect

    Olson, D.

    2014-08-01

    Under this CRADA the parties will develop intermediates or materials that can be employed as the active layer in dye sensitized solar cells printed polymer systems, or small molecule organic photovoltaics.

  17. Beamline 11.3.1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    11.3.1 Print Tuesday, 20 October 2009 09:22 Small-molecule crystallography Beamline 11.3.1 web site Scientific disciplines: Structural chemistry, magnetic materials, microporous...

  18. Chemistry & Materials Science

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    greenhouse gas carbon dioxide to small molecules such as formic acid, formaldehyde, and methanol. Read More JiangCummingsCoverLarge.gif Promise for Onion-Like Carbons as...

  19. Organic Light-Emitting Diodes (OLEDs) and Optically-Detected Magnetic Resonance (ODMR) studies on organic materials

    SciTech Connect

    Cai, Min

    2011-01-01

    Organic semiconductors have evolved rapidly over the last decades and currently are considered as the next-generation technology for many applications, such as organic light-emitting diodes (OLEDs) in flat-panel displays (FPDs) and solid state lighting (SSL), and organic solar cells (OSCs) in clean renewable energy. This dissertation focuses mainly on OLEDs. Although the commercialization of the OLED technology in FPDs is growing and appears to be just around the corner for SSL, there are still several key issues that need to be addressed: (1) the cost of OLEDs is very high, largely due to the costly current manufacturing process; (2) the efficiency of OLEDs needs to be improved. This is vital to the success of OLEDs in the FPD and SSL industries; (3) the lifetime of OLEDs, especially blue OLEDs, is the biggest technical challenge. All these issues raise the demand for new organic materials, new device structures, and continued lower-cost fabrication methods. In an attempt to address these issues, we used solution-processing methods to fabricate highly efficient small molecule OLEDs (SMOLEDs); this approach is costeffective in comparison to the more common thermal vacuum evaporation. We also successfully made efficient indium tin oxide (ITO)-free SMOLEDs to further improve the efficiency of the OLEDs. We employed the spin-dependent optically-detected magnetic resonance (ODMR) technique to study the luminescence quenching processes in OLEDs and organic materials in order to understand the intrinsic degradation mechanisms. We also fabricated polymer LEDs (PLEDs) based on a new electron-accepting blue-emitting polymer and studied the effect of molecular weight on the efficiency of PLEDs. All these studies helped us to better understand the underlying relationship between the organic semiconductor materials and the OLEDs’ performance, and will subsequently assist in further enhancing the efficiency of OLEDs. With strongly improved device performance (in addition to

  20. Eleventh international symposium on radiopharmaceutical chemistry

    SciTech Connect

    1995-12-31

    This document contains abstracts of papers which were presented at the Eleventh International Symposium on Radiopharmaceutical Chemistry. Sessions included: radiopharmaceuticals for the dopaminergic system, strategies for the production and use of labelled reactive small molecules, radiopharmaceuticals for measuring metabolism, radiopharmaceuticals for the serotonin and sigma receptor systems, labelled probes for molecular biology applications, radiopharmaceuticals for receptor systems, radiopharmaceuticals utilizing coordination chemistry, radiolabelled antibodies, radiolabelling methods for small molecules, analytical techniques in radiopharmaceutical chemistry, and analytical techniques in radiopharmaceutical chemistry.

  1. IMS - MS Data Extractor

    Energy Science and Technology Software Center

    2015-10-20

    An automated drift time extraction and computed associated collision cross section software tool for small molecule analysis with ion mobility spectrometry-mass spectrometry (IMS-MS). The software automatically extracts drift times and computes associated collision cross sections for small molecules analyzed using ion mobility spectrometry-mass spectrometry (IMS-MS) based on a target list of expected ions provided by the user.

  2. Slide 1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Understanding Small Molecule Interactions in Metal-Organic Frameworks: Coupling Experiment with Theory Scientific Achievement A combined experimental and theoretical approach proves essential for the elucidation of small-molecule interactions in a model MOF system known as M 2 (dobdc). Significance and Impact The study of extensive families like M 2 (dobdc) provides a platform to test the efficacy and accuracy of developing computational methodologies in slightly varying chemical environments, a

  3. Low thermal budget photonic processing of highly conductive Cu interconnects based on CuO nanoinks. Potential for flexible printed electronics

    DOE PAGES [OSTI]

    Rager, Matthew S.; Aytug, Tolga; Veith, Gabriel M.; Joshi, Pooran C.

    2015-12-31

    The developing field of printed electronics nanoparticle based inks such as CuO show great promise as a low-cost alternative to other metal-based counterparts (e.g., silver). In particular, CuO inks significantly eliminate the issue of particle oxidation, before and during the sintering process, that is prevalent in Cu-based formulations. We report here the scalable and low-thermal budget photonic fabrication of Cu interconnects employing a roll-to-roll compatible pulse-thermal-processing (PTP) technique that enables phase reduction and subsequent sintering of inkjet-printed CuO patterns onto flexible polymer templates. Detailed investigations of curing and sintering conditions were performed to understand the impact of PTP system conditionsmore » on the electrical performance of the Cu patterns. Specifically, the impact of energy and power of photonic pulses on print conductivity was systematically studied by varying the following key processing parameters: pulse intensity, duration and sequence. Through optimization of such parameters, highly conductive prints in < 1 s with resistivity values as low as 100 n m has been achieved. We also observed that the introduction of an initial ink-drying step in ambient atmosphere, after the printing and before sintering, leads to significant improvements in mechanical integrity and electrical performance of the printed Cu patterns. Moreover, the viability of CuO reactive inks, coupled with the PTP technology and pre ink-drying protocols, has also been demonstrated for the additive integration of a low-cost Cu temperature sensor onto a flexible polymer substrate.« less

  4. NREL Researchers Demonstrate External Quantum Efficiency Surpassing 100% in a Quantum Dot Solar Cell (Fact Sheet)

    SciTech Connect

    Not Available

    2011-12-01

    A new device that produces and collects multiple electrons per photon could yield inexpensive, high-efficiency photovoltaics. A new device developed through research at the National Renewable Energy Laboratory (NREL) reduces conventional losses in photovoltaic (PV) solar cells, potentially increasing the power conversion efficiency-but not the cost-of the solar cells. Solar cells convert optical energy from the sun into usable electricity; however, almost 50% of the incident energy is lost as heat with present-day technologies. High-efficiency, multi-junction cells reduce this heat loss, but their cost is significantly higher. NREL's new device uses excess energy in solar photons to create extra charges rather than heat. This was achieved using 5-nanometer-diameter quantum dots of lead selenide (PbSe) tightly packed into a film. The researchers chemically treated the film, and then fabricated a device that yielded an external quantum efficiency (number of electrons produced per incident photon) exceeding 100%, a value beyond that of all current solar cells for any incident photon. Quantum dots are known to efficiently generate multiple excitons (a bound electron-hole pair) per absorbed high-energy photon, and this device definitively demonstrates the collection of multiple electrons per photon in a PV cell. The internal quantum efficiency corrects for photons that are not absorbed in the photoactive layer and shows that the PbSe film generates 30% to 40% more electrons in the high-energy spectral region than is possible with a conventional solar cell. While the unoptimized overall power conversion efficiency is still low (less than 5%), the results have important implications for PV because such high quantum efficiency can lead to more electrical current produced than possible using present technologies. Furthermore, this fabrication is also amenable to inexpensive, high-throughput roll-to-roll manufacturing.

  5. Low thermal budget photonic processing of highly conductive Cu interconnects based on CuO nanoinks. Potential for flexible printed electronics

    SciTech Connect

    Rager, Matthew S.; Aytug, Tolga; Veith, Gabriel M.; Joshi, Pooran C.

    2015-12-31

    The developing field of printed electronics nanoparticle based inks such as CuO show great promise as a low-cost alternative to other metal-based counterparts (e.g., silver). In particular, CuO inks significantly eliminate the issue of particle oxidation, before and during the sintering process, that is prevalent in Cu-based formulations. We report here the scalable and low-thermal budget photonic fabrication of Cu interconnects employing a roll-to-roll compatible pulse-thermal-processing (PTP) technique that enables phase reduction and subsequent sintering of inkjet-printed CuO patterns onto flexible polymer templates. Detailed investigations of curing and sintering conditions were performed to understand the impact of PTP system conditions on the electrical performance of the Cu patterns. Specifically, the impact of energy and power of photonic pulses on print conductivity was systematically studied by varying the following key processing parameters: pulse intensity, duration and sequence. Through optimization of such parameters, highly conductive prints in < 1 s with resistivity values as low as 100 n m has been achieved. We also observed that the introduction of an initial ink-drying step in ambient atmosphere, after the printing and before sintering, leads to significant improvements in mechanical integrity and electrical performance of the printed Cu patterns. Moreover, the viability of CuO reactive inks, coupled with the PTP technology and pre ink-drying protocols, has also been demonstrated for the additive integration of a low-cost Cu temperature sensor onto a flexible polymer substrate.

  6. Metathesis depolymerizable surfactants

    DOEpatents

    Jamison, Gregory M.; Wheeler, David R.; Loy, Douglas A.; Simmons, Blake A.; Long, Timothy M.; McElhanon, James R.; Rahimian, Kamyar; Staiger, Chad L.

    2008-04-15

    A class of surfactant molecules whose structure includes regularly spaced unsaturation in the tail group and thus, can be readily decomposed by ring-closing metathesis, and particularly by the action of a transition metal catalyst, to form small molecule products. These small molecules are designed to have increased volatility and/or enhanced solubility as compared to the original surfactant molecule and are thus easily removed by solvent extraction or vacuum extraction at low temperature. By producing easily removable decomposition products, the surfactant molecules become particularly desirable as template structures for preparing meso- and microstructural materials with tailored properties.

  7. TRANSPARENT COATINGS FOR SOLAR CELLS RESEARCH

    SciTech Connect

    Glatkowski, P.J.; Landis, D.A.

    2013-04-16

    patterning and alignment, advances in commercial and research materials and field effect schemes. In addition, Eikos continued to develop improved efficiency coating materials and transfer methods suitable for batch and continuous roll-to-roll fabrication requirements. Finally, Eikos collaborated with NREL and the PV-community at large in fabricating and characterizing Invisicon® enabled solar cells.

  8. Critical Research for Cost-Effective Photoelectrochemical Production of Hydrogen

    SciTech Connect

    Xu, Liwei; Deng, Xunming; Abken, Anka; Cao, Xinmin; Du, Wenhui; Vijh, Aarohi; Ingler, William; Chen, Changyong; Fan, Qihua; Collins, Robert; Compaan, Alvin; Yan, Yanfa; Giolando, Dean; Turner, John

    2014-10-29

    The objective of this project is to develop critical technologies required for cost-effective production of hydrogen from sunlight and water using a-Si triple junction solar cell based photo-electrodes. In this project, Midwest Optoelectronics, LLC (MWOE) and its collaborating organizations utilize triple junction a-Si thin film solar cells as the core element to fabricate photoelectrochemical (PEC) cells. Triple junction a-Si/a-SiGe/a-SiGe solar cell is an ideal material for making cost-effective PEC system which uses sun light to split water and generate hydrogen. It has the following key features: 1) It has an open circuit voltage (Voc ) of ~ 2.3V and has an operating voltage around 1.6V. This is ideal for water splitting. There is no need to add a bias voltage or to inter-connect more than one solar cell. 2) It is made by depositing a-Si/a-SiGe/aSi-Ge thin films on a conducting stainless steel substrate which can serve as an electrode. When we immerse the triple junction solar cells in an electrolyte and illuminate it under sunlight, the voltage is large enough to split the water, generating oxygen at the Si solar cell side (for SS/n-i-p/sunlight structure) and hydrogen at the back, which is stainless steel side. There is no need to use a counter electrode or to make any wire connection. 3) It is being produced in large rolls of 3ft wide and up to 5000 ft long stainless steel web in a 25MW roll-to-roll production machine. Therefore it can be produced at a very low cost. After several years of research with many different kinds of material, we have developed promising transparent, conducting and corrosion resistant (TCCR) coating material; we carried out extensive research on oxygen and hydrogen generation catalysts, developed methods to make PEC electrode from production-grade a-Si solar cells; we have designed and tested various PEC module cases and carried out extensive outdoor testing; we were able to obtain a solar to hydrogen conversion efficiency (STH

  9. Empirical assessment of a prismatic daylight-redirecting window film in a full-scale office testbed

    SciTech Connect

    Thanachareonkit, Anothai; Lee, Eleanor S.; McNeil, Andrew

    2013-08-31

    Daylight redirecting systems with vertical windows have the potential to offset lighting energy use in deep perimeter zones. Microstructured prismatic window films can be manufactured using low-cost, roll-to-roll fabrication methods and adhered to the inside surface of existing windows as a retrofit measure or installed as a replacement insulating glass unit in the clerestory portion of the window wall. A clear film patterned with linear, 50-250 micrometer high, four-sided asymmetrical prisms was fabricated and installed in the south-facing, clerestory low-e, clear glazed windows of a full-scale testbed facility. Views through the film were distorted. The film was evaluated in a sunny climate over a two-year period to gauge daylighting and visual comfort performance. The daylighting aperture was small (window-towall ratio of 0.18) and the lower windows were blocked off to isolate the evaluation to the window film. Workplane illuminance measurements were made in the 4.6 m (15 ft) deep room furnished as a private office. Analysis of discomfort glare was conducted using high dynamic range imaging coupled with the evalglare software tool, which computes the daylight glare probability and other metrics used to evaluate visual discomfort. The window film was found to result in perceptible levels of discomfort glare on clear sunny days from the most conservative view point in the rear of the room looking toward the window. Daylight illuminance levels at the rear of the room were significantly increased above the reference window condition, which was defined as the same glazed clerestory window but with an interior Venetian blind (slat angle set to the cut-off angle), for the equinox to winter solstice period on clear sunny days. For partly cloudy and overcast sky conditions, daylight levels were improved slightly. To reduce glare, the daylighting film was coupled with a diffusing film in an insulating glazing unit. The diffusing film retained the directionality of the

  10. News Item

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    4, 2016 Time: 11:00 am Speaker: Anne Milasincic Andrews, UCLA Title: Chemical Neurotransmission and Functional Nanomaterials Location: 67-3111 Chemla Room Abstract: Numerous small molecules including amino acids, amino acid derivatives, and peptides have been identified as chemical neurotransmitters. Neuronal cells using different neurotransmitters have spatially distinct patterns that translate into highly heterogeneous chemistries in brain extracellular microenvironments. Accordingly,

  11. Optogalvanic intracavity quantitative detector and method for its use

    DOEpatents

    Zalewski, E.F.; Keller, R.A.; Apel, C.T.

    1983-09-06

    The disclosure relates to an optogalvanic intracavity detector and method for its use. Measurement is made of the amount of light absorbed by atoms, small molecules and ions in a laser cavity utilizing laser-produced changes in plasmas containing the same atoms, molecules, or ions. 6 figs.

  12. Optogalvanic intracavity quantitative detector and method for its use

    DOEpatents

    Zalewski, Edward F.; Keller, Richard A.; Apel, Charles T.

    1983-01-01

    The disclosure relates to an optogalvanic intracavity detector and method for its use. Measurement is made of the amount of light absorbed by atoms, small molecules and ions in a laser cavity utilizing laser-produced changes in plasmas containing the same atoms, molecules, or ions.

  13. Optogalvanic intracavity quantitative detector and method for its use

    DOEpatents

    Zalewski, E.F.; Keller, R.A.; Apel, C.T.

    1981-02-25

    The disclosure relates to an optogalvanic intracavity detector and method for its use. Measurement is made of the amount of light absorbed by atoms, small molecules and ions in a laser cavity utilizing laser-produced changes in plasmas containing the same atoms, molecules or ions.

  14. Disordered organic electronic materials based on non-benzenoid 1,6-methano[10]annulene rings

    DOEpatents

    Tovar, John D; Streifel, Benjamin C; Peart, Patricia A

    2014-10-07

    Conjugated polymers and small molecules including the nonplanar aromatic 1,6-methano[10]annulene ring structure along with aromatic subunits, such as diketopyrrolopyrrole, and 2,1,3-benzothiadiazole, substituted with alkyl chains in a "Tail In," "Tail Out," or "No Tail" regiochemistry are disclosed.

  15. Center for Advanced Solar Photophysics | Members

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    I will start by defining the class of materials of interest, which is solution-processed nanomaterials, including colloidally synthesized and free-standing plasma-fabricated...

  16. Shape-controlled narrow-gap SnTe nanostructures: From nanocubes...

    Office of Scientific and Technical Information (OSTI)

    colloidal semiconductor nanocrystals (NCs) is an important step toward the next generation of solution-processable photovoltaics, photodetectors, and thermoelectric devices. ...

  17. Switching phase separation mode by varying the hydrophobicity...

    Office of Scientific and Technical Information (OSTI)

    Switching phase separation mode by varying the hydrophobicity of polymer additives in solution-processed semiconducting small-moleculepolymer blends Citation Details In-Document ...

  18. Microsoft Word - P3HT_verticalchain bh

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    polymer thin films is of great interest for building more efficient solution processed organic electronic devices, e.g. photovoltaic (OPV) and light emitting (OLED) devices. ...

  19. Ultra-high Charge Carrier Mobility in an Organic Semiconductor...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    polymer thin films is of great interest for building more efficient solution processed organic electronic devices, e.g. photovoltaic (OPV) and light emitting (OLED) devices. ...

  20. Microsoft Word - Yang_seminar_012011.docx

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    8600 High performance organic and inorganic thin film solar cell via solution process Yang Yang Department of Materials Science and Engineering University of California, Los...

  1. New Research Projects > Research > The Energy Materials Center...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    - Coates Research Initiative - Abrua Research Initiative - Schlom New Research Projects Transport Dynamics and Carbonation Tolerance in Solution Processable Ionomers: Enabling a...

  2. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ConferenceEvent Journal Article Miscellaneous ... WA (United States) Idaho Chemical Processing Plant, Idaho ... PIM-1 as a Solution-Processable "Molecular Basket" for CO 2 ...

  3. Shape-controlled narrow-gap SnTe nanostructures: From nanocubes...

    Office of Scientific and Technical Information (OSTI)

    step toward the next generation of solution-processable photovoltaics, ... Type: Accepted Manuscript Journal Name: Journal of the American Chemical Society Additional Journal ...

  4. Profile for Hisato Yamaguchi

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Materials chemistry Carbon nanotubes Nanostructured ... and imaging Optics and fiber optics Transport ... Ions: The Key to All-Plastic, Solution-Processed ...

  5. Method of fabricating an optoelectronic device having a bulk heterojunction

    DOEpatents

    Shtein, Max (Ann Arbor, MI); Yang, Fan (Princeton, NJ); Forrest, Stephen R. (Princeton, NJ)

    2008-10-14

    A method of fabricating an optoelectronic device comprises: depositing a first layer having protrusions over a first electrode, in which the first layer comprises a first organic small molecule material; depositing a second layer on the first layer such that the second layer is in physical contact with the first layer; in which the smallest lateral dimension of the protrusions are between 1 to 5 times the exciton diffusion length of the first organic small molecule material; and depositing a second electrode over the second layer to form the optoelectronic device. A method of fabricating an organic optoelectronic device having a bulk heterojunction is also provided and comprises: depositing a first layer with protrusions over an electrode by organic vapor phase deposition; depositing a second layer on the first layer where the interface of the first and second layers forms a bulk heterojunction; and depositing another electrode over the second layer.

  6. Increasing the efficiency of organic solar cells by photonic and electrostatic-field enhancements

    SciTech Connect

    Nalwa, Kanwar

    2011-01-01

    Organic photovoltaic (OPV) technology is an attractive solar-electric conversion paradigm due to the promise of low cost roll-to-roll production and amenability to flexible substrates. Power conversion efficiency (PCE) exceeding 7% has recently been achieved. OPV cells suffer from low charge carrier mobilities of polymers, leading to recombination losses, higher series resistances and lower fill-factors. Thus, it is imperative to develop fabrication methodologies that can enable efficient optical absorption in films thinner than optical absorption length. Active layers conformally deposited on light-trapping, microscale textured, grating-type surfaces is one possible approach to achieve this objective. In this study, 40% theoretical increase in photonic absorption over flat OPVs is shown for devices with textured geometry by the simulation results. For verifying this theoretical result and improving the efficiency of OPVs by light trapping, OPVs were fabricated on grating-type textured substrates possessing t pitch and -coat PV active-layer on these textured substrates led to over filling of the valleys and shunts at the crest, which severely affected the performance of the resultant PV devices. Thus, it is established that although the optical design is important for OPV performance but the potential of light trapping can only be effectively tapped if the textures are amenable for realizing a conformal active layer. It is discovered that if the height of the underlying topographical features is reduced to sub-micron regime (e.g. 300 nm) and the pitch is increased to more than a micron (e.g. 2 μm), the textured surface becomes amenable to coating a conformal PV active-layer. The resultant PV cells showed 100% increase in average light absorption near the band edge due to trapping of higher wavelength photons, and 20% improvement in power conversion efficiency as compared with the flat PV cell. Another factor that severely limits the performance of OPVs is

  7. Interfacial Behavior of Polymers: Using Interfaces to Manipulate Polymers

    SciTech Connect

    Russell, Thomas P.

    2015-02-26

    most rapid solvent removal process drives the copolymer film to below its glass transition temperature, freezing in the lateral order. We have quantitatively described the ordering and the parameters influencing the disruption of the ordering in these studies. We have also used e-beam lithography to generate shallow trench patterns on planar surface where the topographic patterning provides an additional constraint on the self-assembly of the block copolymer. The pitches of the trenches were varied while the depth and the trench width of patterns were maintained by constant at 89 and 30nm, respectively. Unidirectional PS-b-PEO line patterns over large area on the shallow trench patterns were obtained by solvent vapor annealing. We extended the solvent annealing process to an in-line coating process using a mini-slot die coater developed in our laboratories. This coater uses minimal materials with operating parameters that can mimic actual industrial processing on a roll-to-roll line. Most important, with this mini-slot die coater, it could also characterize the structure of the film using grazing incidence x-ray scattering. Using the fundamental characterization of the ordering of the block copolymers, we could optimize the coating conditions to enhance lateral ordering of block copolymer in a well-defined manner. The structures produced in this process are directly transferable to flexible electronics where the arrays of block copolymer microdomains can be used for the fabrication of nanostructured components. We have also controlled the orientation of BCP microdomains at the air and substrate interfaces by manipulating the interfacial interactions with selective solvents. This has enabled us to generate nanoporous membranes where the size of the pores is dictated by the size of the bloc copolymer microdomains. We have produced robust nanoporous membranes that can tolerate high pressures and have high throughput using thick films of block copolymers. Exceptional size

  8. Adaptive Liquid Crystal Windows

    SciTech Connect

    Taheri, Bahman; Bodnar, Volodymyr

    2011-12-31

    consumption by ALCWs allows for on-board power electronics for automatic matching of transmission through windows to varying climate conditions without drawing the power from the power grid. ALCWs are capable of transmitting more sunlight in winters to assist in heating and less sunlight in summers to minimize overheating. As such, they can change the window from being a source of energy loss to a source of energy gain. In addition, the scalable AMIs roll-to-roll process, proved by making 1ft 1ftALCW prototype panels, allows for cost-effective production of large-scale window panels along with capability to change easily their color and shape. In addition to architectural glazing in houses and commercial buildings, ALCWs can be used in other applications where control of sunlight is needed, such as green houses, used by commercial produce growers and botanical gardens, cars, aircrafts, etc.

  9. CEEM Final Technical Report

    SciTech Connect

    Bowers, John

    2014-11-26

    The mission of the Center for Energy Efficient Materials (CEEM) was to serve the Department of Energy and the nation as a center of excellence dedicated to advancing basic research in nano-structured materials and devices for applications to solar electricity, thermoelectric conversion of waste heat to electricity, and solidstate lighting. The foundation of CEEM was based on the unique capabilities of UCSB and its partner institutions to control, synthesize, characterize, model, and apply materials at the nanoscale for more efficient sustainable energy resources. This unique expertise was a key source of the synergy that unified the research of the Center. Although the Center’s focus was basic research, It’s longer-term objective has been to transfer new materials and devices into the commercial sector where they will have a substantial impact on the nation’s need for efficient sustainable energy resources. As one measure of the impact of the Center, two start-up companies were formed based on its research. In addition, Center participants published a total of 210 archival journal articles, of which 51 were exclusively sponsored by the DOE grant. The work of the Center was structured around four specific tasks: Organic Solar Cells, Solid-State Lighting, Thermoelectrics, and High Efficiency Multi-junction Photovoltaic devices. A brief summary of each follows – detailed descriptions are in Sections 4 & 5 of this report. Research supported through CEEM led to an important shift with respect to the choice of materials used for the fabrication of solution deposited organic solar cells. Solution deposition opens the opportunity to manufacture solar cells via economically-viable high throughput tools, such as roll to roll printing. Prior to CEEM, most organic semiconductors utilized for this purpose involved polymeric materials, which, although they can form thin films reliably, suffer from batch to batch variations due to the statistical nature of the chemical

  10. Development of low-cost technology for the next generation of high efficiency solar cells composed of earth abundant elements

    SciTech Connect

    Agrawal, Rakesh

    2014-09-28

    The development of renewable, affordable, and environmentally conscious means of generating energy on a global scale represents a grand challenge of our time. Due to the “permanence” of radiation from the sun, solar energy promises to remain a viable and sustainable power source far into the future. Established single-junction photovoltaic technologies achieve high power conversion efficiencies (pce) near 20% but require complicated manufacturing processes that prohibit the marriage of large-scale throughput (e.g. on the GW scale), profitability, and quality control. Our approach to this problem begins with the synthesis of nanocrystals of semiconductor materials comprising earth abundant elements and characterized by material and optoelectronic properties ideal for photovoltaic applications, namely Cu2ZnSn(S,Se)4 (CZTSSe). Once synthesized, such nanocrystals are formulated into an ink, coated onto substrates, and processed into completed solar cells in such a way that enables scale-up to high throughput, roll-to-roll manufacturing processes. This project aimed to address the major limitation to CZTSSe solar cell pce’s – the low open-circuit voltage (Voc) reported throughout literature for devices comprised of this material. Throughout the project significant advancements have been made in fundamental understanding of the CZTSSe material and device limitations associated with this material system. Additionally, notable improvements have been made to our nanocrystal based processing technique to alleviate performance limitations due to the identified device limitations. Notably, (1) significant improvements have been made in reducing intra- and inter-nanoparticle heterogeneity, (2) improvements in device performance have been realized with novel cation substitution in Ge-alloyed CZTGeSSe absorbers, (3) systematic analysis of absorber sintering has been conducted to optimize the selenization process for large grain CZTSSe absorbers, (4) novel electrical

  11. Structure of Chinese Herbal-based Medicine Captured by ATP on a Human tRNA

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Synthetase | Stanford Synchrotron Radiation Lightsource Structure of Chinese Herbal-based Medicine Captured by ATP on a Human tRNA Synthetase Thursday, October 31, 2013 For thousands of years the Chinese have been using the Chang Shan herb (Dichroa febrifuga Lour) to treat malaria-induced fevers (1). The active ingredient in the herb was eventually shown to be a small molecule known as febrifugine. A halogenated derivative of febrifugine, called halofuginone (HF), has been tested in clinical

  12. Draft genome sequence of the dimorphic yeast Yarrowia lipolytica, strain W29

    SciTech Connect

    Pomraning, Kyle R.; Baker, Scott E.

    2015-11-25

    Here we present the draft genome sequence of the dimorphic ascomycete yeast Yarrowia lipolytica strain W29 (ATCC20460TM). Y. lipolytica is a commonly employed model for industrial production of lipases, small molecules, and more recently for its ability to accumulate lipids. It has also been used to study genome evolution in yeast and filamentous fungi due to its position as an early diverging branch of the subphylum Sacchromycotina.

  13. Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors

    DOEpatents

    Liu, Yi; He, Bo; Pun, Andrew

    2016-04-19

    A novel electron acceptor based on bay-annulated indigo (BAI) was synthesized and used for the preparation of a series of high performance donor-acceptor small molecules and polymers. The resulting materials possess low-lying LUMO energy level and small HOMO-LUMO gaps, while their films exhibited high crystallinity upon thermal treatment, commensurate with high field effect mobilities and ambipolar transfer characteristics.

  14. Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors

    DOEpatents

    Liu, Yi; He, Bo; Pun, Andrew

    2015-11-24

    A novel electron acceptor based on bay-annulated indigo (BAI) was synthesized and used for the preparation of a series of high performance donor-acceptor small molecules and polymers. The resulting materials possess low-lying LUMO energy level and small HOMO-LUMO gaps, while their films exhibited high crystallinity upon thermal treatment, commensurate with high field effect mobilities and ambipolar transfer characteristics.

  15. 2007 Inorganic Reaction Mechanisms Gordon Research Conference-February 18-23

    SciTech Connect

    Andreja Bakac Nancy Ryan Gray

    2008-01-01

    This conference focuses on kinetic, mechanistic, and thermodynamic studies of reactions that play a role in fields as diverse as catalysis, energy, bioinorganic chemistry, green chemistry, organometallics, and activation of small molecules (oxygen, nitrogen, carbon monoxide, carbon dioxide, alkanes). Participants from universities, industry, and national laboratories present results and engage in discussions of pathways, intermediates, and outcome of various reactions of inorganic, organic, coordination, organometallic, and biological species. This knowledge is essential for rational development and design of novel reactions, compounds, and catalysts.

  16. Organic Photovoltaics | Center for Energy Efficient Materials

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Organic Photovoltaics As an overarching goal, the CEEM OPV group seeks to understand conjugated polymer and small molecule semiconductor blends that function as the active layer in solar cell devices. The effort brings together a cohesive and mutually complementary set of experts to understand what may appear at first sight to be unrelated phenomena. Indeed, the collective CEEM OPV effort very recently led to the design, processing, structural characterization, theoretical understanding and

  17. Atomic, molecular, and nuclear quantum dynamics and control in (strong)

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    visible to x-ray (laser) fields | Stanford Synchrotron Radiation Lightsource Atomic, molecular, and nuclear quantum dynamics and control in (strong) visible to x-ray (laser) fields Wednesday, July 20, 2016 - 3:00pm SLAC, Redtail Hawk Conference Room 108A Speaker: Thomas Pfeifer, MPIK Heidelberg Program Description Electrons bound in atoms and small molecules represent some of the most fundamental quantum systems. These systems are so well known and reliable that they serve as optical

  18. Matrix Infrared Spectroscopic and Computational Investigations of Novel Small Uranium Containing Molecules - Final Technical Report

    SciTech Connect

    Andrews, Lester

    2014-10-17

    Direct reactions of f-element uranium, thorium and lanthanide metal atoms were investigated with small molecules. These metal atoms were generated by laser ablation and mixed with the reagent molecules then condensed with noble gases at 4K. The products were analyzed by absorption of infrared light to measure vibrational frequencies which were confirmed by quantum chemical calculations. We have learned more about the reactivity of uranium atoms with common molecules, which will aid in the develolpment of further applications of uranium.

  19. Reddy, J. S.; Kale, T. S.; Balaji, G.; Chandrasekaran, A.; Thayumanavan, S*

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Reddy, J. S.; Kale, T. S.; Balaji, G.; Chandrasekaran, A.; Thayumanavan, S* Effect of Fluorinated Substituents on Electro- chemical and Charge Transport Properties Reddy, J. S.et al. J. Phys. Chem. Lett. 2011, 2, 648-654. (DOI: 10.1021/jz200126s) Small molecule semiconductors based on cyclopenta-dithiophene (CPD) hole conductors were electronically "tuned" by incorporation of electron withdrawing groups, including fluorinated substituents. Conversion of an otherwise p-type material

  20. Factors influencing photocurrent generation in organic bulk heterojunction

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    solar cells: interfacial energetics and blend microstructure | MIT-Harvard Center for Excitonics Factors influencing photocurrent generation in organic bulk heterojunction solar cells: interfacial energetics and blend microstructure April 29, 2009 at 3pm/36-428 Jenny Nelson Department of Physics Imperial College London jenny-nelson_000 abstract: The efficiency of photocurrent generation in conjugated polymer:small molecule blend solar is strongly influenced both by the energy level alignment

  1. Stability Breakout Session

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Stability Breakout Session I Chemical Stability * What are the Reactions? i. Products must be identified (loss of IEC is not enough) ii. Establish reaction mechanism(s) iii. Measure the kinetics II Reaction of membrane with OH - /HCO 3 - /CO 3 2- at various hydration levels - nucleophilicity and basicity of anion species i. Cations a) Small molecule analogues b) Effects of hydration state and temperature c) Cation design R 4 N + ???? Families of cations * Ammoniums * Guanadiniums * Sulfoniums *

  2. VFP Research Projects | The Ames Laboratory

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Research Projects Ames Lab provides hands-on research opportunities in materials science in the following research areas: Mathematical modeling of the aptamers and its effect on small molecule transport into the cell (Marit Nilsen-Hamilton) Synthesis and Characterization of a Hafnium Derivative of the MOF UiO-66-NH2 and its use in Biomass Related Catalysis (Wenyu Huang) Reliable Nanomanufacturing of Ge-Sn Alloys for Solar Energy Conversion (Javier Vela) Past Programs

  3. Workshop: Synchrotron Applications in Chemical Catalysis | Stanford

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Synchrotron Radiation Lightsource Synchrotron Applications in Chemical Catalysis Tuesday, October 25, 2011 - 8:00am 2011 SSRL/LCLS Annual Users Conference This workshop, part of the 2011 SSRL/LCLS Annual Users Conference, will focus on understanding processes in homogeneous (both biological and small molecule) and heterogeneous catalysis, using synchrotron-based methods. The workshop will cover more traditional applications (using XANES and EXAFS), as well as applications of XES, RIXS and

  4. Slide 1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    predict binding enthalpies of 14 small molecules in 10 unique isostructural metal-organic frameworks, M- MOF-74. 140 systems were elucidated quantitatively in the most rigorous and extensive ab initio study to date. Significance and Impact Newly-proposed MOFs and new understanding of MOF-adsorbate binding chemistry could lead to efficient and inexpensive removal of CO2 and other contaminants from gases mixtures (e.g. flue gas). Research Details - Our calculations employ a nonlocal van der Waals

  5. Structure of Molecular Thin Films for Organic Electronics | Stanford

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Synchrotron Radiation Lightsource Structure of Molecular Thin Films for Organic Electronics Friday, April 6, 2012 - 1:00pm SSRL Conference Room 137-322 Bert Nickel, Physics Faculty and CeNS, Ludwig-Maximilians-University, München Thin films made out of conjugated small molecules and polymers exhibit very interesting semiconducting properties. While some applications such as light emitting diodes (OLED) are already on the market, other application such as solar cells, integrated circuits,

  6. 1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Biosecurity and Health Science and technology designed to battle pathogens Read caption + Harshini Mukundan (left) watches as fellow Los Alamos bioscientist Elizabeth Hong- Geller loads a vertical electrophoresis gel, used to separate proteins and small molecules. This technique is useful for developing improved methods to detect pathogens. Overview of Research and Highlights Los Alamos scientists are developing science and technology to improve pathogen detection, create better therapeutics,

  7. Meta-analysis of global metabolomics and proteomics data to link alterations with phenotype

    DOE PAGES [OSTI]

    Patti, Gary J.; Tautenhahn, Ralf; Fonslow, Bryan R.; Cho, Yonghoon; Deutschbauer, Adam; Arkin, Adam; Northen, Trent; Siuzdak, Gary

    2011-01-01

    Global metabolomics has emerged as a powerful tool to interrogate cellular biochemistry at the systems level by tracking alterations in the levels of small molecules. One approach to define cellular dynamics with respect to this dysregulation of small molecules has been to consider metabolic flux as a function of time. While flux measurements have proven effective for model organisms, acquiring multiple time points at appropriate temporal intervals for many sample types (e.g., clinical specimens) is challenging. As an alternative, meta-analysis provides another strategy for delineating metabolic cause and effect perturbations. That is, the combination of untargeted metabolomic data from multiplemore » pairwise comparisons enables the association of specific changes in small molecules with unique phenotypic alterations. We recently developed metabolomic software called metaXCMS to automate these types of higher order comparisons. Here we discuss the potential of metaXCMS for analyzing proteomic datasets and highlight the biological value of combining meta-results from both metabolomic and proteomic analyses. The combined meta-analysis has the potential to facilitate efforts in functional genomics and the identification of metabolic disruptions related to disease pathogenesis.« less

  8. Yining Zeng | Bioenergy | NREL

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Featured Publications "Square-Centimeter Solution-Processed Planar CH3NH3PbI3 Perovskite Solar Cells with Efficiency Exceeding 15%," http:dx.doi.org10.1002adma.201502586 (2015) ...

  9. Structure of All-Polymer Solar Cells Impedes Efficiency

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    ... Solution-processed organic solar cells are attracting substantial, world-wide attention due to their potential as a low-cost photovoltaic technology. The active thin layer in such ...

  10. High Efficiency CdTe Ink-Based Solar Cells Using Nanocrystals (Fact Sheet)

    SciTech Connect

    Not Available

    2015-01-01

    This NREL Highlight is being developed for the 2015 February Alliance S&T Board meeting and describes a solution-processable ink to produce high-efficiency solar cells using low temperature and simple processing.

  11. Polymer Solar Cells: New Materials, 3D Morphology, and Tandem...

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    on the quantum and energy efficiency by which photons from the sun are absorbed and can be converted ... Using this strategy a solution processed polymer tandem cell with an ...

  12. Multi-layer articles and methods of making same

    DOEpatents

    Fritzemeier, Leslie G.; Zhang, Wei; Palm, Walter C.; Rupich, Martin W.

    2005-05-17

    The invention relates to superconductor articles, and compositions and methods for making superconductor articles. The methods can include using a precursor solution having a relatively small concentration of total free acid. The articles can include more than one layer of superconductor material in which at least one layer of superconductor material can be formed by a solution process, such as a solution process involving the use of metalorganic precursors.

  13. Quantifying Stochastic Noise in Cultured Circadian Reporter Cells

    DOE PAGES [OSTI]

    John, Peter C.; Doyle, III, Francis J.

    2015-11-20

    We report that stochastic noise at the cellular level has been shown to play a fundamental role in circadian oscillations, influencing how groups of cells entrain to external cues and likely serving as the mechanism by which cell-autonomous rhythms are generated. Despite this importance, few studies have investigated how clock perturbations affect stochastic noise—even as increasing numbers of high-throughput screens categorize how gene knockdowns or small molecules can change clock period and amplitude. This absence is likely due to the difficulty associated with measuring cell-autonomous stochastic noise directly, which currently requires the careful collection and processing of single-cell data. Inmore » this study, we show that the damping rate of population-level bioluminescence recordings can serve as an accurate measure of overall stochastic noise, and one that can be applied to future and existing high-throughput circadian screens. Using cell-autonomous fibroblast data, we first show directly that higher noise at the single-cell results in faster damping at the population level. Next, we show that the damping rate of cultured cells can be changed in a dose-dependent fashion by small molecule modulators, and confirm that such a change can be explained by single-cell noise using a mathematical model. We further demonstrate the insights that can be gained by applying our method to a genome-wide siRNA screen, revealing that stochastic noise is altered independently from period, amplitude, and phase. Finally, we hypothesize that the unperturbed clock is highly optimized for robust rhythms, as very few gene perturbations are capable of simultaneously increasing amplitude and lowering stochastic noise. Ultimately, this study demonstrates the importance of considering the effect of circadian perturbations on stochastic noise, particularly with regard to the development of small-molecule circadian therapeutics.« less

  14. Tellurium-Containing Conjugated Materials for Solar Cells: From Sulfur to Tellurium

    SciTech Connect

    Park Y. S.; Kale, T.; Wu, Q.; Ocko, B.M.; Black, C.T., Grubbs, R.B.

    2013-04-03

    A series of diketopyrrolopyrrole(DPP)-based small molecules have been synthesized by palladium-catalyzed coupling reactions. Electron-donating moieties (benzothiophene, benzoselenophene, and benzotellurophene) are bridged by an electron-withdrawing DPP unit to generate donor-acceptor-donor (D-A-D) type molecules. We observe red-shifts in absorption spectra of these compounds by varying heteroatoms from sulfur to tellurium. In bulk heterojunction solar cells with [6,6]phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor, we obtain power conversion efficiencies of 2.4% (benzothiophene), 4.1% (benzoselenophene), and 3.0% (benzotellurophene), respectively.

  15. Photothermal Superheating of Water with Ion-Implanted Silicon Nanowires

    SciTech Connect

    Roder, Paden B.; Manandhar, Sandeep; Smith, Bennett E.; Zhou, Xuezhe; Shutthanandan, V.; Pauzauskie, Peter J.

    2015-07-21

    Nanoparticle-mediated photothermal (PT) cancer therapy has been a major focus in nanomedicine due to its potential as an effective, non-invasive, and targeted alternative to traditional cancer therapy based on small-molecule pharmaceuticals[1,2]. Gold nanocrystals have been a primary focus of PT research[3], which can be attributed to their size tunability[4], well understood conjugation chemistry[5], and efficient absorption of NIR radiation in the tissue transparency window (800 nm – 1 μm) due to their size-dependent localized surface plasmon resonances[6].

  16. Nanofiltration across Defect-Sealed Nanoporous Monolayer Graphene

    SciTech Connect

    O'Hern, Sean C.; Jang, Doojoon; Bose, Suman; Idrobo Tapia, Juan Carlos; Song, Yi; Laoui, Tahar; Kong, Jing; Karnik, Rohit

    2015-04-27

    Monolayer nanoporous graphene represents an ideal membrane for molecular separations, but its practical realization is impeded by leakage through defects in the ultrathin graphene. Here, we report a multiscale leakage-sealing process that exploits the nonpolar nature and impermeability of pristine graphene to selectively block defects, resulting in a centimeter-scale membrane that can separate two fluid reservoirs by an atomically thin layer of graphene. After introducing subnanometer pores in graphene, the membrane exhibited rejection of multivalent ions and small molecules and water flux consistent with prior molecular dynamics simulations. The results indicate the feasibility of constructing defect-tolerant monolayer graphene membranes for nanofiltration, desalination, and other separation processes.

  17. Two glass transitions in miscible polymer blends?

    SciTech Connect

    Dudowicz, Jacek; Freed, Karl F.; Douglas, Jack F.

    2014-06-28

    In contrast to mixtures of two small molecule fluids, miscible binary polymer blends often exhibit two structural relaxation times and two glass transition temperatures. Qualitative explanations postulate phenomenological models of local concentration enhancements due to chain connectivity in ideal, fully miscible systems. We develop a quantitative theory that explains qualitative trends in the dynamics of real miscible polymer blends which are never ideal mixtures. The theory is a synthesis of the lattice cluster theory of blend thermodynamics, the generalized entropy theory for glass-formation in polymer materials, and the Kirkwood-Buff theory for concentration fluctuations in binary mixtures.

  18. X-ray structures of checkpoint kinase 2 in complex with inhibitors that target its gatekeeper-dependent hydrophobic pocket

    SciTech Connect

    Lountos, George T.; Jobson, Andrew G.; Tropea, Joseph E.; Self, Christopher R.; Zhang, Guangtao; Pommier, Yves; Shoemaker, Robert H.; Waugh, David S.

    2012-09-17

    The serine/threonine checkpoint kinase 2 (Chk2) is an attractive molecular target for the development of small molecule inhibitors to treat cancer. Here, we report the rational design of Chk2 inhibitors that target the gatekeeper-dependent hydrophobic pocket located behind the adenine-binding region of the ATP-binding site. These compounds exhibit IC{sub 50} values in the low nanomolar range and are highly selective for Chk2 over Chk1. X-ray crystallography was used to determine the structures of the inhibitors in complex with the catalytic kinase domain of Chk2 to verify their modes of binding.

  19. Correlated electron pseudopotentials for 3d-transition metals

    SciTech Connect

    Trail, J. R. Needs, R. J.

    2015-02-14

    A recently published correlated electron pseudopotentials (CEPPs) method has been adapted for application to the 3d-transition metals, and to include relativistic effects. New CEPPs are reported for the atoms Sc ? Fe, constructed from atomic quantum chemical calculations that include an accurate description of correlated electrons. Dissociation energies, molecular geometries, and zero-point vibrational energies of small molecules are compared with all electron results, with all quantities evaluated using coupled cluster singles doubles and triples calculations. The CEPPs give better results in the correlated-electron calculations than Hartree-Fock-based pseudopotentials available in the literature.

  20. Isomer-sensitive deboronation in reductive aminations of aryl boronic acids

    SciTech Connect

    Jones, Brad Howard; Wheeler, David R.; Wheeler, Jill S.; Miller, Lance Lee; Alam, Todd M.; Spoerke, Erik David

    2015-09-05

    Deboronation is observed during the reductive amination of formylphenylboronic acid (FPBA) to the amine termini and side chains of peptides. This deboronation is sensitive to the isomerism of the boronic acid (BA), with ortho-FPBA yielding complete deboronation in the preparation of an N-terminally-modified dipeptide. The observed behavior is also clearly mediated by the chemical identity of the amine substrate. These results reveal a previously undocumented subtlety of BA functionalization and highlight the importance of thorough spectroscopic characterization in the preparation of peptide and small molecule BAs.

  1. Isomer-sensitive deboronation in reductive aminations of aryl boronic acids

    DOE PAGES [OSTI]

    Jones, Brad Howard; Wheeler, David R.; Wheeler, Jill S.; Miller, Lance Lee; Alam, Todd M.; Spoerke, Erik David

    2015-09-05

    Deboronation is observed during the reductive amination of formylphenylboronic acid (FPBA) to the amine termini and side chains of peptides. This deboronation is sensitive to the isomerism of the boronic acid (BA), with ortho-FPBA yielding complete deboronation in the preparation of an N-terminally-modified dipeptide. The observed behavior is also clearly mediated by the chemical identity of the amine substrate. These results reveal a previously undocumented subtlety of BA functionalization and highlight the importance of thorough spectroscopic characterization in the preparation of peptide and small molecule BAs.

  2. Spectroscopic and dynamical studies of highly energized small polyatomic molecules

    SciTech Connect

    Field, R.W.; Silbey, R.J.

    1993-12-01

    The authors have initiated a program to perform spectroscopic and dynamic studies of small molecules. Large amplitude motions in excited acetylene were discussed along with plans to record the dispersed fluorescence (DF) and the stimulated emission pumping (SEP) spectra. SEP spectra were reported for the formyl radical. A Fourier transform spectrometer was discussed with respect to its ability to probe the structure of radicals. This instrument is capable of performing studies using various techniques such as magnetic rotation spectroscopy and sub-Doppler sideband-OODR Zeman (SOODRZ) spectroscopy.

  3. VUV studies of molecular photofragmentation dynamics

    SciTech Connect

    White, M.G.

    1993-12-01

    State-resolved, photoion and photoelectron methods are used to study the neutral fragmentation and ionization dynamics of small molecules relevant to atmospheric and combustion chemistry. Photodissociation and ionization are initiated by coherent VUV radiation and the fragmentation dynamics are extracted from measurements of product rovibronic state distributions, kinetic energies and angular distributions. The general aim of these studies is to investigate the multichannel interactions between the electronic and nuclear motions which determine the evolution of the photoexcited {open_quotes}complex{close_quotes} into the observed asymptotic channels.

  4. Kinetic data base for combustion modeling

    SciTech Connect

    Tsang, W.; Herron, J.T.

    1993-12-01

    The aim of this work is to develop a set of evaluated rate constants for use in the simulation of hydrocarbon combustion. The approach has been to begin with the small molecules and then introduce larger species with the various structural elements that can be found in all hydrocarbon fuels and decomposition products. Currently, the data base contains most of the species present in combustion systems with up to four carbon atoms. Thus, practically all the structural grouping found in aliphatic compounds have now been captured. The direction of future work is the addition of aromatic compounds to the data base.

  5. Recovery of Uranium from Seawater: Preparation and Development of Polymer-Supported Extractants

    SciTech Connect

    Spiro, Alexandratos

    2013-12-01

    A new series of polymer-supported extractants is proposed for the removal and recovery of uranium from seawater. The objective is to produce polymers with improved stability, loading capacity, and sorption kinetics compared to what is found with amidoximes. The target ligands are diphosphonates and aminomethyldiphosphonates. Small molecule analogues, especially of aminomethyldiphos-phonates, have exceptionally high stability constants for the uranyl ion. The polymeric diphosphonates will have high affinities due to their ability to form six-membered rings with the uranyl ion while the aminomethyldiphosphonates may have yet higher affinities due to possible tridentate coordination and their greater acidity. A representative set of the polymers to be prepared are indicated.

  6. Method and apparatus for combinatorial chemistry

    DOEpatents

    Foote, Robert S.

    2012-06-05

    A method and apparatus are provided for performing light-directed reactions in spatially addressable channels within a plurality of channels. One aspect of the invention employs photoactivatable reagents in solutions disposed into spatially addressable flow streams to control the parallel synthesis of molecules immobilized within the channels. The reagents may be photoactivated within a subset of channels at the site of immobilized substrate molecules or at a light-addressable site upstream from the substrate molecules. The method and apparatus of the invention find particularly utility in the synthesis of biopolymer arrays, e.g., oligonucleotides, peptides and carbohydrates, and in the combinatorial synthesis of small molecule arrays for drug discovery.

  7. Method and apparatus for combinatorial chemistry

    DOEpatents

    Foote, Robert S.

    2007-02-20

    A method and apparatus are provided for performing light-directed reactions in spatially addressable channels within a plurality of channels. One aspect of the invention employs photoactivatable reagents in solutions disposed into spatially addressable flow streams to control the parallel synthesis of molecules immobilized within the channels. The reagents may be photoactivated within a subset of channels at the site of immobilized substrate molecules or at a light-addressable site upstream from the substrate molecules. The method and apparatus of the invention find particularly utility in the synthesis of biopolymer arrays, e.g., oligonucleotides, peptides and carbohydrates, and in the combinatorial synthesis of small molecule arrays for drug discovery.

  8. 2015 Publications Resulting from the Use of NERSC Resources

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    5 2015 Publications Resulting from the Use of NERSC Resources On their Allocation Year 2016 ERCAP Request Forms Principal Investigators reported 2,078 refereed publications (published or in press) for the preceding 12 months, based on using, at least in part, NERSC resources. Carter Abney Abney, C.W.; Mayes, R. T.; Piechowicz, M.; Lin, Z.; Bryantsev, V.S.; Veith, G.M.; Dai, S.; & Lin, W. "XAFS Investigation of Polyamidoxime-Bound Uranyl Contests the Paradigm from Small Molecule

  9. Thermotropic Uniaxial and Biaxial Nematic and Smectic Phases in Bent-Core Mesogens

    SciTech Connect

    Prasad, Venna; Kang, Shin-Woong; Suresh, K.A.; Joshi, Leela; Wang, Qingbing; Kumar, Satyendra

    2010-07-20

    Two azo substituted achiral bent-core mesogens have been synthesized. Optical polarizing microscopy and synchrotron X-ray scattering studies of both compounds reveal the existence of the thermotropic uniaxial and biaxial nematic and three smectic phases at different temperatures in these single component small molecule systems. The transition from the uniaxial to biaxial nematic phase is confirmed to be second order. The transitions from the biaxial nematic to the underlying smectic phase and between the smectic phases have barely discernible heat capacity signatures and thus are also second order.

  10. 1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Counting small RNA in disease-causing organisms June 17, 2013 Small molecules of RNA (tens to hundreds of nucleotides in length) play a key regulatory role in bacteria. Due to their small size, directly measuring the number of small RNA (sRNA) present in a single bacterium has proven so far to be an impossible task. Standard methods of measuring the number of specific nucleic acid molecules present in a single cell suffer from too much background and false positives when scientists attempt to

  11. TFB:TPDSi2 interfacial layer usable in organic photovoltaic cells

    SciTech Connect

    Marks, Iobin J.; Hains, Alexander W.

    2011-02-15

    The present invention, in one aspect, relates to a solar cell. In one embodiment, the solar cell includes an anode; an active organic layer comprising an electron-donating organic material and an electron-accepting organic material; and an interfacial layer formed between the anode and active organic layer, where the interfacial layer comprises a hole-transporting polymer characterized with a hole-mobility higher than that of the electron-donating organic material in the active organic layer, and a small molecule that has a high hole-mobility and is capable of crosslinking on contact with air.

  12. Structure of the Brachydanio Rerio Polo-Like Kinase 1 (Plk1) Catalytic Domain in Complex With An Extended Inhibitor Targeting the Adaptive Pocket of the Enzyme

    SciTech Connect

    Elling, R.A.; Fucini, R.V.; Hanan, E.J.; Barr, K.J.; Zhu, J.; Paulvannan, K.; Yang, W.; Romanowski, M.J.

    2009-05-18

    Polo-like kinase 1 (Plk1) is a member of the Polo-like kinase family of serine/threonine kinases involved in the regulation of cell-cycle progression and cytokinesis and is an attractive target for the development of anticancer therapeutics. The catalytic domain of this enzyme shares significant primary amino-acid homology and structural similarity with another mitotic kinase, Aurora A. While screening an Aurora A library of ATP-competitive compounds, a urea-containing inhibitor with low affinity for mouse Aurora A but with submicromolar potency for human and zebrafish Plk1 (hPlk1 and zPlk1, respectively) was identified. A crystal structure of the zebrafish Plk1 kinase domain-inhibitor complex reveals that the small molecule occupies the purine pocket and extends past the catalytic lysine into the adaptive region of the active site. Analysis of the structures of this protein-inhibitor complex and of similar small molecules cocrystallized with other kinases facilitates understanding of the specificity of the inhibitor for Plk1 and documents for the first time that Plk1 can accommodate extended ATP-competitive compounds that project toward the adaptive pocket and help the enzyme order its activation segment.

  13. Method of fabricating an optoelectronic device having a bulk heterojunction

    DOEpatents

    Shtein, Max (Princeton, NJ); Yang, Fan (Princeton, NJ); Forrest, Stephen R. (Princeton, NJ)

    2008-09-02

    A method of fabricating an organic optoelectronic device having a bulk heterojunction comprises the steps of: depositing a first layer over a first electrode by organic vapor phase deposition, wherein the first layer comprises a first organic small molecule material; depositing a second layer on the first layer such that the second layer is in physical contact with the first layer, wherein the interface of the second layer on the first layer forms a bulk heterojunction; and depositing a second electrode over the second layer to form the optoelectronic device. In another embodiment, a first layer having protrusions is deposited over the first electrode, wherein the first layer comprises a first organic small molecule material. For example, when the first layer is an electron donor layer, the first electrode is an anode, the second layer is an electron acceptor layer, and the second electrode is a cathode. As a further example, when the first layer is an electron acceptor layer, the first electrode is a cathode, the second layer is an electron donor layer, and the second electrode is an anode.

  14. Structural Analysis of the Regulatory Domain of ExsA, a Key Transcriptional Regulator of the Type Three Secretion System in Pseudomonas aeruginosa

    SciTech Connect

    Shrestha, Manisha; Xiao, Yi; Robinson, Howard; Schubot, Florian D.

    2015-08-28

    Pseudomonas aeruginosa employs a type three secretion system to facilitate infections in mammalian hosts. The operons encoding genes of structural components of the secretion machinery and associated virulence factors are all under the control of the AraC-type transcriptional activator protein, ExsA. ExsA belongs to a unique subfamily of AraC-proteins that is regulated through protein-protein contacts rather than small molecule ligands. Prior to infection, ExsA is inhibited through a direct interaction with the anti-activator ExsD. To activate ExsA upon host cell contact this interaction is disrupted by the anti-antiactivator protein ExsC. Here we report the crystal structure of the regulatory domain of ExsA, which is known to mediate ExsA dimerization as well as ExsD binding. The crystal structure suggests two models for the ExsA dimer. Both models confirmed the previously shown involvement of helix α-3 in ExsA dimerization but one also suggest a role for helix α-2. These structural data are supported by the observation that a mutation in α-2 greatly diminished the ability of ExsA to activate transcription in vitro. Lastly, additional in vitro transcription studies revealed that a conserved pocket, used by AraC and the related ToxT protein for the binding of small molecule regulators, although present in ExsA is not involved in binding of ExsD.

  15. Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

    SciTech Connect

    Dudowicz, Jacek Freed, Karl F.; Douglas, Jack F.

    2015-10-07

    Standard Flory-Huggins (FH) theory is utilized to describe the enigmatic cosolvency and cononsolvency phenomena for systems of polymers dissolved in mixed solvents. In particular, phase boundaries (specifically upper critical solution temperature spinodals) are calculated for solutions of homopolymers B in pure solvents and in binary mixtures of small molecule liquids A and C. The miscibility (or immiscibility) patterns for the ternary systems are classified in terms of the FH binary interaction parameters (χ{sub αβ}) and the ratio r = ϕ{sub A}/ϕ{sub C} of the concentrations ϕ{sub A} and ϕ{sub C} of the two solvents. The trends in miscibility are compared to those observed for blends of random copolymers (A{sub x}C{sub 1−x}) with homopolymers (B) and to those deduced for A/B/C solutions of polymers B in liquid mixtures of small molecules A and C that associate into polymeric clusters (A{sub p}C{sub q}){sub i}, (i = 1, 2, …, ∞). Although the classic FH theory is able to explain cosolvency and cononsolvency phenomena, the theory does not include a consideration of the mutual association of the solvent molecules and the competitive association between the solvent molecules and the polymer. These interactions can be incorporated in refinements of the FH theory, and the present paper provides a foundation for such extensions for modeling the rich thermodynamics of polymers in mixed solvents.

  16. Benzobisoxazole cruciforms: A tunable, cross-conjugated platform for the generation of deep blue OLED materials

    DOE PAGES [OSTI]

    Chavez, III, Ramiro; Cai, Min; Tlach, Brian; Wheeler, David L.; Kaudal, Rajiv; Tsyrenova, Ayuna; Tomlinson, Aimee L.; Shinar, Ruth; Shinar, Joseph; Jeffries-EL, Malika

    2016-01-20

    Four new cross-conjugated small molecules based on a central benzo[1,2-d:4,5-d']bisoxazole moiety possessing semi-independently tunable HOMO and LUMO levels were synthesized and the properties of these materials were evaluated experimentally and theoretically. The molecules were thermally stable with 5% weight loss occurring well above 350 °C. The cruciforms all exhibited blue emission in solution ranging from 433–450 nm. Host–guest OLEDs fabricated from various concentrations of these materials using the small molecule host 4,4'-bis(9-carbazolyl)-biphenyl (CBP) exhibited deep blue-emission with Commission Internationale de L'Eclairage (CIE) coordinates of (0.15 ≤ x ≤ 0.17, 0.05 ≤ y ≤ 0.11), and maximum luminance efficiencies as highmore » as ~2 cd A–1. Lastly, these results demonstrate the potential of benzobisoxazole cruciforms as emitters for developing high-performance deep blue OLEDs.« less

  17. Towards microfluidic reactors for cell-free protein synthesis at the point-of-care

    DOE PAGES [OSTI]

    Timm, Andrea C.; Shankles, Peter G.; Foster, Carmen M.; Doktycz, Mitchel John; Retterer, Scott T.

    2015-12-22

    Cell-free protein synthesis (CFPS) is a powerful technology that allows for optimization of protein production without maintenance of a living system. Integrated within micro- and nano-fluidic architectures, CFPS can be optimized for point-of care use. Here, we describe the development of a microfluidic bioreactor designed to facilitate the production of a single-dose of a therapeutic protein, in a small footprint device at the point-of-care. This new design builds on the use of a long, serpentine channel bioreactor and is enhanced by integrating a nanofabricated membrane to allow exchange of materials between parallel reactor and feeder channels. This engineered membrane facilitatesmore » the exchange of metabolites, energy, and inhibitory species, prolonging the CFPS reaction and increasing protein yield. Membrane permeability can be altered by plasma-enhanced chemical vapor deposition and atomic layer deposition to tune the exchange rate of small molecules. This allows for extended reaction times and improved yields. Further, the reaction product and higher molecular weight components of the transcription/translation machinery in the reactor channel can be retained. As a result, we show that the microscale bioreactor design produces higher protein yields than conventional tube-based batch formats, and that product yields can be dramatically improved by facilitating small molecule exchange within the dual-channel bioreactor.« less

  18. Towards microfluidic reactors for cell-free protein synthesis at the point-of-care

    SciTech Connect

    Timm, Andrea C.; Shankles, Peter G.; Foster, Carmen M.; Doktycz, Mitchel John; Retterer, Scott T.

    2015-12-22

    Cell-free protein synthesis (CFPS) is a powerful technology that allows for optimization of protein production without maintenance of a living system. Integrated within micro- and nano-fluidic architectures, CFPS can be optimized for point-of care use. Here, we describe the development of a microfluidic bioreactor designed to facilitate the production of a single-dose of a therapeutic protein, in a small footprint device at the point-of-care. This new design builds on the use of a long, serpentine channel bioreactor and is enhanced by integrating a nanofabricated membrane to allow exchange of materials between parallel reactor and feeder channels. This engineered membrane facilitates the exchange of metabolites, energy, and inhibitory species, prolonging the CFPS reaction and increasing protein yield. Membrane permeability can be altered by plasma-enhanced chemical vapor deposition and atomic layer deposition to tune the exchange rate of small molecules. This allows for extended reaction times and improved yields. Further, the reaction product and higher molecular weight components of the transcription/translation machinery in the reactor channel can be retained. As a result, we show that the microscale bioreactor design produces higher protein yields than conventional tube-based batch formats, and that product yields can be dramatically improved by facilitating small molecule exchange within the dual-channel bioreactor.

  19. Thin Film Packaging Solutions for High Efficiency OLED Lighting Products

    SciTech Connect

    2008-06-30

    as having less than 10% change in transmission during the 15,000 hour test period; (3) demonstrated thin film encapsulation of a phosphorescent OLED device with 1,500 hours of lifetime at 60 C and 80% RH; (4) demonstrated that a thin film laminate encapsulation, in addition to the direct thin film deposition process, of a polymer OLED device was another feasible packaging strategy for OLED lighting. The thin film laminate strategy was developed to mitigate defects, demonstrate roll-to-roll process capability for high volume throughput (reduce costs) and to support a potential commercial pathway that is less dependent upon integrated manufacturing since the laminate could be sold as a rolled good; (5) demonstrated that low cost 'blue' glass substrates could be coated with a siloxane barrier layer for planarization and ion-protection and used in the fabrication of a polymer OLED lighting device. This study further demonstrated that the substrate cost has potential for huge cost reductions from the white borosilicate glass substrate currently used by the OLED lighting industry; (6) delivered four-square feet of white phosphorescent OLED technology, including novel high efficiency devices with 82 CRI, greater than 50 lm/W efficiency, and more than 1,000 hours lifetime in a product concept model shelf; (7) presented and or published more than twenty internal studies (for private use), three external presentations (OLED workshop-for public use), and five technology-related external presentations (industry conferences-for public use); and (8) issued five patent applications, which are in various maturity stages at time of publication. Delivery of thin film encapsulated white phosphorescent OLED lighting technology remains a challenging technical achievement, and it seems that commercial availability of thin, bright, white OLED light that meets market requirements will continue to require research and development effort. However, there will be glass encapsulated white OLED

  20. Mechanism-Based Design of Green Oxidation Catalysts

    SciTech Connect

    Rybak-Akimova, Elena

    2015-03-16

    In modern era of scarce resources, developing chemical processes that can eventually generate useful materials and fuels from readily available, simple, cheap, renewable starting materials is of paramount importance. Small molecules, such as dioxygen, dinitrogen, water, or carbon dioxide, can be viewed as ideal sources of oxygen, nitrogen, or carbon atoms in synthetic applications. Living organisms perfected the art of utilizing small molecules in biosynthesis and in generating energy; photosynthesis, which couples carbohydrate synthesis from carbon dioxide with photocatalytic water splitting, is but one impressive example of possible catalytic processes. Small molecule activation in synthetic systems remains challenging, and current efforts are focused on developing catalytic reactions that can convert small molecules into useful building blocks for generating more complicated organic molecules, including fuels. Modeling nature is attractive in many respects, including the possibility to use non-toxic, earth-abundant metals in catalysis. Specific systems investigated in our work include biomimetic catalytic oxidations with dioxygen, hydrogen peroxide, and related oxygen atom donors. More recently, a new direction was been also pursued in the group, fixation of carbon dioxide with transition metal complexes. Mechanistic understanding of biomimetic metal-catalyzed oxidations is critical for the design of functional models of metalloenzymes, and ultimately for the rational synthesis of useful, selective and efficient oxidation catalysts utilizing dioxygen and hydrogen peroxide as terminal oxidants. All iron oxidases and oxygenases (both mononuclear and dinuclear) utilize metal-centered intermediates as reactive species in selective substrate oxidation. In contrast, free radical pathways (Fenton chemistry) are common for traditional inorganic iron compounds, producing hydroxyl radicals as very active, non-selective oxidants. Recent developments, however, changed this

  1. Multilevel adaptive solution procedure for material nonlinear problems in visual programming environment

    SciTech Connect

    Kim, D.; Ghanem, R.

    1994-12-31

    Multigrid solution technique to solve a material nonlinear problem in a visual programming environment using the finite element method is discussed. The nonlinear equation of equilibrium is linearized to incremental form using Newton-Rapson technique, then multigrid solution technique is used to solve linear equations at each Newton-Rapson step. In the process, adaptive mesh refinement, which is based on the bisection of a pair of triangles, is used to form grid hierarchy for multigrid iteration. The solution process is implemented in a visual programming environment with distributed computing capability, which enables more intuitive understanding of solution process, and more effective use of resources.

  2. CX-001035: Categorical Exclusion Determination

    Energy.gov [DOE]

    Solution Processable Transparent Conductive Hole Injection Electrode for Organic Light Emitting Diode (OLED) Solid State LightingCX(s) Applied: B3.6Date: 03/02/2010Location(s): Sunnyvale, CaliforniaOffice(s): Energy Efficiency and Renewable Energy, National Energy Technology Laboratory

  3. CX-001036: Categorical Exclusion Determination

    Energy.gov [DOE]

    Solution Processable Transparent Conductive Hole Injection Electrode for Organic Light Emitting Diode (OLED) Solid State Lighting (Pennsylvania)CX(s) Applied: B3.6Date: 03/02/2010Location(s): Pittsburgh, PennsylvaniaOffice(s): Energy Efficiency and Renewable Energy, National Energy Technology Laboratory

  4. Semiconducting compounds and devices incorporating same

    DOEpatents

    Marks, Tobin J.; Facchetti, Antonio; Boudreault, Pierre-Luc; Miyauchi, Hiroyuki

    2016-01-19

    Disclosed are molecular and polymeric compounds having desirable properties as semiconducting materials. Such compounds can exhibit desirable electronic properties and possess processing advantages including solution-processability and/or good stability. Organic transistor and photovoltaic devices incorporating the present compounds as the active layer exhibit good device performance.

  5. Slide 1

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Sub-nm Porous Membrane via Directed Nanotube Growth Center for Gas Separations Relevant to Clean Energy Technologies Xu et al, ACS Nano 2011, 5, 1376 1. Solution processible sub- nanometer membrane over macroscopic area 2. Fabrication process compatible with commercial membrane modification 3. Macroscopically aligned nanotubes to enhance permeability and selectivity 4. Tunable nanotube sizes for molecular separation

  6. Synthesis and photovoltaic application of coper (I) sulfide nanocrystals

    SciTech Connect

    Wu, Yue; Wadia, Cyrus; Ma, Wanli; Sadtler, Bryce; Alivisatos, A.Paul

    2008-06-24

    We present the rational synthesis of colloidal copper(I) sulfide nanocrystals and demonstrate their application as an active light absorbing component in combination with CdS nanorods to make a solution-processed solar cell with 1.6percent power conversion efficiency on both conventional glass substrates and flexible plastic substrates with stability over a 4 month testing period.

  7. Sent packing: protein engineering generates a new crystal form of Pseudomonas aeruginosa DsbA1 with increased catalytic surface accessibility

    SciTech Connect

    McMahon, Roisin M. Coinçon, Mathieu; Tay, Stephanie; Heras, Begoña; Morton, Craig J.; Scanlon, Martin J.; Martin, Jennifer L.

    2015-11-26

    The crystal structure of a P. aeruginosa DsbA1 variant is more suitable for fragment-based lead discovery efforts to identify inhibitors of this antimicrobial drug target. In the reported structures the active site of the protein can simultaneously bind multiple ligands introduced in the crystallization solution or via soaking. Pseudomonas aeruginosa is an opportunistic human pathogen for which new antimicrobial drug options are urgently sought. P. aeruginosa disulfide-bond protein A1 (PaDsbA1) plays a pivotal role in catalyzing the oxidative folding of multiple virulence proteins and as such holds great promise as a drug target. As part of a fragment-based lead discovery approach to PaDsbA1 inhibitor development, the identification of a crystal form of PaDsbA1 that was more suitable for fragment-soaking experiments was sought. A previously identified crystallization condition for this protein was unsuitable, as in this crystal form of PaDsbA1 the active-site surface loops are engaged in the crystal packing, occluding access to the target site. A single residue involved in crystal-packing interactions was substituted with an amino acid commonly found at this position in closely related enzymes, and this variant was successfully used to generate a new crystal form of PaDsbA1 in which the active-site surface is more accessible for soaking experiments. The PaDsbA1 variant displays identical redox character and in vitro activity to wild-type PaDsbA1 and is structurally highly similar. Two crystal structures of the PaDsbA1 variant were determined in complex with small molecules bound to the protein active site. These small molecules (MES, glycerol and ethylene glycol) were derived from the crystallization or cryoprotectant solutions and provide a proof of principle that the reported crystal form will be amenable to co-crystallization and soaking with small molecules designed to target the protein active-site surface.

  8. MO-G-BRF-07: Anomalously Fast Diffusion of Carbon Nanotubes Carriers in 3D Tissue Model

    SciTech Connect

    Wang, Y; Bahng, J; Kotov, N

    2014-06-15

    Purpose: We aim to investigate and understand diffusion process of carbon nanotubes (CNTs) and other nanoscale particles in tissue and organs. Methods: In this research, we utilized a 3D model tissue of hepatocellular carcinoma (HCC)cultured in inverted colloidal crystal (ICC) scaffolds to compare the diffusivity of CNTs with small molecules such as Rhodamine and FITC in vitro, and further investigated the transportation of CNTs with and without targeting ligand, TGFβ1. The real-time permeation profiles of CNTs in HCC tissue model with high temporal and spatial resolution was demonstrated by using standard confocal microscopy. Quantitative analysis of the diffusion process in 3D was carried out using luminescence intensity in a series of Z-stack images obtained for different time points of the diffusion process after initial addition of CNTs or small molecules to the cell culture and the image data was analyzed by software ImageJ and Mathematica. Results: CNTs display diffusion rate in model tissues substantially faster than small molecules of the similar charge such as FITC, and the diffusion rate of CNTs are significantly enhanced with targeting ligand, TGFβ1. Conclusion: In terms of the advantages of in-vitro model, we were able to have access to measuring the rate of CNT penetration at designed conditions with variable parameters. And the findings by using this model, changed our understanding about advantages of CNTs as nanoscale drug carriers and provides design principles for making new drug carriers for both treatment and diagnostics. Additionally the fast diffusion opens the discussion of the best possible drug carriers to reach deep parts of cancerous tissues, which is often a prerequisite for successful cancer treatment. This work was supported by the Center for Photonic and Multiscale Nanomaterials funded by National Science Foundation Materials Research Science and Engineering Center program DMR 1120923. The work was also partially supported by NSF

  9. Osmoregulation in Methanogens (and Other Interesting Organisms)

    SciTech Connect

    Roberts, Mary Fedarko

    2014-12-03

    Our research has been aimed at (i) identifying, (ii) determining mode of regulation, and (iii) understanding how different classes of compatible solutes (also termed osmolytes) affect macromolecular stability in response to osmotic and thermal stress. For solutes we have identified (e.g., di-inositol-1,1’-phosphate (DIP)), we used NMR to elucidate biosynthetic pathways and then cloned suspected enzymes in the pathway to explore how they are regulated. Compatible solutes are thought to protect proteins from thermal and osmotic stresses by being excluded from the surface, allowing critical water molecules to interact with the protein. This implies there are no specific binding interactions between osmolytes and proteins. However, we and others have often observed very specific solute effects for proteins that suggest a more direct interaction between solute and protein is likely can occur. Measuring such a weak interaction is extremely difficult. We have developed a solution NMR method, high-resolution field cycling relaxometry, that can measure spin-lattice relaxation rates as a function of magnetic field from 11.7 (the field of a 500 MHz spectrometer) to 0.003 T. The methodology is ideal for nuclei in small molecules with moderately long relaxation times at high fields – phosphate groups (31P), enriched carbonyls (13C), or methyl groups (1H). The protein of interest is spin-labeled to introduce a large dipole on it that will dominate the relaxation of nuclei on any small molecules that bind transiently. The key is to measure relaxation below 1-2 T (and extract nuclei-spin label distances in the bound complex) where the small molecule relaxation will be dominated by dipolar mechanisms with a correlation time indicative of the large protein complex. Our explorations of an inositol monophosphatase (the last step in DIP generation) localized four discrete binding sides for the thermoprotectant α-glutamate. This is a novel approach, and while the work did not fully

  10. Aggresome-like structure induced by isothiocyanates is novel proteasome-dependent degradation machinery

    SciTech Connect

    Mi, Lixin; Gan, Nanqin; Chung, Fung-Lung

    2009-10-16

    Unwanted or misfolded proteins are either refolded by chaperones or degraded by the ubiquitin-proteasome system (UPS). When UPS is impaired, misfolded proteins form aggregates, which are transported along microtubules by motor protein dynein towards the juxta-nuclear microtubule-organizing center to form aggresome, a single cellular garbage disposal complex. Because aggresome formation results from proteasome failure, aggresome components are degraded through the autophagy/lysosome pathway. Here we report that small molecule isothiocyanates (ITCs) can induce formation of aggresome-like structure (ALS) through covalent modification of cytoplasmic {alpha}- and {beta}-tubulin. The formation of ALS is related to neither proteasome inhibition nor oxidative stress. ITC-induced ALS is a proteasome-dependent assembly for emergent removal of misfolded proteins, suggesting that the cell may have a previously unknown strategy to cope with misfolded proteins.

  11. Density-functional errors in ionization potential with increasing system size

    SciTech Connect

    Whittleton, Sarah R.; Sosa Vazquez, Xochitl A.; Isborn, Christine M.; Johnson, Erin R.

    2015-05-14

    This work investigates the effects of molecular size on the accuracy of density-functional ionization potentials for a set of 28 hydrocarbons, including series of alkanes, alkenes, and oligoacenes. As the system size increases, delocalization error introduces a systematic underestimation of the ionization potential, which is rationalized by considering the fractional-charge behavior of the electronic energies. The computation of the ionization potential with many density-functional approximations is not size-extensive due to excessive delocalization of the incipient positive charge. While inclusion of exact exchange reduces the observed errors, system-specific tuning of long-range corrected functionals does not generally improve accuracy. These results emphasize that good performance of a functional for small molecules is not necessarily transferable to larger systems.

  12. Porous Vycor membranes modified by chemical vapor deposition of boron nitride for gas separation

    SciTech Connect

    Levy, R.A.; Ravindranath, C.; Krasnoperov, L.N.; Opyrchal, J.; Ramos, E.S.

    1997-01-01

    This study focuses on the characterization of porous Vycor membranes modified by chemical vapor deposition of boron nitride (B-N-C-H) for gas separation. The B-N-C-H films were deposited on mesoporous Vycor tubes using triethylamine borane complex and ammonia as precursors. The effects of deposition temperature and reactant flow geometry on permselectivity of membranes with respect to various permeant gases were investigated. High selectivities (up to 50,000) were achieved between small molecules (He, H{sub 2}) and large molecules (N{sub 2}, Ar, C{sub 6}H{sub 5}CH{sub 3}). The measured activation energies for the He and H{sub 2} permeability are 9.5 kcal/mol and 12 kcal/mol, respectively. The membranes synthesized at lower temperatures and lower ammonia flow rates showed good mechanical and chemical stability.

  13. Research Performance Progress Report

    SciTech Connect

    Theopold, Klaus H.

    2015-11-30

    The focus of this project was catalysis by ‘proton coupled electron transfer’ (PCET) to metal bound fragments derived from the most abundant small molecules (i. e. O2 and N2). There are many important chemical challenges that are tied to this fundamental reaction type. Among these are: metal catalyzed oxidations of organic molecules utilizing O2 as the oxidant; reduction of O2 to water close to the thermodynamic potential – in other words, the cathode of any fuel cell based on reactions with O 2; transfer of reduced nitrogen species to organic substrates; fixation of nitrogen at modest temperatures and pressures. Any one of these problems has obvious implications for the generation and/or utilization of energy on a large scale.

  14. Imaging of Lipids and Metabolites Using Nanospray Desorption Electrospray Ionization Mass Spectrometry

    SciTech Connect

    Lanekoff, Ingela; Laskin, Julia

    2015-01-17

    In recent years, mass spectroscopy imaging (MSI) has emerged as a foundational technique in metabolomics and drug screening providing deeper understanding of complex mechanistic pathways within biochemical systems and biological organisms. We have been invited to contribute a chapter to a new Springer series volume, entitled Mass Spectrometry Imaging of Small Molecules. The volume is planned for the highly successful lab protocol series Methods in Molecular Biology, published by Humana Press, USA. The volume is aimed to equip readers with step-by-step mass spectrometric imaging protocols and bring rapidly maturing methods of MS imaging to life science researchers. The chapter will provide a detailed protocol of ambient MSI by use of nanospray desorption electrospray ionization.

  15. Activity-Based Protein Profiling of Microbes

    SciTech Connect

    Sadler, Natalie C.; Wright, Aaron T.

    2015-02-01

    Activity-Based Protein Profiling (ABPP) in conjunction with multimodal characterization techniques has yielded impactful findings in microbiology, particularly in pathogen, bioenergy, drug discovery, and environmental research. Using small molecule chemical probes that react irreversibly with specific proteins or protein families in complex systems has provided insights in enzyme functions in central metabolic pathways, drug-protein interactions, and regulatory protein redox, for systems ranging from photoautotrophic cyanobacteria to mycobacteria, and combining live cell or cell extract ABPP with proteomics, molecular biology, modeling, and other techniques has greatly expanded our understanding of these systems. New opportunities for application of ABPP to microbial systems include: enhancing protein annotation, characterizing protein activities in myriad environments, and reveal signal transduction and regulatory mechanisms in microbial systems.

  16. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2,4-pentanediol

    DOE PAGES [OSTI]

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2,4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozymemore » and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.« less

  17. High regularity of Z-DNA revealed by ultra high-resolution crystal structure at 0.55;#8201;Å

    SciTech Connect

    Brzezinski, Krzysztof; Brzuszkiewicz, Anna; Dauter, Miroslawa; Kubicki, Maciej; Jaskolski, Mariusz; Dauter, Zbigniew

    2011-12-02

    The crystal structure of a Z-DNA hexamer duplex d(CGCGCG){sub 2} determined at ultra high resolution of 0.55 {angstrom} and refined without restraints, displays a high degree of regularity and rigidity in its stereochemistry, in contrast to the more flexible B-DNA duplexes. The estimations of standard uncertainties of all individually refined parameters, obtained by full-matrix least-squares optimization, are comparable with values that are typical for small-molecule crystallography. The Z-DNA model generated with ultra high-resolution diffraction data can be used to revise the stereochemical restraints applied in lower resolution refinements. Detailed comparisons of the stereochemical library values with the present accurate Z-DNA parameters, shows in general a good agreement, but also reveals significant discrepancies in the description of guanine-sugar valence angles and in the geometry of the phosphate groups.

  18. Highly efficient organic multi-junction solar cells with a thiophene based donor material

    SciTech Connect

    Meerheim, Rico Krner, Christian; Leo, Karl

    2014-08-11

    The efficiency of organic solar cells can be increased by serial stacked subcells even upon using the same absorber material. For the multi-junction devices presented here, we use the small molecule donor material DCV5T-Me. The subcell currents were matched by optical transfer matrix simulation, allowing an efficiency increase from 8.3% for a single junction up to 9.7% for a triple junction cell. The external quantum efficiency of the subcells, measured under appropriate light bias illumination, is spectrally shifted due to the microcavity of the complete stack, resulting in a broadband response and an increased cell current. The increase of the power conversion efficiency upon device stacking is even stronger for large area cells due to higher influence of the resistance of the indium tin oxide anode, emphasizing the advantage of multi-junction devices for large-area applications.

  19. Metal-silicane: Stability and properties

    SciTech Connect

    Yang, Huan-Cheng; Wang, Jing, E-mail: jwang@hebtu.edu.cn [Department of Physics and Hebei Advanced Thin Film Laboratory, Hebei Normal University, Shijiazhuang 050024 (China); Liu, Ying [Department of Physics and Hebei Advanced Thin Film Laboratory, Hebei Normal University, Shijiazhuang 050024 (China); National Key Laboratory for Materials Simulation and Design, Beijing 100083 (China)

    2014-08-28

    The decoration of silicane using 16 different metal adatoms and the adsorption of small molecules are studied using first-principles calculations. Of the 16 metal adatoms, Li, Na, K, Ca, In, and Sc show a larger binding energy with silicane than their corresponding cohesive energy in the bulk, which suggests they can form 2D layers on the surface of silicane. The band analysis indicates that decoration with metal atoms can effectively tailor the electronic properties of silicane. The adsorption for hydrogen and carbon monoxide on Li-silicane system demonstrates that each Li atom can adsorb a maximum of five H{sub 2} or four CO molecules with the average adsorption energy of 0.18 and 0.23 eV/atom, respectively. The calculated results suggest that metal-silicane systems can provide more information for applications as hydrogen-storage or environment-protection materials.

  20. Crystallographic Analysis of Murine Constitutive Androstane Receptor Ligand-Binding Domain Complexed with 5[alpha]-androst-16-en-3[alpha]-ol

    SciTech Connect

    Vincent, J.; Shan, L.; Fan, M.; Brunzelle, J.S.; Forman, B.M.; Fernandez, E.J.

    2010-03-08

    The constitutive androstane receptor (CAR) is a member of the nuclear receptor superfamily. In contrast to classical nuclear receptors, which possess small-molecule ligand-inducible activity, CAR exhibits constitutive transcriptional activity in the apparent absence of ligand. CAR is among the most important transcription factors; it coordinately regulates the expression of microsomal cytochrome P450 genes and other drug-metabolizing enzymes. The murine CAR ligand-binding domain (LBD) was coexpressed with the steroid receptor coactivator protein (SRC-1) receptor-interacting domain (RID) in Escherichia coli. The mCAR LBD subunit was purified away from SRC-1 by affinity, anion-exchange and size-exclusion chromatography, crystallized with androstenol and the structure of the complex determined by molecular replacement.

  1. Design and Formation of a Large, Tetrahedral, Metal-ligand Cluster Using 1,1'-Binaphthyl Ligands

    SciTech Connect

    Biros, Shannon M.; Yeh, Robert M.; Raymond, Kenneth N.

    2008-03-13

    Many chemists have been fascinated with the development of discrete supramolecular structures that encapsulate guest molecules. These structures can be assembled through covalent or hydrogen bonds, electrostatic or metal-ligand interactions. These host structures have provided valuable insight into the forces involved in small molecule recognition. Our work has focused on the design and study of metal-ligand clusters of varying sizes. The naphthalene [M{sub 4}L{sub 6}]{sup 12-} cluster 1, shown in Figure 1, has demonstrated diastereoselective guest binding and chiral induction properties as well as the ability to catalyze reactions carried out inside the cavity in an enzyme-like manner. However, the size of the cavity (ca. 300-500 {angstrom}{sup 3}) has often limited the scope of substrates for these transformations.

  2. Functional inhibition of UQCRB suppresses angiogenesis in zebrafish

    SciTech Connect

    Cho, Yoon Sun; Jung, Hye Jin; Seok, Seung Hyeok; Payumo, Alexander Y.; Chen, James K.; Kwon, Ho Jeong

    2013-04-19

    Highlights: ► This is the first functional characterization of UQCRB in vivo model. ► Angiogenesis is inhibited with UQCRB loss of function in zebrafish. ► UQCRB is introduced as a prognostic marker for mitochondria- and angiogenesis-related diseases. -- Abstract: As a subunit of mitochondrial complex III, UQCRB plays an important role in complex III stability, electron transport, and cellular oxygen sensing. Herein, we report UQCRB function regarding angiogenesis in vivo with the zebrafish (Danio rerio). UQCRB knockdown inhibited angiogenesis in zebrafish leading to the suppression of VEGF expression. Moreover, the UQCRB-targeting small molecule terpestacin also inhibited angiogenesis and VEGF levels in zebrafish, supporting the role of UQCRB in angiogenesis. Collectively, UQCRB loss of function by either genetic and pharmacological means inhibited angiogenesis, indicating that UQCRB plays a key role in this process and can be a prognostic marker of angiogenesis- and mitochondria-related diseases.

  3. Organic Based Nanocomposite Solar Cells: Cooperative Research and Development Final Report, CRADA Number CRD-04-145

    SciTech Connect

    Olson, D.

    2013-01-01

    This CRADA will focus on the development of organic-based solar cells. Key interfacial issues in these cells will be investigated. In this rapidly emerging technology, it is increasingly clear that cell architecture will need to be at the nanoscale and the interfacial issues between organic elements (small molecule and polymer), transparent conducting oxides, and contact metallizations are critical. Thus this work will focus on the development of high surface area and nanostructured nanocarpets of inorganic oxides, the development of appropriate surface binding/acceptor molecules for the inorganic/organic interface, and the development of next-generation organic materials. Work will be performed in all three areas jointly at NREL and Konarka (with their partner in the third area of the University of Delaware). Results should be more rapid progress toward cheap large-area photovoltaic cells.

  4. Nanofiltration across Defect-Sealed Nanoporous Monolayer Graphene

    DOE PAGES [OSTI]

    O'Hern, Sean C.; Jang, Doojoon; Bose, Suman; Idrobo Tapia, Juan Carlos; Song, Yi; Laoui, Tahar; Kong, Jing; Karnik, Rohit

    2015-04-27

    Monolayer nanoporous graphene represents an ideal membrane for molecular separations, but its practical realization is impeded by leakage through defects in the ultrathin graphene. Here, we report a multiscale leakage-sealing process that exploits the nonpolar nature and impermeability of pristine graphene to selectively block defects, resulting in a centimeter-scale membrane that can separate two fluid reservoirs by an atomically thin layer of graphene. After introducing subnanometer pores in graphene, the membrane exhibited rejection of multivalent ions and small molecules and water flux consistent with prior molecular dynamics simulations. The results indicate the feasibility of constructing defect-tolerant monolayer graphene membranes formore » nanofiltration, desalination, and other separation processes.« less

  5. Organic photosensitive cells grown on rough electrode with nano-scale morphology control

    DOEpatents

    Yang, Fan; Forrest, Stephen R.

    2011-06-07

    An optoelectronic device and a method for fabricating the optoelectronic device includes a first electrode disposed on a substrate, an exposed surface of the first electrode having a root mean square roughness of at least 30 nm and a height variation of at least 200 nm, the first electrode being transparent. A conformal layer of a first organic semiconductor material is deposited onto the first electrode by organic vapor phase deposition, the first organic semiconductor material being a small molecule material. A layer of a second organic semiconductor material is deposited over the conformal layer. At least some of the layer of the second organic semiconductor material directly contacts the conformal layer. A second electrode is deposited over the layer of the second organic semiconductor material. The first organic semiconductor material is of a donor-type or an acceptor-type relative to the second organic semiconductor material, which is of the other material type.

  6. A report on emergent uranyl binding phenomena by an amidoxime phosphonic acid co-polymer

    DOE PAGES [OSTI]

    Abney, C. W.; Das, S.; Mayes, R. T.; Kuo, L. -J.; Wood, J.; Gill, G.; Piechowicz, M.; Lin, Z.; Lin, W.; Dai, S.

    2016-08-01

    Development of technology to harvest the uranium dissolved in seawater would enable access to vast quantities of this critical metal for nuclear power generation. Amidoxime polymers are the most promising platform for achieving this separation, yet design of advanced adsorbents is hindered by uncertainty regarding the uranium binding mode. In this work we use XAFS to investigate the uranium coordination environment in an amidoxime-phosphonic acid copolymer adsorbent. In contrast to the binding mode predicted computationally and from small molecule studies, a cooperative chelating model is favoured, attributable to emergent behavior resulting from inclusion of amidoxime in a polymer. Samples exposedmore » to seawater also display a feature consistent with a 2-oxo-bridged transition metal, suggesting formation of an in situ specific binding site. As a result, these findings challenge long held assumptions and provide new opportunities for the design of advanced adsorbent materials.« less

  7. Simulations of singlet exciton diffusion in organic semiconductors: a review

    DOE PAGES [OSTI]

    Bjorgaard, Josiah A.; Kose, Muhammet Erkan

    2014-12-22

    Our review describes the various aspects of simulation strategies for exciton diffusion in condensed phase thin films of organic semiconductors. Several methods for calculating energy transfer rate constants are discussed along with procedures for how to account for energetic disorder. Exciton diffusion can be modelled by using kinetic Monte-Carlo methods or master equations. Recent literature on simulation efforts for estimating exciton diffusion lengths of various conjugated polymers and small molecules are introduced. Moreover, these studies are discussed in the context of the effects of morphology on exciton diffusion and the necessity of accurate treatment of disorder for comparison of simulationmore » results with those of experiment.« less

  8. Technical Report (Final): Development of Solid State Reagents for Preparing Radiolabeled Imaging Agents

    SciTech Connect

    Kabalka, George W

    2011-05-20

    The goal of this research was on the development of new, rapid, and efficient synthetic methods for incorporating short-lived radionuclides into agents of use in measuring dynamic processes. The initial project period (Year 1) was focused on the preparation of stable, solid state precursors that could be used to efficiently incorporate short-lived radioisotopes into small molecules of use in biological applications (environmental, plant, and animal). The investigation included development and evaluation of new methods for preparing carbon-carbon and carbon-halogen bonds for use in constructing the substrates to be radiolabeled. The second phase (Year 2) was focused on developing isotope incorporation techniques using the stable, boronated polymeric precursors. The final phase (Year 3), was focused on the preparation of specific radiolabeled agents and evaluation of their biodistribution using micro-PET and micro-SPECT. In addition, we began the development of a new series of polymeric borane reagents based on polyethylene glycol backbones.

  9. Time-Resolved SAXS/WAXS Study of the Phase Behavior and Microstructural Evolution of Drug/PEG Solid Dispersions

    SciTech Connect

    Zhu, Qing; Harris, Michael T.; Taylor, Lynne S.

    2013-03-07

    Simultaneous small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) was employed to elucidate the physical state and location of various small molecule drugs blended with polyethylene glycol (PEG), as well as the time dependent microstructural evolution of the systems. Samples were prepared by comelting physical mixtures of the drug and PEG, followed by solidification at 25 C. The model drugs selected encompassed a wide variety of physicochemical properties in terms of crystallization tendency and potential for interaction with PEG. It was observed that compounds which crystallized rapidly and had weak interactions with PEG tended to be excluded from the interlamellar region of the PEG matrix. In contrast, drugs which had favorable interactions with PEG were incorporated into the interlamellar regions of the polymer up until the point at which the drug crystallized whereby phase separation occurred. These factors are likely to impact the effectiveness of drug/PEG systems as drug delivery systems.

  10. 2013 INORGANIC REACTION MECHANISMS GORDON RESEARCH CONFERENCE (MARCH 3-8, 2013 - HOTEL GALVEZ, GALVESTON TX)

    SciTech Connect

    Abu-Omar, Mahdi M.

    2012-12-08

    The 2013 Gordon Conference on Inorganic Reaction Mechanisms will present cutting-edge research on the molecular aspects of inorganic reactions involving elements from throughout the periodic table and state-of-the art techniques that are used in the elucidation of reaction mechanisms. The Conference will feature a wide range of topics, such as homogeneous and heterogeneous catalysis, metallobiochemistry, electron-transfer in energy reactions, polymerization, nitrogen fixation, green chemistry, oxidation, solar conversion, alkane functionalization, organotransition metal chemistry, and computational chemistry. The talks will cover themes of current interest including energy, materials, and bioinorganic chemistry. Sections cover: Electron-Transfer in Energy Reactions; Catalytic Polymerization and Oxidation Chemistry; Kinetics and Spectroscopy of Heterogeneous Catalysts; Metal-Organic Chemistry and its Application in Synthesis; Green Energy Conversion;Organometallic Chemistry and Activation of Small Molecules; Advances in Kinetics Modeling and Green Chemistry; Metals in Biology and Disease; Frontiers in Catalytic Bond Activation and Cleavage.

  11. Main chain acid-degradable polymers for the delivery of bioactive materials

    DOEpatents

    Frechet, Jean M. J.; Standley, Stephany M.; Jain, Rachna; Lee, Cameron C.

    2012-03-20

    Novel main chain acid degradable polymer backbones and drug delivery systems comprised of materials capable of delivering bioactive materials to cells for use as vaccines or other therapeutic agents are described. The polymers are synthesized using monomers that contain acid-degradable linkages cleavable under mild acidic conditions. The main chain of the resulting polymers readily degrade into many small molecules at low pH, but remain relatively stable and intact at physiological pH. The new materials have the common characteristic of being able to degrade by acid hydrolysis under conditions commonly found within the endosomal or lysosomal compartments of cells thereby releasing their payload within the cell. The materials can also be used for the delivery of therapeutics to the acidic regions of tumors and other sites of inflammation.

  12. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2,4-pentanediol

    SciTech Connect

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2,4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozyme and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.

  13. Multi-channel medical imaging system

    DOEpatents

    Frangioni, John V.

    2016-05-03

    A medical imaging system provides simultaneous rendering of visible light and fluorescent images. The system may employ dyes in a small-molecule form that remain in a subject's blood stream for several minutes, allowing real-time imaging of the subject's circulatory system superimposed upon a conventional, visible light image of the subject. The system may provide an excitation light source to excite the fluorescent substance and a visible light source for general illumination within the same optical guide used to capture images. The system may be configured for use in open surgical procedures by providing an operating area that is closed to ambient light. The systems described herein provide two or more diagnostic imaging channels for capture of multiple, concurrent diagnostic images and may be used where a visible light image may be usefully supplemented by two or more images that are independently marked for functional interest.

  14. Multi-channel medical imaging system

    DOEpatents

    Frangioni, John V

    2013-12-31

    A medical imaging system provides simultaneous rendering of visible light and fluorescent images. The system may employ dyes in a small-molecule form that remain in the subject's blood stream for several minutes, allowing real-time imaging of the subject's circulatory system superimposed upon a conventional, visible light image of the subject. The system may provide an excitation light source to excite the fluorescent substance and a visible light source for general illumination within the same optical guide used to capture images. The system may be configured for use in open surgical procedures by providing an operating area that is closed to ambient light. The systems described herein provide two or more diagnostic imaging channels for capture of multiple, concurrent diagnostic images and may be used where a visible light image may be usefully supplemented by two or more images that are independently marked for functional interest.

  15. Ligand-gated Diffusion Across the Bacterial Outer Membrane

    SciTech Connect

    B Lepore; M Indic; H Pham; E Hearn; D Patel; B van den Berg

    2011-12-31

    Ligand-gated channels, in which a substrate transport pathway is formed as a result of the binding of a small-molecule chemical messenger, constitute a diverse class of membrane proteins with important functions in prokaryotic and eukaryotic organisms. Despite their widespread nature, no ligand-gated channels have yet been found within the outer membrane (OM) of Gram-negative bacteria. Here we show, using in vivo transport assays, intrinsic tryptophan fluorescence and X-ray crystallography, that high-affinity (submicromolar) substrate binding to the OM long-chain fatty acid transporter FadL from Escherichia coli causes conformational changes in the N terminus that open up a channel for substrate diffusion. The OM long-chain fatty acid transporter FadL from E. coli is a unique paradigm for OM diffusion-driven transport, in which ligand gating within a {beta}-barrel membrane protein is a prerequisite for channel formation.

  16. Origin of Entropy Convergence in Hydrophobic Hydration and Protein Folding

    SciTech Connect

    Garde, S.; Hummer, G.; Garcia, A.E.; Paulaitis, M.E.; Pratt, L.R. [Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States)] [Theoretical Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); [Center for Molecular and Engineering Thermodynamics, Department of Chemical Engineering, University of Delaware, Newark, Delaware 19716 (United States); [Department of Chemical Engineering, Johns Hopkins University, Baltimore, Maryland 21218 (United States)

    1996-12-01

    An information theory model of hydrophobic effects is used to construct a molecular explanation why hydrophobic solvation entropies of protein unfolding measured by high sensitivity calorimetry converge to zero at a common convergence temperature. The entropy convergence follows directly from the weak temperature dependence of occupancy fluctuations {l_angle}{delta}{ital n}{sup 2}{r_angle} for molecular-scale volumes in water. The macroscopic expression of the contrasting entropic behavior of water relative to common organic solvents is the {ital relative} temperature insensitivity of the water isothermal compressibility compared to hydrocarbon liquids. The information theory model used provides a quantitative description of small molecule hydration and, in addition, predicts that the value of the entropy at convergence is slightly {ital negative}. Interpretations of entropic contributions to protein folding should account for this result. {copyright} {ital 1996 The American Physical Society.}

  17. Phosphoglycerate Mutase 1 Coordinates Glycolysis and Biosynthesis to Promote Tumor Growth

    SciTech Connect

    Hitosugi, Taro; Zhou, Lu; Elf, Shannon; Fan, Jun; Kang, Hee-Bum; Seo, Jae Ho; Shan, Changliang; Dai, Qing; Zhang, Liang; Xie, Jianxin; Gu, Ting-Lei; Jin, Peng; Alečković, Masa; LeRoy, Gary; Kang, Yibin; Sudderth, Jessica A.; DeBerardinis, Ralph J.; Luan, Chi-Hao; Chen, Georgia Z.; Muller, Susan; Shin, Dong M.; Owonikoko, Taofeek K.; Lonial, Sagar; Arellano, Martha L.; Khoury, Hanna J.; Khuri, Fadlo R.; Lee, Benjamin H.; Ye, Keqiang; Boggon, Titus J.; Kang, Sumin; He, Chuan; Chen, Jing

    2012-11-12

    It is unclear how cancer cells coordinate glycolysis and biosynthesis to support rapidly growing tumors. We found that the glycolytic enzyme phosphoglycerate mutase 1 (PGAM1), commonly upregulated in human cancers due to loss of TP53, contributes to biosynthesis regulation partially by controlling intracellular levels of its substrate, 3-phosphoglycerate (3-PG), and product, 2-phosphoglycerate (2-PG). 3-PG binds to and inhibits 6-phosphogluconate dehydrogenase in the oxidative pentose phosphate pathway (PPP), while 2-PG activates 3-phosphoglycerate dehydrogenase to provide feedback control of 3-PG levels. Inhibition of PGAM1 by shRNA or a small molecule inhibitor PGMI-004A results in increased 3-PG and decreased 2-PG levels in cancer cells, leading to significantly decreased glycolysis, PPP flux and biosynthesis, as well as attenuated cell proliferation and tumor growth.

  18. Solvent Immersion Imprint Lithography

    SciTech Connect

    Vasdekis, Andreas E.; Wilkins, Michael J.; Grate, Jay W.; Kelly, Ryan T.; Konopka, Allan; Xantheas, Sotiris S.; Chang, M. T.

    2014-06-21

    The mechanism of polymer disolution was explored for polymer microsystem prototyping, including microfluidics and optofluidics. Polymer films are immersed in a solvent, imprinted and finally brought into contact with a non-modified surface to permanently bond. The underlying polymer-solvent interactions were experimentally and theoretically investigated, and enabled rapid polymer microsystem prototyping. During imprinting, small molecule integration in the molded surfaces was feasible, a principle applied to oxygen sensing. Polystyrene (PS) was employed for microbiological studies at extreme environmental conditions. The thermophile anaerobe Clostridium Thermocellum was grown in PS pore-scale micromodels, revealing a double mean generation lifetime than under ideal culture conditions. Microsystem prototyping through directed polymer dissolution is simple and accessible, while simultaneous patterning, bonding, and surface/volume functionalization are possible in less than one minute.

  19. Binding-induced folding of prokaryotic ubiquitin-like protein on the mycobacterium proteasomal ATPase targets substrates for degradation

    SciTech Connect

    Wang, T.; Li, H.; Darwin, K. H.

    2010-11-01

    Mycobacterium tuberculosis uses a proteasome system that is analogous to the eukaryotic ubiquitin-proteasome pathway and is required for pathogenesis. However, the bacterial analog of ubiquitin, prokaryotic ubiquitin-like protein (Pup), is an intrinsically disordered protein that bears little sequence or structural resemblance to the highly structured ubiquitin. Thus, it was unknown how pupylated proteins were recruited to the proteasome. Here, we show that the Mycobacterium proteasomal ATPase (Mpa) has three pairs of tentacle-like coiled coils that recognize Pup. Mpa bound unstructured Pup through hydrophobic interactions and a network of hydrogen bonds, leading to the formation of an {alpha}-helix in Pup. Our work describes a binding-induced folding recognition mechanism in the Pup-proteasome system that differs mechanistically from substrate recognition in the ubiquitin-proteasome system. This key difference between the prokaryotic and eukaryotic systems could be exploited for the development of a small molecule-based treatment for tuberculosis.

  20. Binding-induced Folding of Prokaryotic Ubiquitin-like Protein on the Mycobacterium Proteasomal ATPase Targets Substrates for Degradation

    SciTech Connect

    T Wang; K Heran Darwin; H Li

    2011-12-31

    Mycobacterium tuberculosis uses a proteasome system that is analogous to the eukaryotic ubiquitin-proteasome pathway and is required for pathogenesis. However, the bacterial analog of ubiquitin, prokaryotic ubiquitin-like protein (Pup), is an intrinsically disordered protein that bears little sequence or structural resemblance to the highly structured ubiquitin. Thus, it was unknown how pupylated proteins were recruited to the proteasome. Here, we show that the Mycobacterium proteasomal ATPase (Mpa) has three pairs of tentacle-like coiled coils that recognize Pup. Mpa bound unstructured Pup through hydrophobic interactions and a network of hydrogen bonds, leading to the formation of an {alpha}-helix in Pup. Our work describes a binding-induced folding recognition mechanism in the Pup-proteasome system that differs mechanistically from substrate recognition in the ubiquitin-proteasome system. This key difference between the prokaryotic and eukaryotic systems could be exploited for the development of a small molecule-based treatment for tuberculosis.

  1. Modeling optical properties of silicon clusters by first principles: From a few atoms to large nanocrystals

    SciTech Connect

    Nurbawono, Argo; Liu, Shuanglong; Zhang, Chun

    2015-04-21

    Time dependent density functional tight binding (TDDFTB) method is implemented with sparse matrix techniques and improved parallelization algorithms. The method is employed to calculate the optical properties of various Si nanocrystals (NCs). The calculated light absorption spectra of small Si NCs from TDDFTB were found to be comparable with many body perturbation methods utilizing planewave basis sets. For large Si NCs (more than a thousand atoms) that are beyond the reach of conventional approaches, the TDDFTB method is able to produce reasonable results that are consistent with prior experiments. We also employed the method to study the effects of surface chemistry on the optical properties of large Si NCs. We learned that the optical properties of Si NCs can be manipulated with small molecule passivations such as methyl, hydroxyl, amino, and fluorine. In general, the shifts and profiles in the absorption spectra can be tuned with suitably chosen passivants.

  2. Strategies for Probing Nanometer-Scale Electrocatalysts: From Single Particles to Catalyst-Membrane Architectures

    SciTech Connect

    Korzeniewski, Carol

    2014-01-20

    The project primary objectives are to prepare and elucidate the promoting properties of materials that possess high activity for the conversion of hydrogen and related small molecules (water, oxygen, carbon monoxide and methanol) in polymer electrolyte fuel cells. One area of research has focused on the study of catalyst materials. Protocols were developed for probing the structure and benchmarking the activity of Pt and Pt bimetallic nanometer-scale catalyst against Pt single crystal electrode standards. A second area has targeted fuel cell membrane and the advancement of simple methods mainly based on vibrational spectroscopy that can be applied broadly in the study of membrane structure and transport properties. Infrared and Raman methods combined with least-squares data modeling were applied to investigate and assist the design of robust, proton conductive membranes, which resist reactant crossover.

  3. Computational methods for molecular docking

    SciTech Connect

    Klebe, G.; Lengauer, T.

    1995-12-31

    This tutorial was one of eight tutorials selected to be presented at the Third International Conference on Intelligent Systems for Molecular Biology which was held in the United Kingdom from July 16 to 19, 1995. Recently, it has been demonstrated that the knowledge of the three-dimensional structure of the protein can be used to derive new protein ligands with improved binding properties. This tutorial focuses on the following questions: What is its binding affinity toward a particular receptor? What are putative conformations of a ligand at the binding site? What are the similarities of different ligands in terms of their recognition capabilities? Where and in which orientation will a ligand bind to the active site? How is a new putative protein ligand selected? An overview is presented of the algorithms which are presently used to handle and predict protein-ligand interactions and to dock small molecule ligands into proteins.

  4. Hierarchical mesoporous/microporous carbon with graphitized frameworks for high-performance lithium-ion batteries

    SciTech Connect

    Lv, Yingying; Fang, Yin; Qian, Xufang; Tu, Bo [Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Fudan University, Shanghai 200433 (China); Wu, Zhangxiong [Department of Chemical Engineering, Monash University, Clayton, VIC 3800 (Australia); Asiri, Abdullah M. [Chemistry Department and The Center of Excellence for Advanced Materials Research, King Abdulaziz University, P.O. Box 80203, Jeddah 21589 (Saudi Arabia); Zhao, Dongyuan, E-mail: dyzhao@fudan.edu.cn [Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Laboratory of Advanced Materials, Fudan University, Shanghai 200433 (China); Department of Chemical Engineering, Monash University, Clayton, VIC 3800 (Australia)

    2014-11-01

    A hierarchical meso-/micro-porous graphitized carbon with uniform mesopores and ordered micropores, graphitized frameworks, and extra-high surface area of ?2200 m{sup 2}/g, was successfully synthesized through a simple one-step chemical vapor deposition process. The commercial mesoporous zeolite Y was utilized as a meso-/ micro-porous template, and the small-molecule methane was employed as a carbon precursor. The as-prepared hierarchical meso-/micro-porous carbons have homogeneously distributed mesopores as a host for electrolyte, which facilitate Li{sup +} ions transport to the large-area micropores, resulting a high reversible lithium ion storage of 1000 mA h/g and a high columbic efficiency of 65% at the first cycle.

  5. Structures of the Wild-Type And Activated Catalytic Domains of Brachydanio Rerio Polo-Like Kinase 1 (Plk1): Changes in the Active-Site Conformation And Interactions With Ligands

    SciTech Connect

    Elling, R.A.; Fucini, R.V.; Romanowski, M.J.

    2009-05-18

    Polo-like kinase 1 (Plk1) is a member of a family of serine/threonine kinases involved in the regulation of cell-cycle progression and cytokinesis and is an attractive target for the development of anticancer therapeutics. A zebrafish homolog of the human Plk1 (hPlk1) kinase domain (KD) was identified that can be expressed in large quantities in bacteria and crystallizes readily, whether in a wild-type form or as a variant containing the activating Thr196-->Asp substitution, in one space group and under similar conditions both in the absence and presence of active-site compounds. This construct was validated by testing a panel of hPlk1 inhibitors against human and zebrafish proteins and it was shown that the selected small molecules inhibited the homologs with a high degree of correlation. Crystal structures of ligand-free wild-type and activated zebrafish Plk1 (zPlk1) KDs revealed the organization of the secondary structural elements around the active site and demonstrated that the activation segment was disordered in the activated form of the domain but possessed a well defined secondary structure in the wild-type enzyme. The cocrystal structure of wild-type zPlk1 KD with ADP documented the hydrolysis of ATP and revealed the phosphorylation site. The cocrystal structure of the activated KD with wortmannin, a covalent inhibitor of Plk1 and PI3 kinases, showed the binding mode of the small molecule to the enzyme and may facilitate the design of more potent Plk1 inhibitors. The work presented in this study establishes the zPlk1 KD as a useful tool for rapid low- and high-throughput structure-based screening and drug discovery of compounds specific for this mitotic target.

  6. Structural Analysis of the Regulatory Domain of ExsA, a Key Transcriptional Regulator of the Type Three Secretion System in Pseudomonas aeruginosa

    DOE PAGES [OSTI]

    Shrestha, Manisha; Xiao, Yi; Robinson, Howard; Schubot, Florian D.

    2015-08-28

    Pseudomonas aeruginosa employs a type three secretion system to facilitate infections in mammalian hosts. The operons encoding genes of structural components of the secretion machinery and associated virulence factors are all under the control of the AraC-type transcriptional activator protein, ExsA. ExsA belongs to a unique subfamily of AraC-proteins that is regulated through protein-protein contacts rather than small molecule ligands. Prior to infection, ExsA is inhibited through a direct interaction with the anti-activator ExsD. To activate ExsA upon host cell contact this interaction is disrupted by the anti-antiactivator protein ExsC. Here we report the crystal structure of the regulatory domainmore » of ExsA, which is known to mediate ExsA dimerization as well as ExsD binding. The crystal structure suggests two models for the ExsA dimer. Both models confirmed the previously shown involvement of helix α-3 in ExsA dimerization but one also suggest a role for helix α-2. These structural data are supported by the observation that a mutation in α-2 greatly diminished the ability of ExsA to activate transcription in vitro. Lastly, additional in vitro transcription studies revealed that a conserved pocket, used by AraC and the related ToxT protein for the binding of small molecule regulators, although present in ExsA is not involved in binding of ExsD.« less

  7. Insulin-Like Growth Factor-Type 1 Receptor Inhibitor NVP-AEW541 Enhances Radiosensitivity of PTEN Wild-Type but Not PTEN-Deficient Human Prostate Cancer Cells

    SciTech Connect

    Isebaert, Sofie F.; Swinnen, Johannes V.; McBride, William H.; Haustermans, Karin M.

    2011-09-01

    Purpose: During the past decade, many clinical trials with both monoclonal antibodies and small molecules that target the insulin-like growth factor-type 1 receptor (IGF-1R) have been launched. Despite the important role of IGF-1R signaling in radioresistance, studies of such agents in combination with radiotherapy are lagging behind. Therefore, the aim of this study was to investigate the effect of the small molecule IGF-1R kinase inhibitor NVP-AEW541 on the intrinsic radioresistance of prostate cancer cells. Methods and Materials: The effect of NVP-AEW541 on cell proliferation, cell viability, IGF-1R signaling, radiosensitivity, cell cycle distribution, and double strand break repair was determined in three human prostate cancer cell lines (PC3, DU145, 22Rv1). Moreover, the importance of the PTEN pathway status was explored by means of transfection experiments with constitutively active Akt or inactive kinase-dead Akt. Results: NVP-AEW541 inhibited cell proliferation and decreased cell viability in a time-and dose-dependent manner in all three cell lines. Radiosensitization was observed in the PTEN wild-type cell lines DU145 and 22Rv1 but not in the PTEN-deficient PC3 cell line. NVP-AEW541-induced radiosensitization coincided with downregulation of phospho-Akt levels and high levels of residual double strand breaks. The importance of PTEN status in the radiosensitization effect was confirmed by transfection experiments with constitutively active Akt or inactive kinase-dead Akt. Conclusions: NVP-AEW541 enhances the effect of ionizing radiation in PTEN wild-type, but not in PTEN-deficient, prostate cancer cells. Proper patient selection based on the PTEN status of the tumor will be critical to the achievement of optimal results in clinical trials in which the combination of radiotherapy and this IGF-1R inhibitor is being explored.

  8. Solution-Based Synthesis of Crystalline Silicon from Liquid Silane through Laser and Chemical Annealing

    DOE PAGES [OSTI]

    Iyer, Ganjigunte R. S.; Hobbie, Erik K.; Guruvenket, Srinivasan; Hoey, Justin M.; Anderson, Kenneth J.; Lovaasen, John; Gette, Cody; Schulz, Douglas L.; Swenson, Orven F.; Elangovan, Arumugasamy; et al

    2012-05-23

    We report a solution process for the synthesis of crystalline silicon from the liquid silane precursor cyclohexasilane (Si6H12). Polysilane films were crystallized through thermal and laser annealing, with plasma hydrogenation at atmospheric pressure generating further structural changes in the films. The evolution from amorphous to microcrystalline is characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), Raman spectroscopy and impedance spectroscopy. A four-decade enhancement in the electrical conductivity is attributed to a disorder-order transition in a bonded Si network. Lastly, our results demonstrate a potentially attractive approach that employs a solution process coupled with ambient post-processing to produce crystallinemore » silicon thin films.« less

  9. Efficient organic solar cells using copper(I) iodide (CuI) hole transport layers

    SciTech Connect

    Peng, Ying; Yaacobi-Gross, Nir; Perumal, Ajay K.; Faber, Hendrik A.; Bradley, Donal D. C.; Anthopoulos, Thomas D. E-mail: t.anthopoulos@imperial.ac.uk; Vourlias, George; Patsalas, Panos A.; He, Zhiqun E-mail: t.anthopoulos@imperial.ac.uk

    2015-06-15

    We report the fabrication of high power conversion efficiency (PCE) polymer/fullerene bulk heterojunction (BHJ) photovoltaic cells using solution-processed Copper (I) Iodide (CuI) as hole transport layer (HTL). Our devices exhibit a PCE value of ∼5.5% which is equivalent to that obtained for control devices based on the commonly used conductive polymer poly(3,4-ethylenedioxythiophene): polystyrenesulfonate as HTL. Inverted cells with PCE >3% were also demonstrated using solution-processed metal oxide electron transport layers, with a CuI HTL evaporated on top of the BHJ. The high optical transparency and suitable energetics of CuI make it attractive for application in a range of inexpensive large-area optoelectronic devices.

  10. Graphene oxide hole transport layers for large area, high efficiency organic solar cells

    SciTech Connect

    Smith, Chris T. G.; Rhodes, Rhys W.; Beliatis, Michail J.; Imalka Jayawardena, K. D. G.; Rozanski, Lynn J.; Mills, Christopher A.; Silva, S. Ravi P.

    2014-08-18

    Graphene oxide (GO) is becoming increasingly popular for organic electronic applications. We present large active area (0.64 cm{sup 2}), solution processable, poly[[9-(1-octylnonyl)-9H-carbazole-2,7-diyl]-2,5-thiophenediyl-2,1, 3-benzothiadiazole-4,7-diyl-2,5-thiophenediyl]:[6,6]-Phenyl C{sub 71} butyric acid methyl ester (PCDTBT:PC{sub 70}BM) organic photovoltaic (OPV) solar cells, incorporating GO hole transport layers (HTL). The power conversion efficiency (PCE) of ∼5% is the highest reported for OPV using this architecture. A comparative study of solution-processable devices has been undertaken to benchmark GO OPV performance with poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) HTL devices, confirming the viability of GO devices, with comparable PCEs, suitable as high chemical and thermal stability replacements for PEDOT:PSS in OPV.

  11. High Efficiency CdTe Ink-Based Solar Cells Using Nanocrystals (Fact Sheet), NREL Highlights in Science, NREL (National Renewable Energy Laboratory)

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    NREL researchers create a solution-processable "ink" to produce high-efficiency solar cells using low temperature and simple processing. Colloidal nanocrystals (NCs) provide a route toward simplified manufacturing of electronic devices compared to vacuum-based technology. Scientists from the National Renewable Energy Laboratory (NREL) collaborated with researchers at the University of Chicago on the colloidal synthesis of 5-10-nm crystals by using the solution as an ink to form large

  12. Perovskite-Fullerene Hybrid Materials Eliminate Hysteresis In Planar Diodes

    Office of Scientific and Technical Information (OSTI)

    (Journal Article) | SciTech Connect Perovskite-Fullerene Hybrid Materials Eliminate Hysteresis In Planar Diodes Citation Details In-Document Search Title: Perovskite-Fullerene Hybrid Materials Eliminate Hysteresis In Planar Diodes Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite-PCBM hybrid solid with significantly reduced

  13. Metal Halide Surface Treatment of Quantum Dots - Energy Innovation Portal

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Advanced Materials Advanced Materials Find More Like This Return to Search Metal Halide Surface Treatment of Quantum Dots National Renewable Energy Laboratory Contact NREL About This Technology Technology Marketing Summary Quantum dot (QD) solids are a solution-processed, composite thin film semiconductor system that is being developed for optoelectronics (display technology, solid state lighting, next generation photovoltaics, photodetector application, etc.). For photovoltaics, in addition to

  14. Structural and magnetic studies of nanocrystalline Y{sub 2}Ir{sub 2}O{sub 7}

    SciTech Connect

    Dwivedi, Vinod Kumar; Mukhopadhyay, Soumik

    2015-06-24

    In this paper, we discuss synthesis of Y{sub 2}Ir{sub 2}O{sub 7} nanoparticles via chemical solution process. Structural analysis shows single cubic phase with Fd-3m space group symmetry. The particle size and distribution were studied by Transmission Electron Microscopy experiments. The average particle size turns out to be 50nm, which is in good agreement with the XRD results. Magnetic characterization shows no evidence of long range ordering even in presence of strong correlations.

  15. Seed Project - Coates > New Research Projects > Research > The Energy

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Materials Center at Cornell New Research Projects In This Section Seed Project - Coates Research Initiative - Abruña Research Initiative - Schlom Transport Dynamics and Carbonation Tolerance in Solution Processable Ionomers: Enabling a Viable Alkaline Anion Exchange Membrane Fuel Cell PI Team members include: Geoffrey Coates and Héctor Abruña. A major advantage of alkaline fuel cells, relative to acidic fuel cells, is their enhanced reaction kinetics for both oxygen reduction and fuel

  16. Low-temperature fabrication of efficient wide-bandgap organolead trihalide perovskite solar cells

    DOE PAGES [OSTI]

    Bi, Cheng; Yuan, Yongbo; Fang, Yanjun; Huang, Jinsong

    2014-11-25

    A mixed halide perovskite solar cell with a 1.72 eV bandgap is developed by incorporating Br into perovskite through a low-temperature solution process. A high efficiency of 13.1% is achieved by carefully tuning the thickness, morphology, and surface passivation of the perovskite layers. Furthermore, the fabrication techniques and conditions are compatible with future perovskite/Si tandem cell studies.

  17. Shape-controlled narrow-gap SnTe nanostructures: From nanocubes to nanorods

    Office of Scientific and Technical Information (OSTI)

    and nanowires (Journal Article) | SciTech Connect Shape-controlled narrow-gap SnTe nanostructures: From nanocubes to nanorods and nanowires Citation Details In-Document Search Title: Shape-controlled narrow-gap SnTe nanostructures: From nanocubes to nanorods and nanowires In this study, the rational design and synthesis of narrow-gap colloidal semiconductor nanocrystals (NCs) is an important step toward the next generation of solution-processable photovoltaics, photodetectors, and

  18. Mesh Morphing Pier Analysis

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Application of Mesh Morphing in STAR-CCM+ to Analysis of Scour at Cylindrical Piers Mesh morphing is a fluid structure interaction capability in STAR-CCM+ to move vertices in the computational mesh in a way that preserves mesh quality when a boundary moves. The equations being solved include terms that account for the motion of the mesh maintaining mass and property balances during the solution process. Initial work on leveraging the mesh morphing FSI capability for efficient application to

  19. Microsoft Word - PolymerSolarCell bh (2)

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    October 2016 Figure 1. Chemical structures of materials used in this study (a) and a schematic illustration of the in-situ x-ray scattering technique (b). Morphology Development of Polymer-Fullerene and Polymer-Polymer Solar Cells during Solution-Shearing Blade Coating Polymer solar cells represent a promising technology that enables solution processing of low-cost, flexible photovoltaic devices for clean energy applications through typical industrial mass production techniques, such as

  20. Ultra-high Charge Carrier Mobility in an Organic Semiconductor by Vertical

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Chain Alignment | Stanford Synchrotron Radiation Lightsource Ultra-high Charge Carrier Mobility in an Organic Semiconductor by Vertical Chain Alignment Thursday, March 31, 2016 The control of the electronic and optical properties of conjugated polymer thin films is of great interest for building more efficient solution processed organic electronic devices, e.g. photovoltaic (OPV) and light emitting (OLED) devices. The crystallinity and the chain orientation in the polymer film has been shown

  1. Size-dependent phase transition in methylammonium lead iodide perovskite

    Office of Scientific and Technical Information (OSTI)

    microplate crystals (Journal Article) | SciTech Connect Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals Citation Details In-Document Search Title: Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase transition in

  2. Enhanced optoelectronic quality of perovskite thin films with

    Office of Scientific and Technical Information (OSTI)

    hypophosphorous acid for planar heterojunction solar cells (Journal Article) | SciTech Connect Journal Article: Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells Citation Details In-Document Search Title: Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells Solution-processed metal halide perovskite semiconductors, such as CH3NH3PbI3, have exhibited

  3. Elucidating the Complex Recombination Kinetics in Organic-Inorganic

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Trihalide Perovskites* | MIT-Harvard Center for Excitonics Elucidating the Complex Recombination Kinetics in Organic-Inorganic Trihalide Perovskites* December 8, 2015 at 4:30pm/36-428 Dane de Quilettes University of Washington deQuilettes-2 Solution processed semiconductors are often plagued by performance limiting defects, surprisingly organometal trihalide perovskites (e.g. CH3NH3PbI3) have exhibited excellent photovoltaic power conversion efficiencies comparable to meticulously refined

  4. Identification of a Novel Drug Lead That Inhibits HCV Infection and Cell-to-Cell Transmission by Targeting the HCV E2 Glycoprotein

    SciTech Connect

    Al Olaby, Reem R.; Cocquerel, Laurence; Zemla, Adam; Saas, Laure; Dubuisson, Jean; Vielmetter, Jost; Marcotrigiano, Joseph; Khan, Abdul Ghafoor; Catalan, Felipe Vences; Perryman, Alexander L.; Freundlich, Joel S.; Forli, Stefano; Levy, Shoshana; Balhorn, Rod; Azzazy, Hassan M.

    2014-10-30

    We report that Hepatitis C Virus (HCV) infects 200 million individuals worldwide. Although several FDA approved drugs targeting the HCV serine protease and polymerase have shown promising results, there is a need for better drugs that are effective in treating a broader range of HCV genotypes and subtypes without being used in combination with interferon and/or ribavirin. Recently, two crystal structures of the core of the HCV E2 protein (E2c) have been determined, providing structural information that can now be used to target the E2 protein and develop drugs that disrupt the early stages of HCV infection by blocking E2’s interaction with different host factors. Using the E2c structure as a template, we have created a structural model of the E2 protein core (residues 421–645) that contains the three amino acid segments that are not present in either structure. Computational docking of a diverse library of 1,715 small molecules to this model led to the identification of a set of 34 ligands predicted to bind near conserved amino acid residues involved in the HCV E2: CD81 interaction. We used surface plasmon resonance detection to screen the ligand set for binding to recombinant E2 protein, and the best binders were subsequently tested to identify compounds that inhibit the infection of Huh-7 cells by HCV. One compound, 281816, blocked E2 binding to CD81 and inhibited HCV infection in a genotype-independent manner with IC50’s ranging from 2.2 µM to 4.6 µM. 281816 blocked the early and late steps of cell-free HCV entry and also abrogated the cell-to-cell transmission of HCV. Collectively the results obtained with this new structural model of E2c suggest the development of small molecule inhibitors such as 281816 that target E2 and disrupt its interaction with CD81 may provide a new paradigm for HCV treatment.

  5. Identification of a Novel Drug Lead That Inhibits HCV Infection and Cell-to-Cell Transmission by Targeting the HCV E2 Glycoprotein

    DOE PAGES [OSTI]

    Al Olaby, Reem R.; Cocquerel, Laurence; Zemla, Adam; Saas, Laure; Dubuisson, Jean; Vielmetter, Jost; Marcotrigiano, Joseph; Khan, Abdul Ghafoor; Catalan, Felipe Vences; Perryman, Alexander L.; et al

    2014-10-30

    We report that Hepatitis C Virus (HCV) infects 200 million individuals worldwide. Although several FDA approved drugs targeting the HCV serine protease and polymerase have shown promising results, there is a need for better drugs that are effective in treating a broader range of HCV genotypes and subtypes without being used in combination with interferon and/or ribavirin. Recently, two crystal structures of the core of the HCV E2 protein (E2c) have been determined, providing structural information that can now be used to target the E2 protein and develop drugs that disrupt the early stages of HCV infection by blocking E2’smore » interaction with different host factors. Using the E2c structure as a template, we have created a structural model of the E2 protein core (residues 421–645) that contains the three amino acid segments that are not present in either structure. Computational docking of a diverse library of 1,715 small molecules to this model led to the identification of a set of 34 ligands predicted to bind near conserved amino acid residues involved in the HCV E2: CD81 interaction. We used surface plasmon resonance detection to screen the ligand set for binding to recombinant E2 protein, and the best binders were subsequently tested to identify compounds that inhibit the infection of Huh-7 cells by HCV. One compound, 281816, blocked E2 binding to CD81 and inhibited HCV infection in a genotype-independent manner with IC50’s ranging from 2.2 µM to 4.6 µM. 281816 blocked the early and late steps of cell-free HCV entry and also abrogated the cell-to-cell transmission of HCV. Collectively the results obtained with this new structural model of E2c suggest the development of small molecule inhibitors such as 281816 that target E2 and disrupt its interaction with CD81 may provide a new paradigm for HCV treatment.« less

  6. Insights into the binding of PARP inhibitors to the catalytic domain of human tankyrase-2

    DOE PAGES [OSTI]

    Qiu, Wei; Lam, Robert; Voytyuk, Oleksandr; Romanov, Vladimir; Gordon, Roni; Gebremeskel, Simon; Vodsedalek, Jakub; Thompson, Christine; Beletskaya, Irina; Battaile, Kevin P.; et al

    2014-07-31

    The poly(ADP-ribose) polymerase (PARP) family represents a new class of therapeutic targets with diverse potential disease indications. PARP1 and PARP2 inhibitors have been developed for breast and ovarian tumors manifesting double-stranded DNA-repair defects, whereas tankyrase 1 and 2 (TNKS1 and TNKS2, also known as PARP5a and PARP5b, respectively) inhibitors have been developed for tumors with elevated β-catenin activity. As the clinical relevance of PARP inhibitors continues to be actively explored, there is heightened interest in the design of selective inhibitors based on the detailed structural features of how small-molecule inhibitors bind to each of the PARP family members. Here, themore » high-resolution crystal structures of the human TNKS2 PARP domain in complex with 16 various PARP inhibitors are reported, including the compounds BSI-201, AZD-2281 and ABT-888, which are currently in Phase 2 or 3 clinical trials. These structures provide insight into the inhibitor-binding modes for the tankyrase PARP domain and valuable information to guide the rational design of future tankyrase-specific inhibitors.« less

  7. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2, 4-pentanediol

    SciTech Connect

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Crystallization of lysozyme with (R)-2-methyl-2, 4-pentanediol produces more ordered crystals and a higher resolution protein structure than crystallization with (S)-2-methyl-2, 4-pentanediol. The results suggest that chiral interactions with chiral additives are important in protein crystal formation. Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2, 4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozyme and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.

  8. Structure and mechanism of the essential two-component signal-transduction system WalKR in Staphylococcus aureus

    DOE PAGES [OSTI]

    Ji, Quanjiang; Chen, Peter J.; Qin, Guangrong; Deng, Xin; Hao, Ziyang; Wawrzak, Zdzislaw; Yeo, Won -Sik; Quang, Jenny Winjing; Cho, Hoonsik; Luo, Guan -Zheng; et al

    2016-03-18

    Most low GC Gram-positive bacteria possess an essential walKR two-component system (TCS) for signal transduction involved in regulating cell wall homoeostasis. Despite the well-established intracellular regulatory mechanism, the role of this TCS in extracellular signal recognition and factors that modulate the activity of this TCS remain largely unknown. Here we identify the extracellular receptor of the kinase ‘WalK’ (erWalK) as a key hub for bridging extracellular signal input and intracellular kinase activity modulation in Staphylococcus aureus. Characterization of the crystal structure of erWalK revealed a canonical Per-Arnt-Sim (PAS) domain for signal sensing. Single amino-acid mutation of potential signal-transduction residues resultedmore » in severely impaired function of WalKR. A small molecule derived from structure-based virtual screening against erWalK is capable of selectively activating the walKR TCS. Lastly, the molecular level characterization of erWalK will not only facilitate exploration of natural signal(s) but also provide a template for rational design of erWalK inhibitors.« less

  9. Catalytic mechanism of a retinoid isomerase essential for vertebrate vision

    DOE PAGES [OSTI]

    Kiser, Philip D.; Zhang, Jianye; Badiee, Mohsen; Li, Qingjiang; Shi, Wuxian; Sui, Xuewu; Golczak, Marcin; Tochtrop, Gregory P.; Palczewski, Krzysztof

    2015-04-20

    Visual function in vertebrates is dependent on the membrane-bound retinoid isomerase RPE65, an essential component of the retinoid cycle pathway that regenerates 11-cis-retinal for rod and cone opsins. The mechanism by which RPE65 catalyzes stereoselective retinoid isomerization has remained elusive because of uncertainty about how retinoids bind to its active site. Here we present crystal structures of RPE65 in complex with retinoid-mimetic compounds, one of which is in clinical trials for the treatment of age-related macular degeneration. The structures reveal the active site retinoid-binding cavity located near the membrane-interacting surface of the enzyme as well as an Fe-bound palmitate ligandmore » positioned in an adjacent pocket. With the geometry of the RPE65–substrate complex clarified, we delineate a mechanism of catalysis that reconciles the extensive biochemical and structural research on this enzyme. Finally, these data provide molecular foundations for understanding a key process in vision and pharmacological inhibition of RPE65 with small molecules.« less

  10. Catalytic mechanism of a retinoid isomerase essential for vertebrate vision

    SciTech Connect

    Kiser, Philip D.; Zhang, Jianye; Badiee, Mohsen; Li, Qingjiang; Shi, Wuxian; Sui, Xuewu; Golczak, Marcin; Tochtrop, Gregory P.; Palczewski, Krzysztof

    2015-04-20

    Visual function in vertebrates is dependent on the membrane-bound retinoid isomerase RPE65, an essential component of the retinoid cycle pathway that regenerates 11-cis-retinal for rod and cone opsins. The mechanism by which RPE65 catalyzes stereoselective retinoid isomerization has remained elusive because of uncertainty about how retinoids bind to its active site. Here we present crystal structures of RPE65 in complex with retinoid-mimetic compounds, one of which is in clinical trials for the treatment of age-related macular degeneration. The structures reveal the active site retinoid-binding cavity located near the membrane-interacting surface of the enzyme as well as an Fe-bound palmitate ligand positioned in an adjacent pocket. With the geometry of the RPE65–substrate complex clarified, we delineate a mechanism of catalysis that reconciles the extensive biochemical and structural research on this enzyme. Finally, these data provide molecular foundations for understanding a key process in vision and pharmacological inhibition of RPE65 with small molecules.

  11. Crystal Structures of SlyA Protein, a Master Virulence Regulator of Salmonella, in Free and DNA-bound States

    SciTech Connect

    Dolan, Kyle T.; Duguid, Erica M.; He, Chuan

    2011-11-17

    SlyA is a master virulence regulator that controls the transcription of numerous genes in Salmonella enterica. We present here crystal structures of SlyA by itself and bound to a high-affinity DNA operator sequence in the slyA gene. SlyA interacts with DNA through direct recognition of a guanine base by Arg-65, as well as interactions between conserved Arg-86 and the minor groove and a large network of non-base-specific contacts with the sugar phosphate backbone. Our structures, together with an unpublished structure of SlyA bound to the small molecule effector salicylate (Protein Data Bank code 3DEU), reveal that, unlike many other MarR family proteins, SlyA dissociates from DNA without large conformational changes when bound to this effector. We propose that SlyA and other MarR global regulators rely more on indirect readout of DNA sequence to exert control over many genes, in contrast to proteins (such as OhrR) that recognize a single operator.

  12. PDock Suite

    Energy Science and Technology Software Center

    2007-03-01

    The PDock suite is a software package for performing molecular docking simulations. PDock was designed to bea modular and extensible software package that interfaces easily with third party codes to quickly evaluate and test different methods for moleuclar docking simulations. Docking calculations start with three dimensional atomistic models of two molecules (usually a protein and small molecule) and predict how they will bind to each other. This problem can be broken down into 2 mainmore » steps: 1) predicting various orientation/conformation combinations (called 'poses') of one molecule to "dock" into the other one and 2) scoring each possible pose. The best scoring pose is predicted to be the biological one. PDock has two main algoritms for performing the first step of docking. The first performs a biased search of poses using its own implementation of the published DOCK algorithm. The second is an evolutionary search algorithm. PDock uses a force-field based scoring scheme with an option of perform a more computationally expensive solvation correction. The PDock suite includes the following programs : PDock (main program); PGrid: for pre-processing input files; ProteinPDock (simplified main ()and input file for special case of protein-protein docking); and CombiPDock (simpliefied main() and input file for special case of combinatorial libraries).« less

  13. Organic Light-Emitting Devices (OLEDS) and Their Optically Detected Magnetic Resonance (ODMR)

    SciTech Connect

    Gang Li

    2003-12-12

    Organic Light-Emitting Devices (OLEDs), both small molecular and polymeric have been studied extensively since the first efficient small molecule OLED was reported by Tang and VanSlyke in 1987. Burroughes' report on conjugated polymer-based OLEDs led to another track in OLED development. These developments have resulted in full color, highly efficient (up to {approx} 20% external efficiency 60 lm/W power efficiency for green emitters), and highly bright (> 140,000 Cd/m{sup 2} DC, {approx}2,000,000 Cd/m{sup 2} AC), stable (>40,000 hr at 5 mA/cm{sup 2}) devices. OLEDs are Lambertian emitters, which intrinsically eliminates the view angle problem of liquid crystal displays (LCDs). Thus OLEDs are beginning to compete with the current dominant LCDs in information display. Numerous companies are now active in this field, including large companies such as Pioneer, Toyota, Estman Kodak, Philipps, DuPont, Samsung, Sony, Toshiba, and Osram, and small companies like Cambridge Display Technology (CDT), Universal Display Corporation (UDC), and eMagin. The first small molecular display for vehicular stereos was introduced in 1998, and polymer OLED displays have begun to appear in commercial products. Although displays are the major application for OLEDs at present, they are also candidates for nest generation solid-state lighting. In this case the light source needs to be white in most cases. Organic transistors, organic solar cells, etc. are also being developed vigorously.

  14. Storing Hydrogen

    SciTech Connect

    Kim, Hyun Jeong; Karkamkar, Abhijeet J.; Autrey, Thomas; Chupas, Peter; Proffen, Thomas E.

    2010-05-31

    Researchers have been studying mesoporous materials for almost two decades with a view to using them as hosts for small molecules and scaffolds for molding organic compounds into new hybrid materials and nanoparticles. Their use as potential storage systems for large quantities of hydrogen has also been mooted. Such systems that might hold large quantities of hydrogen safely and in a very compact volume would have enormous potential for powering fuel cell vehicles, for instance. A sponge-like form of silicon dioxide, the stuff of sand particles and computer chips, can soak up and store other compounds including hydrogen. Studies carried out at the XOR/BESSRC 11-ID-B beamline at the APS have revealed that the nanoscopic properties of the hydrogenrich compound ammonia borane help it store hydrogen more efficiently than usual. The material may have potential for addressing the storage issues associated with a future hydrogen economy. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  15. Millimeter-wave optical double resonance schemes for rapid assignment of perturbed spectra, with applications to the C{sup ~} {sup 1}B{sub 2} state of SO{sub 2}

    SciTech Connect

    Park, G. Barratt E-mail: barratt.park@gmail.com; Womack, Caroline C.; Jiang, Jun; Field, Robert W.; Whitehill, Andrew R.; Ono, Shuhei

    2015-04-14

    Millimeter-wave detected, millimeter-wave optical double resonance (mmODR) spectroscopy is a powerful tool for the analysis of dense, complicated regions in the optical spectra of small molecules. The availability of cavity-free microwave and millimeter wave spectrometers with frequency-agile generation and detection of radiation (required for chirped-pulse Fourier-transform spectroscopy) opens up new schemes for double resonance experiments. We demonstrate a multiplexed population labeling scheme for rapid acquisition of double resonance spectra, probing multiple rotational transitions simultaneously. We also demonstrate a millimeter-wave implementation of the coherence-converted population transfer scheme for background-free mmODR, which provides a ∼10-fold sensitivity improvement over the population labeling scheme. We analyze perturbations in the C{sup ~} state of SO{sub 2}, and we rotationally assign a b{sub 2} vibrational level at 45 328 cm{sup −1} that borrows intensity via a c-axis Coriolis interaction. We also demonstrate the effectiveness of our multiplexed mmODR scheme for rapid acquisition and assignment of three predissociated vibrational levels of the C{sup ~} state of SO{sub 2} between 46 800 and 47 650 cm{sup −1}.

  16. Molecular dynamics simulations of cholesterol-rich membranes using a coarse-grained force field for cyclic alkanes

    SciTech Connect

    MacDermaid, Christopher M. Klein, Michael L.; Fiorin, Giacomo; Kashyap, Hemant K.; DeVane, Russell H.; Shinoda, Wataru; Klauda, Jeffery B.

    2015-12-28

    The architecture of a biological membrane hinges upon the fundamental fact that its properties are determined by more than the sum of its individual components. Studies on model membranes have shown the need to characterize in molecular detail how properties such as thickness, fluidity, and macroscopic bending rigidity are regulated by the interactions between individual molecules in a non-trivial fashion. Simulation-based approaches are invaluable to this purpose but are typically limited to short sampling times and model systems that are often smaller than the required properties. To alleviate both limitations, the use of coarse-grained (CG) models is nowadays an established computational strategy. We here present a new CG force field for cholesterol, which was developed by using measured properties of small molecules, and can be used in combination with our previously developed force field for phospholipids. The new model performs with precision comparable to atomistic force fields in predicting the properties of cholesterol-rich phospholipid bilayers, including area per lipid, bilayer thickness, tail order parameter, increase in bending rigidity, and propensity to form liquid-ordered domains in ternary mixtures. We suggest the use of this model to quantify the impact of cholesterol on macroscopic properties and on microscopic phenomena involving localization and trafficking of lipids and proteins on cellular membranes.

  17. Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

    DOE PAGES [OSTI]

    Bang, Suhee; Lee, Yong -Min; Hong, Seungwoo; Cho, Kyung -Bin; Nishida, Yusuke; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2014-09-14

    Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η2:η2-O2)–Mn+ (Mn+ = Sr2+, Ca2+, Zn2+, Lu3+, Y3+ and Sc3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca2+ and Sr2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities of complexes formed with stronger Lewis acidities were found to be markedly different. Inmore » conclusion, complexes that contain Ca2+ or Sr2+ ions were oxidized by an electron acceptor to release O2, whereas the release of O2 did not occur for complexes that bind stronger Lewis acids. Furthermore, we discuss these results in the light of the functional role of the Ca2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex.« less

  18. High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures

    DOE PAGES [OSTI]

    Musah, Rabi A.; Espinoza, Edgard O.; Cody, Robert B.; Lesiak, Ashton D.; Christensen, Earl D.; Moore, Hannah E.; Maleknia, Simin; Drijhout, Falko P.

    2015-07-09

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. Moreover, a range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. In this paper, we illustrate how the method can be used to: (1) distinguishmore » between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required.« less

  19. High Throughput Ambient Mass Spectrometric Approach to Species Identification and Classification from Chemical Fingerprint Signatures

    SciTech Connect

    Musah, Rabi A.; Espinoza, Edgard O.; Cody, Robert B.; Lesiak, Ashton D.; Christensen, Earl D.; Moore, Hannah E.; Maleknia, Simin; Drijhout, Falko P.

    2015-07-09

    A high throughput method for species identification and classification through chemometric processing of direct analysis in real time (DART) mass spectrometry-derived fingerprint signatures has been developed. The method entails introduction of samples to the open air space between the DART ion source and the mass spectrometer inlet, with the entire observed mass spectral fingerprint subjected to unsupervised hierarchical clustering processing. Moreover, a range of both polar and non-polar chemotypes are instantaneously detected. The result is identification and species level classification based on the entire DART-MS spectrum. In this paper, we illustrate how the method can be used to: (1) distinguish between endangered woods regulated by the Convention for the International Trade of Endangered Flora and Fauna (CITES) treaty; (2) assess the origin and by extension the properties of biodiesel feedstocks; (3) determine insect species from analysis of puparial casings; (4) distinguish between psychoactive plants products; and (5) differentiate between Eucalyptus species. An advantage of the hierarchical clustering approach to processing of the DART-MS derived fingerprint is that it shows both similarities and differences between species based on their chemotypes. Furthermore, full knowledge of the identities of the constituents contained within the small molecule profile of analyzed samples is not required.

  20. Azasugar inhibitors as pharmacological chaperones for Krabbe disease

    SciTech Connect

    Hill, Chris H.; Viuff, Agnete H.; Spratley, Samantha J.; Salamone, Stéphane; Christensen, Stig H.; Read, Randy J.; Moriarty, Nigel W.; Jensen, Henrik H.; Deane, Janet E.

    2015-03-23

    Krabbe disease is a devastating neurodegenerative disorder characterized by rapid demyelination of nerve fibers. This disease is caused by defects in the lysosomal enzyme β-galactocerebrosidase (GALC), which hydrolyzes the terminal galactose from glycosphingolipids. These lipids are essential components of eukaryotic cell membranes: substrates of GALC include galactocerebroside, the primary lipid component of myelin, and psychosine, a cytotoxic metabolite. Mutations of GALC that cause misfolding of the protein may be responsive to pharmacological chaperone therapy (PCT), whereby small molecules are used to stabilize these mutant proteins, thus correcting trafficking defects and increasing residual catabolic activity in cells. Here we describe a new approach for the synthesis of galacto-configured azasugars and the characterization of their interaction with GALC using biophysical, biochemical and crystallographic methods. We identify that the global stabilization of GALC conferred by azasugar derivatives, measured by fluorescence-based thermal shift assays, is directly related to their binding affinity, measured by enzyme inhibition. X-ray crystal structures of these molecules bound in the GALC active site reveal which residues participate in stabilizing interactions, show how potency is achieved and illustrate the penalties of aza/iminosugar ring distortion. The structure–activity relationships described here identify the key physical properties required of pharmacological chaperones for Krabbe disease and highlight the potential of azasugars as stabilizing agents for future enzyme replacement therapies. This work lays the foundation for new drug-based treatments of Krabbe disease.

  1. On the role of chemical reactions in initiating ultraviolet laser ablation in poly(methyl methacrylate)

    SciTech Connect

    Prasad, Manish; Conforti, Patrick F.; Garrison, Barbara J.

    2007-05-15

    The role of chemical reactions is investigated versus the thermal and mechanical processes occurring in a polymer substrate during irradiation by a laser pulse and subsequent ablation. Molecular dynamics simulations with an embedded Monte Carlo based reaction scheme were used to study ultraviolet ablation of poly(methyl methacrylate) at 157 nm. We discuss the onset of ablation, the mechanisms leading to ablation, and the role of stress relaxation of the polymer matrix during ablation. Laser induced heating and chemical decomposition of the polymer substrate are considered as ablation pathways. It is shown that heating the substrate can set off ablation via mechanical failure of the material only for very short laser pulses. For longer pulses, the mechanism of ejection is thermally driven limited by the critical number of bonds broken in the substrate. Alternatively, if the photon energy goes towards direct bond breaking, it initiates chemical reactions, polymer unzipping, and formation of gaseous products, leading to a nearly complete decomposition of the top layers of substrates. The ejection of small molecules has a hollowing out effect on the weakly connected substrates which can lead to lift-off of larger chunks. Excessive pressure buildup upon the creation of gaseous molecules does not lead to enhanced yield. The larger clusters are thermally ejected, and an entrainment of larger polymer fragments in gaseous molecules is not observed.

  2. Design Molecular Recognition Materials for Chiral Sensors, Separtations and Catalytic Materials

    SciTech Connect

    Jia, S.; Nenoff, T.M.; Provencio, P.; Qiu, Y.; Shelnutt, J.A.; Thoma, S.G.; Zhang, J.

    1998-11-01

    The goal is the development of materials that are highly sensitive and selective for chid chemicals and biochemical (such as insecticides, herbicides, proteins, and nerve agents) to be used as sensors, catalysts and separations membranes. Molecular modeling methods are being used to tailor chiral molecular recognition sites with high affinity and selectivity for specified agents. The work focuses on both silicate and non-silicate materials modified with chirally-pure fictional groups for the catalysis or separations of enantiomerically-pure molecules. Surfactant and quaternary amine templating is being used to synthesize porous frameworks, containing mesopores of 30 to 100 angstroms. Computer molecukw modeling methods are being used in the design of these materials, especially in the chid surface- modi~ing agents. Molecular modeling is also being used to predict the catalytic and separations selectivities of the modified mesoporous materials. The ability to design and synthesize tailored asymmetric molecular recognition sites for sensor coatings allows a broader range of chemicals to be sensed with the desired high sensitivity and selectivity. Initial experiments target the selective sensing of small molecule gases and non-toxic model neural compounds. Further efforts will address designing sensors that greatly extend the variety of resolvable chemical species and forming a predictive, model-based method for developing advanced sensors.

  3. Organic light-emitting devices using spin-dependent processes

    DOEpatents

    Vardeny, Z. Valy; Wohlgenannt, Markus

    2010-03-23

    The maximum luminous efficiency of organic light-emitting materials is increased through spin-dependent processing. The technique is applicable to all electro-luminescent processes in which light is produced by singlet exciton decay, and all devices which use such effects, including LEDs, super-radiant devices, amplified stimulated emission devices, lasers, other optical microcavity devices, electrically pumped optical amplifiers, and phosphorescence (Ph) based light emitting devices. In preferred embodiments, the emissive material is doped with an impurity, or otherwise modified, to increase the spin-lattice relaxation rate (i.e., decrease the spin-lattice time), and hence raise the efficiency of the device. The material may be a polymer, oligomer, small molecule, single crystal, molecular crystal, or fullerene. The impurity is preferably a magnetic or paramagnetic substance. The invention is applicable to IR, UV, and other electromagnetic radiation generation and is thus not limited to the visible region of the spectrum. The methods of the invention may also be combined with other techniques used to improve device performance.

  4. Effect of Molecular Weight on the Ion Transport Mechanism in Polymerized Ionic Liquids

    DOE PAGES [OSTI]

    Fan, Fei; Wang, Weiyu; Holt, Adam P.; Feng, Hongbo; Uhrig, David; Lu, Xinyi; Hong, Tao; Wang, Yangyang; Kang, Nam-Goo; Mays, Jimmy; et al

    2016-06-07

    The unique properties of ionic liquids (ILs) have made them promising candidates for electrochemical applications. Polymerization of the corresponding ILs results in a new class of materials called polymerized ionic liquids (PolyILs). Though PolyILs offer the possibility to combine the high conductivity of ILs and the high mechanical strength of polymers, their conductivities are typically much lower than that of the corresponding small molecule ILs. In this study, seven PolyILs were synthesized having degrees of polymerization ranging from 1 to 333, corresponding to molecular weights (MW) from 482 to 160 400 g/mol. Depolarized dynamic light scattering, broadband dielectric spectroscopy, rheology,more » and differential scanning calorimetry were employed to systematically study the influence of MW on the mechanism of ionic transport and segmental dynamics in these materials. Finally, the modified Walden plot analysis reveals that the ion conductivity transforms from being closely coupled with structural relaxation to being strongly decoupled from it as MW increases.« less

  5. The role of membrane fluidization in the gel-assisted formation of giant polymersomes

    DOE PAGES [OSTI]

    Greene, Adrienne C.; Henderson, Ian M.; Gomez, Andrew; Paxton, Walter F.; VanDelinder, Virginia; Bachand, George D.; Hinderberger, Dariush

    2016-07-13

    Polymersomes are being widely explored as synthetic analogs of lipid vesicles based on their enhanced stability and potential uses in a wide variety of applications in (e.g., drug delivery, cell analogs, etc.). Controlled formation of giant polymersomes for use in membrane studies and cell mimetic systems, however, is currently limited by low-yield production methodologies. Here, we describe for the first time, how the size distribution of giant poly(ethylene glycol)-poly(butadiene) (PEO-PBD) polymersomes formed by gel-assisted rehydration may be controlled based on membrane fluidization. We first show that the average diameter and size distribution of PEO-PBD polymersomes may be readily increased bymore » increasing the temperature of the rehydration solution. Further, we describe a correlative relationship between polymersome size and membrane fluidization through the addition of sucrose during rehydration, enabling the formation of PEO-PBD polymersomes with a range of diameters, including giant-sized vesicles (>100 μm). This correlative relationship suggests that sucrose may function as a small molecule fluidizer during rehydration, enhancing polymer diffusivity during formation and increasing polymersome size. Altogether the ability to easily regulate the size of PEO-PBD polymersomes based on membrane fluidity, either through temperature or fluidizers, has broadly applicability in areas including targeted therapeutic delivery and synthetic biology.« less

  6. Structural basis for the blockade of MATE multidrug efflux pumps

    SciTech Connect

    Radchenko, Martha; Symersky, Jindrich; Nie, Rongxin; Lu, Min

    2015-08-06

    Multidrug and toxic compound extrusion (MATE) transporters underpin multidrug resistance by using the H+ or Na+ electrochemical gradient to extrude different drugs across cell membranes. MATE transporters can be further parsed into the DinF, NorM and eukaryotic subfamilies based on their amino-acid sequence similarity. Here we report the 3.0 Å resolution X-ray structures of a protonation-mimetic mutant of an H+-coupled DinF transporter, as well as of an H+-coupled DinF and a Na+-coupled NorM transporters in complexes with verapamil, a small-molecule pharmaceutical that inhibits MATE-mediated multidrug extrusion. Combining structure-inspired mutational and functional studies, we confirm the biological relevance of our crystal structures, reveal the mechanistic differences among MATE transporters, and suggest how verapamil inhibits MATE-mediated multidrug efflux. Our findings offer insights into how MATE transporters extrude chemically and structurally dissimilar drugs and could inform the design of new strategies for tackling multidrug resistance.

  7. Kinetic characterization of ebselen, chelerythrine and apomorphine as glutaminase inhibitors

    SciTech Connect

    Thomas, Ajit G.; Rojas, Camilo; Tanega, Cordelle; Shen, Min; Simeonov, Anton; Boxer, Matthew B.; Auld, Douglas S.; Ferraris, Dana V.; Tsukamoto, Takashi; Department of Neurology, Johns Hopkins University School of Medicine, Baltimore, MD 21205 ; Slusher, Barbara S.

    2013-08-23

    Highlights: Ebselen, chelerythrine and apomorphine were identified as glutaminase inhibitors. These had greater affinities and efficiency of inhibition than known prototypes. Their previously reported biological activity could be due to glutaminase inhibition. -- Abstract: Glutaminase catalyzes the hydrolysis of glutamine to glutamate and plays a central role in the proliferation of neoplastic cells via glutaminolysis, as well as in the generation of excitotoxic glutamate in central nervous system disorders such as HIV-associated dementia (HAD) and multiple sclerosis. Both glutaminase siRNA and glutaminase inhibition have been shown to be effective in in vitro models of cancer and HAD, suggesting a potential role for small molecule glutaminase inhibitors. However, there are no potent, selective inhibitors of glutaminase currently available. The two prototypical glutaminase inhibitors, BPTES and DON, are either insoluble or non-specific. In a search for more drug-like glutaminase inhibitors, we conducted a screen of 1280 in vivo active drugs (Library of Pharmacologically Active Compounds (LOPAC{sup 1280})) and identified ebselen, chelerythrine and (R)-apomorphine. The newly identified inhibitors exhibited 10 to 1500-fold greater affinities than DON and BPTES and over 100-fold increased efficiency of inhibition. Although non-selective, it is noteworthy that the affinity of ebselen for glutaminase is more potent than any other activity yet described. It is possible that the previously reported biological activity seen with these compounds is due, in part, to glutaminase inhibition. Ebselen, chelerythrine and apomorphine complement the armamentarium of compounds to explore the role of glutaminase in disease.

  8. Design of Bcl-2 and Bcl-xL Inhibitors with Subnanomolar Binding Affinities Based upon a New Scaffold

    SciTech Connect

    Zhou, Haibin; Chen, Jianfang; Meagher, Jennifer L.; Yang, Chao-Yie; Aguilar, Angelo; Liu, Liu; Bai, Longchuan; Cong, Xin; Cai, Qian; Fang, Xueliang; Stuckey, Jeanne A.; Wang, Shaomeng

    2014-10-02

    Employing a structure-based strategy, we have designed a new class of potent small-molecule inhibitors of the anti-apoptotic proteins Bcl-2 and Bcl-xL. An initial lead compound with a new scaffold was designed based upon the crystal structure of Bcl-xL and U.S. Food and Drug Administration (FDA) approved drugs and was found to have an affinity of 100 {micro}M for both Bcl-2 and Bcl-xL. Linking this weak lead to another weak-affinity fragment derived from Abbott's ABT-737 led to an improvement of the binding affinity by a factor of >10,000. Further optimization ultimately yielded compounds with subnanomolar binding affinities for both Bcl-2 and Bcl-xL and potent cellular activity. The best compound (21) binds to Bcl-xL and Bcl-2 with K{sub i} < 1 nM, inhibits cell growth in the H146 and H1417 small-cell lung cancer cell lines with IC{sub 50} values of 60-90 nM, and induces robust cell death in the H146 cancer cell line at 30-100 nM.

  9. Nutlin-3 down-regulates retinoblastoma protein expression and inhibits muscle cell differentiation

    SciTech Connect

    Walsh, Erica M.; Niu, MengMeng; Bergholz, Johann; Jim Xiao, Zhi-Xiong

    2015-05-29

    The p53 tumor suppressor gene plays a critical role in regulation of proliferation, cell death and differentiation. The MDM2 oncoprotein is a major negative regulator for p53 by binding to and targeting p53 for proteasome-mediated degradation. The small molecule inhibitor, nutlin-3, disrupts MDM2-p53 interaction resulting in stabilization and activation of p53 protein. We have previously shown that nutlin-3 activates p53, leading to MDM2 accumulation as concomitant of reduced retinoblastoma (Rb) protein stability. It is well known that Rb is important in muscle development and myoblast differentiation and that rhabdomyosarcoma (RMS), or cancer of the skeletal muscle, typically harbors MDM2 amplification. In this study, we show that nutlin-3 inhibited myoblast proliferation and effectively prevented myoblast differentiation, as evidenced by lack of expression of muscle differentiation markers including myogenin and myosin heavy chain (MyHC), as well as a failure to form multinucleated myotubes, which were associated with dramatic increases in MDM2 expression and decrease in Rb protein levels. These results indicate that nutlin-3 can effectively inhibit muscle cell differentiation. - Highlights: • Nutlin-3 inhibits myoblast proliferation and prevents differentiation into myotubes. • Nutlin-3 increases MDM2 expression and down-regulates Rb protein levels. • This study has implication in nutlin-3 treatment of rhabdomyosarcomas.

  10. Simulation of modulated protein crystal structure and diffraction data in a supercell and in superspace

    SciTech Connect

    Lovelace, Jeffrey J.; Simone, Peter D.; Petříček, Václav; Borgstahl, Gloria E. O.

    2013-06-01

    A computer simulation was created for a modulated protein structure along with structure factors in a periodic supercell and in superspace for the purpose of developing and validating software modifications that will be used to solve and refine modulated protein crystals. The toolbox for computational protein crystallography is full of easy-to-use applications for the routine solution and refinement of periodic diffraction data sets and protein structures. There is a gap in the available software when it comes to aperiodic crystallographic data. Current protein crystallography software cannot handle modulated data, and small-molecule software for aperiodic crystallography cannot work with protein structures. To adapt software for modulated protein data requires training data to test and debug the changed software. Thus, a comprehensive training data set consisting of atomic positions with associated modulation functions and the modulated structure factors packaged as both a three-dimensional supercell and as a modulated structure in (3+1)D superspace has been created. The (3+1)D data were imported into Jana2006; this is the first time that this has been performed for protein data.

  11. Processing incommensurately modulated protein diffraction data with Eval15

    SciTech Connect

    Porta, Jason; Lovelace, Jeffrey J.; Schreurs, Antoine M. M.; Kroon-Batenburg, Loes M. J.; Borgstahl, Gloria E. O.

    2011-07-01

    Data processing of an incommensurately modulated profilin–actin crystal is described. Recent challenges in biological X-ray crystallography include the processing of modulated diffraction data. A modulated crystal has lost its three-dimensional translational symmetry but retains long-range order that can be restored by refining a periodic modulation function. The presence of a crystal modulation is indicated by an X-ray diffraction pattern with periodic main reflections flanked by off-lattice satellite reflections. While the periodic main reflections can easily be indexed using three reciprocal-lattice vectors a*, b*, c*, the satellite reflections have a non-integral relationship to the main lattice and require a q vector for indexing. While methods for the processing of diffraction intensities from modulated small-molecule crystals are well developed, they have not been applied in protein crystallography. A recipe is presented here for processing incommensurately modulated data from a macromolecular crystal using the Eval program suite. The diffraction data are from an incommensurately modulated crystal of profilin–actin with single-order satellites parallel to b*. The steps taken in this report can be used as a guide for protein crystallographers when encountering crystal modulations. To our knowledge, this is the first report of the processing of data from an incommensurately modulated macromolecular crystal.

  12. A charge carrier transport model for donor-acceptor blend layers

    SciTech Connect

    Fischer, Janine Widmer, Johannes; Koerner, Christian; Vandewal, Koen; Leo, Karl; Kleemann, Hans; Tress, Wolfgang; Riede, Moritz

    2015-01-28

    Highly efficient organic solar cells typically comprise donor-acceptor blend layers facilitating effective splitting of excitons. However, the charge carrier mobility in the blends can be substantially smaller than in neat materials, hampering the device performance. Currently, available mobility models do not describe the transport in blend layers entirely. Here, we investigate hole transport in a model blend system consisting of the small molecule donor zinc phthalocyanine (ZnPc) and the acceptor fullerene C{sub 60} in different mixing ratios. The blend layer is sandwiched between p-doped organic injection layers, which prevent minority charge carrier injection and enable exploiting diffusion currents for the characterization of exponential tail states from a thickness variation of the blend layer using numerical drift-diffusion simulations. Trap-assisted recombination must be considered to correctly model the conductivity behavior of the devices, which are influenced by local electron currents in the active layer, even though the active layer is sandwiched in between p-doped contacts. We find that the density of deep tail states is largest in the devices with 1:1 mixing ratio (E{sub t} = 0.14 eV, N{sub t} = 1.2 × 10{sup 18 }cm{sup −3}) directing towards lattice disorder as the transport limiting process. A combined field and charge carrier density dependent mobility model are developed for this blend layer.

  13. Comparison and analysis of zinc and cobalt-based systems as catalytic entities for the hydration of carbon dioxide

    DOE PAGES [OSTI]

    Lau, E. Y.; Wong, S. E.; Baker, S. E.; Bearinger, J. P.; Koziol, L.; Valdez, C. A.; Satcher, J. H.; Aines, R. D.; Lightstone, F. C.

    2013-06-20

    In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO 2) to bicarbonate under physiological conditions. Efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn 2+ or the Co 2+ ion and studied their reaction coordinate for CO 2 hydration. These calculations demonstrated that the ability of the complexmore » to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Moreover, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts.« less

  14. Comparison and analysis of zinc and cobalt-based systems as catalytic entities for the hydration of carbon dioxide

    SciTech Connect

    Lau, E. Y.; Wong, S. E.; Baker, S. E.; Bearinger, J. P.; Koziol, L.; Valdez, C. A.; Satcher, J. H.; Aines, R. D.; Lightstone, F. C.

    2013-06-20

    In nature, the zinc metalloenzyme carbonic anhydrase II (CAII) efficiently catalyzes the conversion of carbon dioxide (CO 2) to bicarbonate under physiological conditions. Efforts have been directed towards the development of small molecule mimetics that can facilitate this process and thus have a beneficial environmental impact, but these efforts have met very limited success. Herein, we undertook quantum mechanical calculations of four mimetics, 1,5,9-triazacyclododedacane, 1,4,7,10-tetraazacyclododedacane, tris(4,5-dimethyl-2-imidazolyl)phosphine, and tris(2-benzimidazolylmethyl)amine, in their complexed form either with the Zn 2+ or the Co 2+ ion and studied their reaction coordinate for CO 2 hydration. These calculations demonstrated that the ability of the complex to maintain a tetrahedral geometry and bind bicarbonate in a unidentate manner were vital for the hydration reaction to proceed favorably. Moreover, these calculations show that the catalytic activity of the examined zinc complexes was insensitive to coordination states for zinc, while coordination states above four were found to have an unfavorable effect on product release for the cobalt counterparts.

  15. Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate

    SciTech Connect

    Dante, Roberto C.; Sánchez-Arévalo, Francisco M.; Chamorro-Posada, Pedro; Vázquez-Cabo, José; Lartundo-Rojas, Luis; and others

    2015-03-15

    The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, the sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures.

  16. On the calculation of internal forces in mechanically stressed polyatomic molecules

    SciTech Connect

    Avdoshenko, Stanislav M.; Konda, Sai Sriharsha M.; Makarov, Dmitrii E.

    2014-10-07

    We discuss how to define and to compute internal forces in a molecule subjected to mechanical stress. Because of the inherently many-body character of intramolecular interactions, internal forces cannot be uniquely defined without specifying a set of internal coordinates used to describe the molecular structure. When such a set is comprised of 3N − 6 interactomic distances (N being the number of atoms) and includes the bond lengths of interest, we show that the associated forces, while satisfying the equation F = ∂V/∂R (where R is the bond length, F is the internal force in this bond, and V is the potential energy of the molecule), can be determined from the molecular geometry alone. We illustrate these ideas using several toy models ranging from small molecules to a graphene sheet and show that the magnitude of the internal force in a bond is not necessarily a good predictor of its strength in response to mechanical loading. At the same time, analysis of internal forces reveals interesting phenomena such as the force multiplication effect, where weak external forces may, e.g., be used to break strong bonds, and offers insight into the catch-bond phenomenon where chemical reactivity is suppressed through application of a force.

  17. Recognition of chromatin by the plant alkaloid, ellipticine as a dual binder

    SciTech Connect

    Banerjee, Amrita; Sanyal, Sulagna; Majumder, Parijat; Chakraborty, Payal; Jana, Kuladip; Dasgupta, Dipak

    2015-07-10

    Recognition of core histone components of chromatin along with chromosomal DNA by a class of small molecule modulators is worth examining to evaluate their intracellular mode of action. A plant alkaloid ellipticine (ELP) which is a putative anticancer agent has so far been reported to function via DNA intercalation, association with topoisomerase II and binding to telomere region. However, its effect upon the potential intracellular target, chromatin is hitherto unreported. Here we have characterized the biomolecular recognition between ELP and different hierarchical levels of chromatin. The significant result is that in addition to DNA, it binds to core histone(s) and can be categorized as a ‘dual binder’. As a sequel to binding with histone(s) and core octamer, it alters post-translational histone acetylation marks. We have further demonstrated that it has the potential to modulate gene expression thereby regulating several key biological processes such as nuclear organization, transcription, translation and histone modifications. - Highlights: • Ellipticine acts a dual binder binding to both DNA and core histone(s). • It induces structural perturbations in chromatin, chromatosome and histone octamer. • It alters histones acetylation and affects global gene expression.

  18. Real-space representation of electron correlation in ?-conjugated systems

    SciTech Connect

    Wang, Jian E-mail: e.j.baerends@vu.nl; Baerends, Evert Jan E-mail: e.j.baerends@vu.nl

    2015-05-28

    ?-electron conjugation and aromaticity are commonly associated with delocalization and especially high mobility of the ? electrons. We investigate if also the electron correlation (pair density) exhibits signatures of the special electronic structure of conjugated systems. To that end the shape and extent of the pair density and derived quantities (exchange-correlation hole, Coulomb hole, and conditional density) are investigated for the prototype systems ethylene, hexatriene, and benzene. The answer is that the effects of ? electron conjugation are hardly discernible in the real space representations of the electron correlation. We find the xc hole to be as localized (confined to atomic or diatomic regions) in conjugated systems as in small molecules. This result is relevant for density functional theory (DFT). The potential of the electron exchange-correlation hole is the largest part of v{sub xc}, the exchange-correlation Kohn-Sham potential. So the extent of the hole directly affects the orbital energies of both occupied and unoccupied Kohn-Sham orbitals and therefore has direct relevance for the excitation spectrum as calculated with time-dependent DFT calculations. The potential of the localized xc hole is comparatively more attractive than the actual hole left behind by an electron excited from a delocalized molecular orbital of a conjugated system.

  19. Basal-subtype and MEK-Pl3K feedback signaling determine susceptibility of breast cancer cells to MEK inhibition

    SciTech Connect

    Mirzoeva, Olga K.; Das, Debopriya; Heiser, Laura M.; Bhattacharya, Sanchita; Siwak, Doris; Gendelman, Rina; Bayani, Nora; Wang, Nicholas J.; Neve, Richard M.; Knight, Zachary; Feiler, Heidi S.; Gascard, Philippe; Parvin, Bahram; Spellman, Paul T.; Shokat, Kevan M.; Wyrobek, Andrew J.; Bissell, Mina J.; McCormick, Frank; Kuo, Wen-Lin; Mills, Gordon B.; Gray, Joe W.; Korn, W. Michael

    2009-01-23

    Specific inhibitors of MEK have been developed that efficiently inhibit the oncogenic RAF-MEK-ERK pathway. We employed a systems-based approach to identify breast cancer subtypes particularly susceptible to MEK inhibitors and to understand molecular mechanisms conferring resistance to such compounds. Basal-type breast cancer cells were found to be particularly susceptible to growth-inhibition by small-molecule MEK inhibitors. Activation of the PI3 kinase pathway in response to MEK inhibition through a negative MEK-EGFR-PI3 kinase feedback loop was found to limit efficacy. Interruption of this feedback mechanism by targeting MEK and PI3 kinase produced synergistic effects, including induction of apoptosis and, in some cell lines, cell cycle arrest and protection from apoptosis induced by proapoptotic agents. These findings enhance our understanding of the interconnectivity of oncogenic signal transduction circuits and have implications for the design of future clinical trials of MEK inhibitors in breast cancer by guiding patient selection and suggesting rational combination therapies.

  20. Covalently crosslinked diels-alder polymer networks.

    SciTech Connect

    Bowman, Christopher; Adzima, Brian J.; Anderson, Benjamin John

    2011-09-01

    This project examines the utility of cycloaddition reactions for the synthesis of polymer networks. Cycloaddition reactions are desirable because they produce no unwanted side reactions or small molecules, allowing for the formation of high molecular weight species and glassy crosslinked networks. Both the Diels-Alder reaction and the copper-catalyzed azide-alkyne cycloaddition (CuAAC) were studied. Accomplishments include externally triggered healing of a thermoreversible covalent network via self-limited hysteresis heating, the creation of Diels-Alder based photoresists, and the successful photochemical catalysis of CuAAC as an alternative to the use of ascorbic acid for the generation of Cu(I) in click reactions. An analysis of the results reveals that these new methods offer the promise of efficiently creating robust, high molecular weight species and delicate three dimensional structures that incorporate chemical functionality in the patterned material. This work was performed under a Strategic Partnerships LDRD during FY10 and FY11 as part of a Sandia National Laboratories/University of Colorado-Boulder Excellence in Science and Engineering Fellowship awarded to Brian J. Adzima, a graduate student at UC-Boulder. Benjamin J. Anderson (Org. 1833) was the Sandia National Laboratories point-of-contact for this fellowship.

  1. Tunable Encapsulation Structure of Block Copolymer Coated Single-Walled Carbon Nanotubes in Aqueous Solution

    DOE PAGES [OSTI]

    Han, Youngkyu; Ahn, Suk-Kyun; Zhang, Zhe; Smith, Gregory Scott; Do, Changwoo

    2015-05-15

    The nano-sized and shape-tunable molecular building blocks can provide great opportunities for the fabrication of precisely controlled nanostructures. In this work, we have fabricated a molecular building block of single-walled carbon nanotubes (SWNTs) coated by PPO-PEO-PPO block copolymers whose encapsulation structure can be controlled via temperature or addition of small molecules. The structure and optical properties of SWNT-block copolymers have been investigated by small angle neutron scattering (SANS), ultraviolet-visible (UV-vis) spectroscopy, atomic force microscopy (AFM), and molecular dynamics (MD) simulation. The structure of the hydrated block copolymer layer surrounding SWNT can be controlled reversibly by varying temperature as well asmore » by irreversibly adding 5-methylsalicylic acid (5MS). Increasing hydrophobicity of the polymers with temperature and strong tendency of 5MS to interact with both block copolymers and orbitals of the SWNTs are likely to be responsible for the significant structural change of the block copolymer encapsulation layer, from loose corona shell to tightly encapsulating compact shell. These result shows an efficient and simple way to fabricate and manipulate carbon-based nano building blocks in aqueous systems with tunable structure.« less

  2. Structural Characterization of Inhibitors with Selectivity against Members of a Homologous Enzyme Family

    SciTech Connect

    Pavlovsky, Alexander G.; Liu, Xuying; Faehnle, Christopher R.; Potente, Nina; Viola, Ronald E.

    2013-01-31

    The aspartate biosynthetic pathway provides essential metabolites for many important biological functions, including the production of four essential amino acids. As this critical pathway is only present in plants and microbes, any disruptions will be fatal to these organisms. An early pathway enzyme, L-aspartate-{beta}-semialdehyde dehydrogenase, produces a key intermediate at the first branch point of this pathway. Developing potent and selective inhibitors against several orthologs in the L-aspartate-{beta}-semialdehyde dehydrogenase family can serve as lead compounds for antibiotic development. Kinetic studies of two small molecule fragment libraries have identified inhibitors that show good selectivity against L-aspartate-{beta}-semialdehyde dehydrogenases from two different bacterial species, Streptococcus pneumoniae and Vibrio cholerae, despite the presence of an identical constellation of active site amino acids in this homologous enzyme family. Structural characterization of enzyme-inhibitor complexes have elucidated different modes of binding between these structurally related enzymes. This information provides the basis for a structure-guided approach to the development of more potent and more selective inhibitors.

  3. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation. [Spiropyrans

    SciTech Connect

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in [approximately]240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH[sub 2]I[sub 2] and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a [approximately]350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  4. Femtosecond dynamics of fundamental reaction processes in liquids: Proton transfer, geminate recombination, isomerization and vibrational relaxation

    SciTech Connect

    Schwartz, B.J.

    1992-11-01

    The fast excited state intramolecular proton transfer of 3-hydroxyflavone is measured and effects of external hydrogen-bonding interactions on the proton transfer are studied. The proton transfer takes place in {approximately}240 fsec in nonpolar environments, but becomes faster than instrumental resolution of 110 fsec in methanol solution. The dynamics following photodissociation of CH{sub 2}I{sub 2} and other small molecules provide the first direct observations of geminate recombination. The recombination of many different photodissociating species occurs on a {approximately}350 fsec time scale. Results show that recombination yields but not rates depend on the solvent environment and suggest that recombination kinetics are dominated by a single collision with surrounding solvent cage. Studies of sterically locked phenyl-substituted butadienes offer new insights into the electronic structure and isomerization behavior of conjugated polyenes. Data show no simple correlation between hinderance of specific large amplitude motions and signatures of isomerizative behavior such as viscosity dependent excited state lifetimes, implying that the isomerization does not provide a suitable for simple condensed phase reaction rate theories. The spectral dynamics of a photochromic spiropyran indicate that recombination, isomerization and vibrational relaxation all play important roles in photoreactivity of complex molecules. The interplay of these microscopic phenomena and their effect on macroscopic properties such as photochromism are discussed. All the results indicate that the initial steps of the photochromic reaction process occur extremely rapidly. Laser system and computer codes for data analysis are discussed.

  5. Reaction product imaging

    SciTech Connect

    Chandler, D.W.

    1993-12-01

    Over the past few years the author has investigated the photochemistry of small molecules using the photofragment imaging technique. Bond energies, spectroscopy of radicals, dissociation dynamics and branching ratios are examples of information obtained by this technique. Along with extending the technique to the study of bimolecular reactions, efforts to make the technique as quantitative as possible have been the focus of the research effort. To this end, the author has measured the bond energy of the C-H bond in acetylene, branching ratios in the dissociation of HI, the energetics of CH{sub 3}Br, CD{sub 3}Br, C{sub 2}H{sub 5}Br and C{sub 2}H{sub 5}OBr dissociation, and the alignment of the CD{sub 3} fragment from CD{sub 3}I photolysis. In an effort to extend the technique to bimolecular reactions the author has studied the reaction of H with HI and the isotopic exchange reaction between H and D{sub 2}.

  6. Medical imaging systems

    DOEpatents

    Frangioni, John V.

    2012-07-24

    A medical imaging system provides simultaneous rendering of visible light and fluorescent images. The system may employ dyes in a small-molecule form that remains in a subject's blood stream for several minutes, allowing real-time imaging of the subject's circulatory system superimposed upon a conventional, visible light image of the subject. The system may also employ dyes or other fluorescent substances associated with antibodies, antibody fragments, or ligands that accumulate within a region of diagnostic significance. In one embodiment, the system provides an excitation light source to excite the fluorescent substance and a visible light source for general illumination within the same optical guide that is used to capture images. In another embodiment, the system is configured for use in open surgical procedures by providing an operating area that is closed to ambient light. More broadly, the systems described herein may be used in imaging applications where a visible light image may be usefully supplemented by an image formed from fluorescent emissions from a fluorescent substance that marks areas of functional interest.

  7. Hydrolysis of biomass material

    DOEpatents

    Schmidt, Andrew J.; Orth, Rick J.; Franz, James A.; Alnajjar, Mikhail

    2004-02-17

    A method for selective hydrolysis of the hemicellulose component of a biomass material. The selective hydrolysis produces water-soluble small molecules, particularly monosaccharides. One embodiment includes solubilizing at least a portion of the hemicellulose and subsequently hydrolyzing the solubilized hemicellulose to produce at least one monosaccharide. A second embodiment includes solubilizing at least a portion of the hemicellulose and subsequently enzymatically hydrolyzing the solubilized hemicellulose to produce at least one monosaccharide. A third embodiment includes solubilizing at least a portion of the hemicellulose by heating the biomass material to greater than 110.degree. C. resulting in an aqueous portion that includes the solubilized hemicellulose and a water insoluble solids portion and subsequently separating the aqueous portion from the water insoluble solids portion. A fourth embodiment is a method for making a composition that includes cellulose, at least one protein and less than about 30 weight % hemicellulose, the method including solubilizing at least a portion of hemicellulose present in a biomass material that also includes cellulose and at least one protein and subsequently separating the solubilized hemicellulose from the cellulose and at least one protein.

  8. Recent developments with metalloprotease inhibitor class of drug candidates for Botulinum neurotoxins

    DOE PAGES [OSTI]

    Kumar, Gyanendra; Swaminathan, Subramanyam

    2015-03-01

    Botulinum Neurotoxins are the most poisonous of all toxins with lethal dose in nanogram quantities. They are also potential biological warfare and bioterrorism agents due to their high toxicity and ease of preparation. On the other hand BoNTs are also being increasingly used for therapeutic and cosmetic purposes, and with that the chances of accidental overdose are increasing. And despite the potential damage they could cause to human health, there are no post-intoxication drugs available so far. But progress is being made in this direction. The crystal structures in native form and bound with substrate peptides have been determined, andmore » these are enabling structure-based drug discovery possible. High throughput assays have also been designed to speed up the screening progress. Substrate-based and small molecule inhibitors have been identified. But turning high affinity inhibitors into clinically viable drug candidates has remained a challenge. We discuss here the latest developments and the future challenges in drug discovery for Botulinum neurotoxins.« less

  9. Azasugar inhibitors as pharmacological chaperones for Krabbe disease

    DOE PAGES [OSTI]

    Hill, Chris H.; Viuff, Agnete H.; Spratley, Samantha J.; Salamone, Stéphane; Christensen, Stig H.; Read, Randy J.; Moriarty, Nigel W.; Jensen, Henrik H.; Deane, Janet E.

    2015-03-23

    Krabbe disease is a devastating neurodegenerative disorder characterized by rapid demyelination of nerve fibers. This disease is caused by defects in the lysosomal enzyme β-galactocerebrosidase (GALC), which hydrolyzes the terminal galactose from glycosphingolipids. These lipids are essential components of eukaryotic cell membranes: substrates of GALC include galactocerebroside, the primary lipid component of myelin, and psychosine, a cytotoxic metabolite. Mutations of GALC that cause misfolding of the protein may be responsive to pharmacological chaperone therapy (PCT), whereby small molecules are used to stabilize these mutant proteins, thus correcting trafficking defects and increasing residual catabolic activity in cells. Here we describe amore » new approach for the synthesis of galacto-configured azasugars and the characterization of their interaction with GALC using biophysical, biochemical and crystallographic methods. We identify that the global stabilization of GALC conferred by azasugar derivatives, measured by fluorescence-based thermal shift assays, is directly related to their binding affinity, measured by enzyme inhibition. X-ray crystal structures of these molecules bound in the GALC active site reveal which residues participate in stabilizing interactions, show how potency is achieved and illustrate the penalties of aza/iminosugar ring distortion. The structure–activity relationships described here identify the key physical properties required of pharmacological chaperones for Krabbe disease and highlight the potential of azasugars as stabilizing agents for future enzyme replacement therapies. This work lays the foundation for new drug-based treatments of Krabbe disease.« less

  10. Recent developments with metalloprotease inhibitor class of drug candidates for Botulinum neurotoxins

    SciTech Connect

    Kumar, Gyanendra; Swaminathan, Subramanyam

    2015-03-01

    Botulinum Neurotoxins are the most poisonous of all toxins with lethal dose in nanogram quantities. They are also potential biological warfare and bioterrorism agents due to their high toxicity and ease of preparation. On the other hand BoNTs are also being increasingly used for therapeutic and cosmetic purposes, and with that the chances of accidental overdose are increasing. And despite the potential damage they could cause to human health, there are no post-intoxication drugs available so far. But progress is being made in this direction. The crystal structures in native form and bound with substrate peptides have been determined, and these are enabling structure-based drug discovery possible. High throughput assays have also been designed to speed up the screening progress. Substrate-based and small molecule inhibitors have been identified. But turning high affinity inhibitors into clinically viable drug candidates has remained a challenge. We discuss here the latest developments and the future challenges in drug discovery for Botulinum neurotoxins.

  11. Crystal structure of the FLT3 kinase domain bound to the inhibitor quizartinib (AC220)

    SciTech Connect

    Zorn, Julie A.; Wang, Qi; Fujimura, Eric; Barros, Tiago; Kuriyan, John; Boggon, Titus J.

    2015-04-02

    More than 30% of acute myeloid leukemia (AML) patients possess activating mutations in the receptor tyrosine kinase FMS-like tyrosine kinase 3 or FLT3. A small-molecule inhibitor of FLT3 (known as quizartinib or AC220) that is currently in clinical trials appears promising for the treatment of AML. Here, we report the co-crystal structure of the kinase domain of FLT3 in complex with quizartinib. FLT3 with quizartinib bound adopts an “Abl-like” inactive conformation with the activation loop stabilized in the “DFG-out” orientation and folded back onto the kinase domain. This conformation is similar to that observed for the uncomplexed intracellular domain of FLT3 as well as for related receptor tyrosine kinases, except for a localized induced fit in the activation loop. The co-crystal structure reveals the interactions between quizartinib and the active site of FLT3 that are key for achieving its high potency against both wild-type FLT3 as well as a FLT3 variant observed in many AML patients. This co-complex further provides a structural rationale for quizartinib-resistance mutations.

  12. Crystal structure of the FLT3 kinase domain bound to the inhibitor quizartinib (AC220)

    DOE PAGES [OSTI]

    Zorn, Julie A.; Wang, Qi; Fujimura, Eric; Barros, Tiago; Kuriyan, John; Boggon, Titus J.

    2015-04-02

    More than 30% of acute myeloid leukemia (AML) patients possess activating mutations in the receptor tyrosine kinase FMS-like tyrosine kinase 3 or FLT3. A small-molecule inhibitor of FLT3 (known as quizartinib or AC220) that is currently in clinical trials appears promising for the treatment of AML. Here, we report the co-crystal structure of the kinase domain of FLT3 in complex with quizartinib. FLT3 with quizartinib bound adopts an “Abl-like” inactive conformation with the activation loop stabilized in the “DFG-out” orientation and folded back onto the kinase domain. This conformation is similar to that observed for the uncomplexed intracellular domain ofmore » FLT3 as well as for related receptor tyrosine kinases, except for a localized induced fit in the activation loop. The co-crystal structure reveals the interactions between quizartinib and the active site of FLT3 that are key for achieving its high potency against both wild-type FLT3 as well as a FLT3 variant observed in many AML patients. This co-complex further provides a structural rationale for quizartinib-resistance mutations.« less

  13. Structural basis for the blockade of MATE multidrug efflux pumps

    DOE PAGES [OSTI]

    Radchenko, Martha; Symersky, Jindrich; Nie, Rongxin; Lu, Min

    2015-08-06

    Multidrug and toxic compound extrusion (MATE) transporters underpin multidrug resistance by using the H+ or Na+ electrochemical gradient to extrude different drugs across cell membranes. MATE transporters can be further parsed into the DinF, NorM and eukaryotic subfamilies based on their amino-acid sequence similarity. Here we report the 3.0 Å resolution X-ray structures of a protonation-mimetic mutant of an H+-coupled DinF transporter, as well as of an H+-coupled DinF and a Na+-coupled NorM transporters in complexes with verapamil, a small-molecule pharmaceutical that inhibits MATE-mediated multidrug extrusion. Combining structure-inspired mutational and functional studies, we confirm the biological relevance of our crystalmore » structures, reveal the mechanistic differences among MATE transporters, and suggest how verapamil inhibits MATE-mediated multidrug efflux. Our findings offer insights into how MATE transporters extrude chemically and structurally dissimilar drugs and could inform the design of new strategies for tackling multidrug resistance.« less

  14. Synthesis and characterization of 6,6’-bis(2-hydroxyphenyl)-2,2’-bipyridine ligand and its interaction with ct-DNA

    SciTech Connect

    Selamat, Norhidayah; Heng, Lee Yook; Hassan, Nurul Izzaty; Karim, Nurul Huda Abd

    2015-09-25

    The tetradentate ligand with four donor atoms OONN was synthesized. Bis(phenoxy)bipyridine ligand was prepared by Suzuki coupling reaction between 6,6’-dibromo-2,2’-bipyridyl and 2-hydroxyphenylboronic acid with presence of palladium (II) acetate. Bis(phenoxy)bipyridine ligand was also synthesized by demethylating of 6,6’-bis(2-methoxyphenyl)-2,2’-bipyridyl ligand through solvent free reaction using pyridine hydrocloride. The formation of both phenoxy and methoxy ligands was confirmed by {sup 1}H, 2D cosy and {sup 13}C NMR spectroscopy, ESI-MS spectrometry, FTIR spectroscopy. The purity of the ligand was confirmed by melting point. Binding studies of small molecules with DNA are useful to understand the reaction mechanism and to provide guidance for the application and design of new and more efficient drugs targeted to DNA. In this study, the binding interaction between the synthesized ligand with calf thymus-DNA (ct-DNA) has been investigated by UV/Vis DNA titration study. From the UV/Vis DNA study, it shows that bis(phenoxy)bipyridine ligand bind with ct-DNA via outside binding with binding contant K{sub b} = 1.19 × 10{sup 3} ± 0.08 M{sup −1}.

  15. Tramonto

    Energy Science and Technology Software Center

    2007-01-01

    Tramonto is a code for performing molecular theory calculations using a matrix-based Newton’s method approach for 1D, 2D, and 3D geometries. More specifically the code solves the integral equations of a particular class of liquid state theory namely density functional theories (DFT) of inhomogeneous fluids in order to predict the structure and thermodynamic properties of fluids near surfaces, in porous media, or near macromolecules. It can also be used to study self-assembling systems such asmore » lamellae forming diblock copolymers or lipid bilayers. The types of fluids currently treated by the code include atomistic fluids (hard spheres, Lennard-Jones, ions, etc), freely-jointed polymers, and small molecules with bond constraints. The system of equations solved by this code are integral equations of finite range. They lead to sparse matrices for large physical systems, but rather dense matrices when the physical systems are small. The systems of equations are solved using a real space matrix based Newton’s method. Standard freely available parallel iterative solvers many be used to solve the problem (see Aztecoo from Sandia’s Trilinos project). Alternatively, specialized Schur complement based solvers developed for more efficient solution of these semi-dense matrices may be used.« less

  16. Multidimensional profiling of cell surface proteins and nuclear markers

    SciTech Connect

    Han, Ju; Chang, Hang; Andarawewa, Kumari; Yaswen, Paul; Helen Barcellos-Hoff, Mary; Parvin, Bahram

    2009-01-30

    Cell membrane proteins play an important role in tissue architecture and cell-cell communication. We hypothesize that segmentation and multidimensional characterization of the distribution of cell membrane proteins, on a cell-by-cell basis, enable improved classification of treatment groups and identify important characteristics that can otherwise be hidden. We have developed a series of computational steps to (i) delineate cell membrane protein signals and associate them with a specific nucleus; (ii) compute a coupled representation of the multiplexed DNA content with membrane proteins; (iii) rank computed features associated with such a multidimensional representation; (iv) visualize selected features for comparative evaluation through heatmaps; and (v) discriminate between treatment groups in an optimal fashion. The novelty of our method is in the segmentation of the membrane signal and the multidimensional representation of phenotypic signature on a cell-by-cell basis. To test the utility of this method, the proposed computational steps were applied to images of cells that have been irradiated with different radiation qualities in the presence and absence of other small molecules. These samples are labeled for their DNA content and E-cadherin membrane proteins. We demonstrate that multidimensional representations of cell-by-cell phenotypes improve predictive and visualization capabilities among different treatment groups, and identify hidden variables.

  17. Investigating the Role of the Outer-Coordination Sphere in [Ni(PPh2NPh-R2)2]2+ Hydrogenase Mimics

    SciTech Connect

    Jain, Avijita; Reback, Matthew L.; Lindstrom, Mary L.; Thogerson, Colleen E.; Helm, Monte L.; Appel, Aaron M.; Shaw, Wendy J.

    2012-06-18

    A series of dipeptide nickel complexes with the general formula, [Ni(PPh2NNNA-amino acid/ester2)2](BF4)2, have been synthesized and characterized (P2N2= 1,5-diaza-3,7-diphosphacyclooctane, amino acid/esters = glutamic acid, alanine, lysine, and aspartic acid). Each of these complexes is an efficient electrocatalyst for H2 production. The contribution of the outer-coordination sphere, specifically the impact of sterics, the ability to protonate and the pKa of amino acid side chain on the hydrogen production activity of these complexes, was investigated. The rates of all of the catalysts ranged over an order of magnitude. The amino acid containing complexes display 2-3 times higher rates of hydrogen production than the corresponding ester complexes, suggesting the significance of protonated species (side chains/backbone of amino acids) in the outer-coordination sphere. The largest had the fastest rates suggesting that catalytic activity is not hindered by sterics. However, the shapes of catalytic waves are indicative of hindered electron transfer and may suggest a competing mechanism for catalysis than that observed for the unsubstituted parent complex. These studies demonstrate the significant contribution that the outer-coordination sphere can have in tuning the catalytic activity of small molecule hydrogenase mimics.

  18. SHELXT – Integrated space-group and crystal-structure determination

    SciTech Connect

    Sheldrick, George M.

    2015-01-01

    SHELXT automates routine small-molecule structure determination starting from single-crystal reflection data, the Laue group and a reasonable guess as to which elements might be present. The new computer program SHELXT employs a novel dual-space algorithm to solve the phase problem for single-crystal reflection data expanded to the space group P1. Missing data are taken into account and the resolution extended if necessary. All space groups in the specified Laue group are tested to find which are consistent with the P1 phases. After applying the resulting origin shifts and space-group symmetry, the solutions are subject to further dual-space recycling followed by a peak search and summation of the electron density around each peak. Elements are assigned to give the best fit to the integrated peak densities and if necessary additional elements are considered. An isotropic refinement is followed for non-centrosymmetric space groups by the calculation of a Flack parameter and, if appropriate, inversion of the structure. The structure is assembled to maximize its connectivity and centred optimally in the unit cell. SHELXT has already solved many thousand structures with a high success rate, and is optimized for multiprocessor computers. It is, however, unsuitable for severely disordered and twinned structures because it is based on the assumption that the structure consists of atoms.

  19. Insights into the binding of PARP inhibitors to the catalytic domain of human tankyrase-2

    SciTech Connect

    Qiu, Wei; Lam, Robert; Voytyuk, Oleksandr; Romanov, Vladimir; Gordon, Roni; Gebremeskel, Simon; Vodsedalek, Jakub; Thompson, Christine; Beletskaya, Irina; Battaile, Kevin P.; Pai, Emil F.; Rottapel, Robert; Chirgadze, Nickolay Y.

    2014-07-31

    The poly(ADP-ribose) polymerase (PARP) family represents a new class of therapeutic targets with diverse potential disease indications. PARP1 and PARP2 inhibitors have been developed for breast and ovarian tumors manifesting double-stranded DNA-repair defects, whereas tankyrase 1 and 2 (TNKS1 and TNKS2, also known as PARP5a and PARP5b, respectively) inhibitors have been developed for tumors with elevated β-catenin activity. As the clinical relevance of PARP inhibitors continues to be actively explored, there is heightened interest in the design of selective inhibitors based on the detailed structural features of how small-molecule inhibitors bind to each of the PARP family members. Here, the high-resolution crystal structures of the human TNKS2 PARP domain in complex with 16 various PARP inhibitors are reported, including the compounds BSI-201, AZD-2281 and ABT-888, which are currently in Phase 2 or 3 clinical trials. These structures provide insight into the inhibitor-binding modes for the tankyrase PARP domain and valuable information to guide the rational design of future tankyrase-specific inhibitors.

  20. Improved Catalysts for Heavy Oil Upgrading Based on Zeolite Y Nanoparticles Encapsulated Stable Nanoporous Host

    SciTech Connect

    Conrad Ingram; Mark Mitchell

    2007-09-30

    The objective of this project is to synthesize nanocrystals of highly acidic zeolite Y nanoclusters, encapsulate them within the channels of mesoporous (nanoporous) silicates or nanoporous organosilicates, and evaluate the 'zeolite Y/Nanoporous host' composites as catalysts for the upgrading of heavy petroleum feedstocks. In comparison to conventionally-used zeolite Y catalysts of micron size particles, the nanocrystals (< 100 nm particle size) which contain shorter path lengths, are expected to allow faster diffusion of large hydrocarbon substrates and the catalysis products within and out of the zeolite's channels and cages (<1 nm size). This is expected to significantly reduce deactivation of the catalyst and to prolong their period of reactivity. Encapsulating zeolite Y nanocrystals within the nanoporous materials is expected to protect its external surfaces and pore entrances from being blocked by large hydrocarbon substrates, since these substrates will initially be converted to small molecules by the nanoporous host (a catalyst in its own right). The project consisted of four major tasks as follows: (1) synthesis of the nanoparticles of zeolite Y (of various chemical compositions) using various techniques such as the addition of organic additives to conventional zeolite Y synthesis mixtures to suppress zeolite Y crystal growth; (2) synthesis of nanoporous silicate host materials of up to 30 nm pore diameter, using poly (alkylene oxide) copolymers which when removed will yield a mesoporous material; (3) synthesis of zeolite Y/Nanoporous Host composite materials as potential catalysts; and (4) evaluation of the catalyst for the upgrading of heavy petroleum feedstocks.

  1. Structure of the Escherichia coli Phosphonate Binding Protein PhnD and Rationally Optimized Phosphonate Biosensors

    SciTech Connect

    Alicea, Ismael; Marvin, Jonathan S.; Miklos, Aleksandr E.; Ellington, Andrew D.; Looger, Loren L.; Schreiter, Eric R.

    2012-09-17

    The phnD gene of Escherichia coli encodes the periplasmic binding protein of the phosphonate (Pn) uptake and utilization pathway. We have crystallized and determined structures of E. coli PhnD (EcPhnD) in the absence of ligand and in complex with the environmentally abundant 2-aminoethylphosphonate (2AEP). Similar to other bacterial periplasmic binding proteins, 2AEP binds near the center of mass of EcPhnD in a cleft formed between two lobes. Comparison of the open, unliganded structure with the closed 2AEP-bound structure shows that the two lobes pivot around a hinge by {approx}70{sup o} between the two states. Extensive hydrogen bonding and electrostatic interactions stabilize 2AEP, which binds to EcPhnD with low nanomolar affinity. These structures provide insight into Pn uptake by bacteria and facilitated the rational design of high signal-to-noise Pn biosensors based on both coupled small-molecule dyes and autocatalytic fluorescent proteins.

  2. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    SciTech Connect

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; Adzic, Radoslav R.

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs). Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.

  3. Protective spin-labeled fluorenes maintain amyloid beta peptide in small oligomers and limit transitions in secondary structure

    DOE PAGES [OSTI]

    Altman, Robin; Ly, Sonny; Hilt, Silvia; Petrlova, Jitka; Maezawa, Izumi; Kálai, Tamás; Hideg, Kálmán; Jin, Lee-Way; Laurence, Ted A.; Voss, John C.

    2015-12-01

    Alzheimer’s disease is characterized by the presence of extracellular plaques comprised of amyloid beta (Aβ) peptides. Soluble oligomers of the Aβ peptide underlie a cascade of neuronal loss and dysfunction associated with Alzheimer's disease. Single particle analyses of Aβ oligomers in solution by fluorescence correlation spectroscopy (FCS) were used to provide real-time descriptions of how spin-labeled fluorenes (SLFs; bi-functional small molecules that block the toxicity of Aβ) prevent and disrupt oligomeric assemblies of Aβ in solution. The FCS results, combined with electron paramagnetic resonance spectroscopy and circular dichroism spectroscopy, demonstrate SLFs can inhibit the growth of Aβ oligomers and disruptmore » existing oligomers while retaining Aβ in a largely disordered state. Furthermore, while the ability of SLF to block Aβ toxicity correlates with a reduction in oligomer size, our results suggest the conformation of Aβ within the oligomer determines the toxicity of the species. Attenuation of Aβ toxicity, which has been associated primarily with the soluble oligomeric form, can be achieved through redistribution of the peptides into smaller oligomers and arrest of the fractional increase in beta secondary structure.« less

  4. Evaluation of Nanolipoprotein Particles (NLPs) as an In Vivo Delivery Platform

    SciTech Connect

    Fischer, Nicholas O.; Weilhammer, Dina R.; Dunkle, Alexis; Thomas, Cynthia; Hwang, Mona; Corzett, Michele; Lychak, Cheri; Mayer, Wasima; Urbin, Salustra; Collette, Nicole; Chiun Chang, Jiun; Loots, Gabriela G.; Rasley, Amy; Blanchette, Craig D.; Ceña, Valentin

    2014-03-27

    Nanoparticles hold great promise for the delivery of therapeutics, yet limitations remain with regards to the use of these nanosystems for efficient long-lasting targeted delivery of therapeutics, including imparting functionality to the platform, in vivo stability, drug entrapment efficiency and toxicity. In order to begin to address these limitations, we evaluated the functionality, stability, cytotoxicity, toxicity, immunogenicity and in vivo biodistribution of nanolipoprotein particles (NLPs), which are mimetics of naturally occurring high-density lipoproteins (HDLs). We also found that a wide range of molecules could be reliably conjugated to the NLP, including proteins, single-stranded DNA, and small molecules. The NLP was also found to be relatively stable in complex biological fluids and displayed no cytotoxicity in vitro at doses as high as 320 µg/ml. In addition, we observed that in vivo administration of the NLP daily for 14 consecutive days did not induce significant weight loss or result in lesions on excised organs. Furthermore, the NLPs did not display overt immunogenicity with respect to antibody generation. Finally, the biodistribution of the NLP in vivo was found to be highly dependent on the route of administration, where intranasal administration resulted in prolonged retention in the lung tissue. Though only a select number of NLP compositions were evaluated, the findings of this study suggest that the NLP platform holds promise for use as both a targeted and non-targeted in vivo delivery vehicle for a range of therapeutics.

  5. Nanoconfined catalytic Ångström-size motors

    SciTech Connect

    Colberg, Peter H. Kapral, Raymond

    2015-11-14

    Self-propelled chemically powered synthetic micron and nano-scale motors are being intensively studied because of the wide range of potential applications that exploit their directed motion. This paper considers even smaller Ångström-size synthetic motors. Such very small motors in bulk solution display effects arising from their self-propulsion. Recent experiments have shown that small-molecule catalysts and single enzyme molecules exhibit properties that have been attributed to their chemical activity. Molecular dynamics is used to investigate the properties of very small Ångström-size synthetic chemically powered sphere-dimer motors in a simple atomic-like solvent confined between walls separated by distances of tens of nanometers. Evidence for strong structural ordering of the motors between the walls, which reflects the finite size of solvent molecules and depends on solvent depletion forces, is provided. Dynamical properties, such as average motor velocity, orientational relaxation, and mean square displacement, are anisotropic and depend on the distance from the walls. This research provides information needed for potential applications that use molecular-scale motors in the complex confined geometries encountered in biology and the laboratory.

  6. Biodegradability of regenerated cellulose films coated with polyurethane/natural polymers interpenetrating polymer networks

    SciTech Connect

    Zhang, L.; Zhou, J.; Huang, J.; Gong, P. Zhou, Q.; Zheng, L.; Du, Y.

    1999-11-01

    Interpenetrating polymer network (IPN) coatings synthesized from castor-oil-based polyurethane (PU) with chitosan, nitrocellulose, or elaeostearin were coated on regenerated cellulose (RC) film for curing at 80--100 C for 2--5 min, providing biodegradable, water-resistant cellulose films coded, respectively, as RCCH, RCNC, and RCEs. The coated films were buried in natural soil for decaying and inoculated with a spore suspension of fungi on the agar medium, respectively, to test biodegradability. The viscosity-average molecular weight, M{sub {eta}}, and the weight of the degraded films decreased sharply with the progress of degradation. The degradation half-lifes, t{sub 1/2}, of the films in soil at 30 C were found to be 19 days for RC, 25 days for RCNC, 32 days for RCCH, and 45 days for the RCEs films. Scanning electron microscopy (SEM) showed that the extent of decay followed in the order RC {gt} RCNC {gt} RCCH {gt} RCEs. SEM, infrared (IR), high-performance liquid chromatography (HPLC), and CO{sub 2} evolution results indicated that the microorganisms directly attacked the water-resistant coating layer and then penetrated into the cellulose to speedily metabolize, while accompanying with producing CO{sub 2}, H{sub 2}O, glucose cleaved from cellulose, and small molecules decomposed from the coatings.

  7. Water Oxidation and Oxygen Monitoring by Cobalt-Modified Fluorine-Doped Tin Oxide Electrodes

    SciTech Connect

    Kent, CA; Concepcion, JJ; Dares, CJ; Torelli, DA; Rieth, AJ; Miller, AS; Hoertz, PG; Meyer, TJ

    2013-06-12

    Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O-2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29 000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of similar to 5

  8. Crystallographic study of FABP5 as an intracellular endocannabinoid transporter

    SciTech Connect

    Sanson, Benot; Wang, Tao; Sun, Jing; Wang, Liqun; Kaczocha, Martin; Ojima, Iwao; Deutsch, Dale; Li, Huilin

    2014-02-01

    FABP5 was recently found to intracellularly transport endocannabinoid signaling lipids. The structures of FABP5 complexed with two endocannabinoids and an inhibitor were solved. Human FABP5 was found to dimerize via a domain-swapping mechanism. This work will help in the development of inhibitors to raise endocannabinoid levels. In addition to binding intracellular fatty acids, fatty-acid-binding proteins (FABPs) have recently been reported to also transport the endocannabinoids anandamide (AEA) and 2-arachidonoylglycerol (2-AG), arachidonic acid derivatives that function as neurotransmitters and mediate a diverse set of physiological and psychological processes. To understand how the endocannabinoids bind to FABPs, the crystal structures of FABP5 in complex with AEA, 2-AG and the inhibitor BMS-309403 were determined. These ligands are shown to interact primarily with the substrate-binding pocket via hydrophobic interactions as well as a common hydrogen bond to the Tyr131 residue. This work advances our understanding of FABP5endocannabinoid interactions and may be useful for future efforts in the development of small-molecule inhibitors to raise endocannabinoid levels.

  9. A spectroscopic view of internal conversion in a small polyatomic molecule: Sub-Doppler intracavity dye laser spectroscopy of thioformaldehyde

    SciTech Connect

    Clouthier, D.J. (Department of Chemistry, University of Kentucky, Lexington, Kentucky 40506-0055 (United States)); Huang, G.; Merer, A.J. (Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, B. C. V6T 1Z1 (Canada))

    1992-08-01

    Intracavity dye laser spectroscopy has been used to obtain sub-Doppler spectra of selected rotational lines in the {ital {tilde A}} {sup 1}{ital A}{sub 2}--{ital {tilde X}} {sup 1}{ital A}{sub 1} 4{sup 1}{sub 0} band of thioformaldehyde with very high resolution and sensitivity. Many of the spectra show extra lines due to perturbations involving high vibrational levels of the ground state. Most of the perturbations observed for {ital K}{sup {prime}}{sub {ital a}} = 0 and 4 are found to correlate well with previous observations of anomalously long single rotational level fluorescence lifetimes and reduced quantum yields (J. Dunlop and D. J. Clouthier, J. Chem. Phys. {bold 93}, 6371 (1990)). {ital S}{sub 1}--{ital S}{sub 0} interaction matrix elements of 0.001--0.006 cm{sup {minus}1} are found for levels involved in simple two level perturbations. The large number of small random perturbations by levels of the ground state is indicative of the first stages of the onset of quantum chaos in a small molecule. Some larger perturbations in the rotational structure are also observed; these are caused by additional local interactions with levels of the nearby triplet state.

  10. Binding of the Respiratory Chain Inhibitor Antimycin to theMitochondrial bc1 Complex: A New Crystal Structure Reveals an AlteredIntramolecular Hydrogen-Bonding Pattern

    SciTech Connect

    Huang, Li-shar; Cobessi, David; Tung, Eric Y.; Berry, Edward A.

    2005-05-10

    Antimycin A (antimycin), one of the first known and most potent inhibitors of the mitochondrial respiratory chain, binds to the quinone reduction site of the cytochrome bc1 complex.Structure-activity-relationship studies have shown that the N-formylamino-salicyl-amide group is responsible for most of the binding specificity, and suggested that a low pKa for the phenolic OH group and an intramolecular H-bond between that OH and the carbonyl O of the salicylamide linkage are important. Two previous X-ray structures of antimycin bound to vertebrate bc1 complex gave conflicting results. A new structure reported here of the bovine mitochondrial bc1 complex at 2.28Angstrom resolution with antimycin bound, allows us for the first time to reliably describe the binding of antimycin and shows that the intramolecular hydrogen bond described in solution and in the small-molecule structure is replaced by one involving the NH rather than carbonyl O of the amide linkage, with rotation of the amide group relative to the aromatic ring. The phenolic OH and formylamino N form H-bonds with conserved Asp228 of cyt b, and the formylamino O H-bonds via a water molecule to Lys227. A strong density the right size and shape for a diatomic molecule is found between the other side of the dilactone ring and the alpha-A helix.

  11. For Stimul-Responsive Polymers with Enhanced Efficiency in Reservoir Recovery Processes

    SciTech Connect

    Charles McCormick; Roger Hester

    2003-02-28

    Acrylamide-based hydrophobically modified (HM) polybetaines containing N-butylphenylacrylamide (BPAM) and varying amounts of either sulfobetaine (3-(2-acrylamido-2-methylpropanedimethylammonio)-1-propanesulfonate, AMPDAPS) or carboxybetaine (4-(2-acrylamido-2-methylpropyldimethylammonio) butanoate, AMPDAB) comonomers were synthesized via micellar copolymerization. The terpolymers were characterized via {sup 13}C NMR and UV spectroscopies, classical and dynamic light scattering, and potentiometric titration. The response of aqueous polymer solutions to various external stimuli, including changes in solution pH, electrolyte concentration, and the addition of small molecule surfactants, was investigated using surface tension and rheological measurements. Low charge density terpolymers were found to show greater viscosity enhancement upon the addition of surfactant compared to the high charge density terpolymers. The addition of sodium dodecyl sulfate (SDS) produced the largest maximum in solution viscosity, while N-dodecyl-N,N,N-trimethylammonium bromide (DTAB), N-dodecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-12), and Triton X-100 tended to show reduced viscosity enhancement. In most cases, the high charge density carboxybetaine terpolymer exhibited diminished solution viscosities upon surfactant addition. In our last report, we discussed solution thermodynamic theory that described changes in polymer coil conformation as a function of solution temperature and polymer molecular weight. These polymers contained no ionic charges. In this report, we expand polymer solution theory to account for the electrostatic interactions present in solutions of charged polymers. Polymers with ionic charges are referred to as polyions or polyelectrolytes.

  12. Correlating the chemical composition and size of various metal oxide substrates with the catalytic activity and stability of as-deposited Pt nanoparticles for the methanol oxidation reaction

    DOE PAGES [OSTI]

    Megan E. Scofield; Wong, Stanislaus S.; Koenigsmann, Christopher; Bobb-Semple, Dara; Tao, Jing; Tong, Xiao; Wang, Lei; Lewis, Crystal S.; Vuklmirovic, Miomir; Zhu, Yimei; et al

    2015-12-09

    The performance of electrode materials in conventional direct alcohol fuel cells (DAFC) is constrained by (i) the low activity of the catalyst materials relative to their overall cost, (ii) the poisoning of the active sites due to the presence of partially oxidized carbon species (such as but not limited to CO, formate, and acetate) produced during small molecule oxidation, and (iii) the lack of catalytic stability and durability on the underlying commercial carbon support. Therefore, as a viable alternative, we have synthesized various metal oxide and perovskite materials of different sizes and chemical compositions as supports for Pt nanoparticles (NPs).more » Our results including unique mechanistic studies demonstrate that the SrRuO3 substrate with immobilized Pt NPs at its surface evinces the best methanol oxidation performance as compared with all of the other substrate materials tested herein, including commercial carbon itself. In addition, data from electron energy loss spectroscopy (EELS) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of electron transfer from bound Pt NPs to surface Ru species within the SrRuO3 substrate itself, thereby suggesting that favorable metal support interactions are responsible for the increased methanol oxidation reaction (MOR) activity of Pt species with respect to the underlying SrRuO3 composite catalyst material.« less

  13. A transferable coarse-grained model for diphenylalanine: How to represent an environment driven conformational transition

    SciTech Connect

    Dalgicdir, Cahit; Sensoy, Ozge; Sayar, Mehmet; Peter, Christine

    2013-12-21

    One of the major challenges in the development of coarse grained (CG) simulation models that aim at biomolecular structure formation processes is the correct representation of an environment-driven conformational change, for example, a folding/unfolding event upon interaction with an interface or upon aggregation. In the present study, we investigate this transferability challenge for a CG model using the example of diphenylalanine. This dipeptide displays a transition from a trans-like to a cis-like conformation upon aggregation as well as upon transfer from bulk water to the cyclohexane/water interface. Here, we show that one can construct a single CG model that can reproduce both the bulk and interface conformational behavior and the segregation between hydrophobic/hydrophilic medium. While the general strategy to obtain nonbonded interactions in the present CG model is to reproduce solvation free energies of small molecules representing the CG beads in the respective solvents, the success of the model strongly depends on nontrivial decisions one has to make to capture the delicate balance between the bonded and nonbonded interactions. In particular, we found that the peptide's conformational behavior is qualitatively affected by the cyclohexane/water interaction potential, an interaction that does not directly involve the peptide at all but merely influences the properties of the hydrophobic/hydrophilic interface. Furthermore, we show that a small modification to improve the structural/conformational properties of the CG model could dramatically alter the thermodynamic properties.

  14. Significant decrease of ADP release rate underlies the potent activity of dimethylenastron to inhibit mitotic kinesin Eg5 and cancer cell proliferation

    SciTech Connect

    Sun, Linlin; Sun, Xiaodong; Xie, Songbo; Yu, Haiyang; Zhong, Diansheng

    2014-05-09

    Highlights: • DIMEN displays higher anti-proliferative activity than enastron. • DIMEN induced mitotic arrest and apoptosis more significantly than enastron. • DIMEN blocked the conformational change of ADP-binding pocket more effectively. • DIMEN hindered ADP release more potently than enastron. - Abstract: Eg5 is a mitotic kinesin that plays a crucial role in the formation of bipolar mitotic spindles, by hydrolyzing ATP to push apart anti-parallel microtubules. Dimethylenastron is potent specific small molecule inhibitor of Eg5. The mechanism by which dimethylenastron inhibits Eg5 function remains unclear. By comparing with enastron, here we report that dimethylenastron prevents the growth of pancreatic and lung cancer cells more effectively, by halting mitotic progression and triggering apoptosis. We analyze their interactions with ADP-bound Eg5 crystal structure, and find that dimethylenastron binds Eg5 motor domain with higher affinity. In addition, dimethylenastron allosterically blocks the conformational change of the “sandwich”-like ADP-binding pocket more effectively. We subsequently use biochemical approach to reveal that dimethylenastron slows ADP release more significantly than enastron. These data thus provide biological, structural and mechanistic insights into the potent inhibitory activity of dimethylenastron.

  15. A mutation in the mitochondrial protein UQCRB promotes angiogenesis through the generation of mitochondrial reactive oxygen species

    SciTech Connect

    Chang, Junghwa; Jung, Hye Jin; Jeong, Seung Hun; Kim, Hyoung Kyu; Han, Jin; Kwon, Ho Jeong

    2014-12-12

    Highlights: • We constructed mitochondrial protein UQCRB mutant stable cell lines on the basis of a human case report. • These mutant cell lines exhibit pro-angiogenic activity with enhanced VEGF expression. • Proliferation of mutant cell lines was regulated by UQCRB inhibitors. • UQCRB may have a functional role in angiogenesis. - Abstract: Ubiquinol-cytochrome c reductase binding protein (UQCRB) is one of the subunits of mitochondrial complex III and is a target protein of the natural anti-angiogenic small molecule terpestacin. Previously, the biological role of UQCRB was thought to be limited to the maintenance of complex III. However, the identification and validation of UQCRB as a target protein of terpestacin enabled the role of UQCRB in oxygen sensing and angiogenesis to be elucidated. To explore the biological role of this protein further, UQCRB mutant stable cell lines were generated on the basis of a human case report. We demonstrated that these cell lines exhibited glycolytic and pro-angiogenic activities via mitochondrial reactive oxygen species (mROS)-mediated HIF1 signal transduction. Furthermore, a morphological abnormality in mitochondria was detected in UQCRB mutant stable cell lines. In addition, the proliferative effect of the UQCRB mutants was significantly regulated by the UQCRB inhibitors terpestacin and A1938. Collectively, these results provide a molecular basis for UQCRB-related biological processes and reveal potential key roles of UQCRB in angiogenesis and mitochondria-mediated metabolic disorders.

  16. Device for isolation of seed crystals during processing of solution

    DOEpatents

    Montgomery, Kenneth E.; Zaitseva, Natalia P.; Deyoreo, James J.; Vital, Russell L.

    1999-01-01

    A device for isolation of see crystals during processing of solutions. The device enables a seed crystal to be introduced into the solution without exposing the solution to contaminants or to sources of drying and cooling. The device constitutes a seed protector which allows the seed to be present in the growth solution during filtration and overheating operations while at the same time preventing the seed from being dissolved by the under saturated solution. When the solution processing has been completed and the solution cooled to near the saturation point, the seed protector is opened, exposing the seed to the solution and allowing growth to begin.

  17. Enhancing the emission directionality of organic light-emitting diodes by using photonic microstructures

    SciTech Connect

    Zhang, Shuyu; Turnbull, Graham A., E-mail: gat@st-andrews.ac.uk, E-mail: idws@st-andrews.ac.uk; Samuel, Ifor D. W., E-mail: gat@st-andrews.ac.uk, E-mail: idws@st-andrews.ac.uk [Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, Fife KY16 9SS (United Kingdom)] [Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, North Haugh, St Andrews, Fife KY16 9SS (United Kingdom)

    2013-11-18

    We report microstructured organic light-emitting diodes (OLEDs) with directional emission based on efficient solution-processable europium-OLEDs patterned by solvent assisted microcontact molding. The angle dependence of the light emission is characterized for OLEDs with square-array photonic crystals with periods between 275?nm and 335?nm. The microstructured devices have emission patterns strongly modified from the Lambertian emission of planar OLEDs and can approximately double the emitted power in a desired angle range in both s- and p-polarizations. The modified emission is attributed to light diffracted out of the waveguide modes of the OLEDs.

  18. Fused thiophene-based conjugated polymers and their use in optoelectronic devices

    SciTech Connect

    Facchetti, Antonio; Marks, Tobin J; Takai, Atsuro; Seger, Mark; Chen, Zhihua

    2015-11-03

    The present teachings relate to certain polymeric compounds and their use as organic semiconductors in organic and hybrid optical, optoelectronic, and/or electronic devices such as photovoltaic cells, light emitting diodes, light emitting transistors, and field effect transistors. The disclosed compounds can provide improved device performance, for example, as measured by power conversion efficiency, fill factor, open circuit voltage, field-effect mobility, on/off current ratios, and/or air stability when used in photovoltaic cells or transistors. The disclosed compounds can have good solubility in common solvents enabling device fabrication via solution processes.

  19. Perovskite&ndash;fullerene hybrid materials suppress hysteresis in planar diodes

    Office of Scientific and Technical Information (OSTI)

    14 Nov 2014 | Accepted 31 Mar 2015 | Published 8 May 2015 DOI: 10.1038/ncomms8081 OPEN Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes Jixian Xu1, Andrei Buin1, Alexander H. Ip1, Wei Li1, Oleksandr Voznyy1, Riccardo Comin1, Mingjian Yuan1, Seokmin Jeon2, Zhijun Ning1, Jeffrey J. McDowell1, Pongsakorn Kanjanaboos1, Jon-Paul Sun3, Xinzheng Lan1, Li Na Quan4, Dong Ha Kim4, Ian G. Hill3, Peter Maksymovych2 & Edward H. Sargent1 Solution-processed planar perovskite

  20. White-blue electroluminescence from a Si quantum dot hybrid light-emitting diode

    SciTech Connect

    Xin, Yunzi; Nishio, Kazuyuki; Saitow, Ken-ichi

    2015-05-18

    A silicon (Si) quantum dot (QD)-based hybrid inorganic/organic light-emitting diode (LED) was fabricated via solution processing. This device exhibited white-blue electroluminescence at a low applied voltage of 6?V, with 78% of the effective emission obtained from the Si QDs. This hybrid LED produced current and optical power densities 280 and 350 times greater than those previously reported for such device. The superior performance of this hybrid device was obtained by both the prepared Si QDs and the optimized layer structure and thereby improving carrier migration through the hybrid LED and carrier recombination in the homogeneous Si QD layer.

  1. Device for isolation of seed crystals during processing of solution

    DOEpatents

    Montgomery, K.E.; Zaitseva, N.P.; Deyoreo, J.J.; Vital, R.L.

    1999-05-18

    A device is described for isolation of seed crystals during processing of solutions. The device enables a seed crystal to be introduced into the solution without exposing the solution to contaminants or to sources of drying and cooling. The device constitutes a seed protector which allows the seed to be present in the growth solution during filtration and overheating operations while at the same time preventing the seed from being dissolved by the under saturated solution. When the solution processing has been completed and the solution cooled to near the saturation point, the seed protector is opened, exposing the seed to the solution and allowing growth to begin. 3 figs.

  2. Progress of Planar Perovskite Solar Cells for Efficiencies above 20% |

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    MIT-Harvard Center for Excitonics Progress of Planar Perovskite Solar Cells for Efficiencies above 20% November 2, 2016 at 3:30 PM/ 36-462 Juan-Pablo Correa-Baena Massachusetts Institute of Technology, Department of Mechanical Engineering j.correa-epfl Perovskite solar cells (PSCs) have achieved certified power conversion efficiencies (PCEs) of 22.1% by low cost and low temperature solution processing. The highest efficiency perovskites are Pb-based with mixed MA/FA cations and Br/I halides

  3. Low-dielectric-constant polyimide aerogel composite films with low water uptake

    Office of Scientific and Technical Information (OSTI)

    5 Sep 2015 | Accepted 15 Mar 2016 | Published 21 Apr 2016 DOI: 10.1038/ncomms11330 Size-dependent phase transition in methylammonium lead iodide perovskite microplate crystals OPEN Dehui Li1, Gongming Wang1,2, Hung-Chieh Cheng3, Chih-Yen Chen1, Hao Wu3, Yuan Liu3, Yu Huang2,3 & Xiangfeng Duan1,2 Methylammonium lead iodide perovskite has attracted considerable recent interest for solution processable solar cells and other optoelectronic applications. The orthorhombic-to-tetragonal phase

  4. Scalable Parallel Algebraic Multigrid Solvers

    SciTech Connect

    Bank, R; Lu, S; Tong, C; Vassilevski, P

    2005-03-23

    The authors propose a parallel algebraic multilevel algorithm (AMG), which has the novel feature that the subproblem residing in each processor is defined over the entire partition domain, although the vast majority of unknowns for each subproblem are associated with the partition owned by the corresponding processor. This feature ensures that a global coarse description of the problem is contained within each of the subproblems. The advantages of this approach are that interprocessor communication is minimized in the solution process while an optimal order of convergence rate is preserved; and the speed of local subproblem solvers can be maximized using the best existing sequential algebraic solvers.

  5. Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells

    Office of Scientific and Technical Information (OSTI)

    May 2015 | Accepted 28 Oct 2015 | Published 30 Nov 2015 DOI: 10.1038/ncomms10030 OPEN Enhanced optoelectronic quality of perovskite thin films with hypophosphorous acid for planar heterojunction solar cells Wei Zhang1, Sandeep Pathak1, Nobuya Sakai1, Thomas Stergiopoulos1, Pabitra K. Nayak1, Nakita K. Noel1, Amir A. Haghighirad1, Victor M. Burlakov1,2, Dane W. deQuilettes3, Aditya Sadhanala4, Wenzhe Li5, Liduo Wang5, David S. Ginger3, Richard H. Friend4 & Henry J. Snaith1 Solution-processed

  6. Zircons and fluids: An experimental investigation with applications for radioactive waste disposal

    SciTech Connect

    Sinha, A.K.; Student, J.; Essex, R.

    1991-01-01

    The long-term stability of nuclear waste forms or barriers is related to changes in physical properties of the material induced through radiation damage and subsequent changes in solubility. Investigations conducted by us on natural zircons (ZrSiO{sub 4}) supports a positive correlation between level of alpha damage and fluid composition to enhanced levels of corrosion. New data are presented on the nature and rate of the solution process. We also present data on our continuing efforts to synthesize and characterize both pure ZrSiO{sub 4} and doped with U, Th, Hf, Dy and P.

  7. Challenges in halide perovskite photovoltaics

    U.S. Department of Energy (DOE) - all webpages (Extended Search)

    Perovskite PV (SUN UP) SuNLaMP project 30291 http://www.nrel.gov/ncpv/ Note on emerging PV: Lab scale, "un-stabilized" or other caveats Before Perovskite PV and post 2009 3.9 % 17.9 % 21.07% 15% - mesoporous TiO 2 2-step deposition 15.4 % co-evaporated Planar PIN 15.9 % MSSC Al 2 O 3 Solution processed CH 3 NH 3 PbI 3 Meteoric rise of efficiency in PV Performance 22.6-23% +23%?? D. B. Mitzi, C. A. Feild, W. Harrison, and A. M. Guloy, "Conducting tin halides with a layered

  8. Chemical Control of Charge Trapping and Charge Transfer Processes at the Organic-Inorganic Interface within Quantum Dot-Organic Complexes

    SciTech Connect

    Weiss, Emily A.

    2015-11-06

    Within the research program funded through the Early Career Research Award we designed complexes of colloidal semiconductor quantum dots (QDs) and organic molecules in which the interfacial chemistry controls the electronic structure and dynamics of the excitonic state of the QD. The program included two main projects; (1) investigation of the mechanisms by which organic surfactants control the quantum confinement of excitonic charge carriers; and (2) development of models for electron transfer between QDs and adsorbed molecules as a function of interfacial chemistry. This project was extremely successful in that our achievements in those two areas addressed the great majority of questions we outlined in the original proposal and answered questions I did not think to ask in that original proposal. Our work led to the discovery of “exciton delocalizing ligands”, which change the electronic structure of colloidal semiconductor nanocrystals by altering, with small synthetic modifications to their surfaces, their most defining characteristic – the quantum confinement of their excited states. It also led to detailed, quantitative descriptions of how the surface chemistry of a QD dictates, thermodynamically and kinetically, the probability of exchange of electrons between the QD and a small molecule. We used two of the three major techniques in the proposal (transient photoluminescence and transient absorption). Electrogenerated chemiluminescence was also proposed, but was too technically difficult with these systems to be useful. Instead, NMR spectroscopy emerged as a major analytical tool in our studies. With the fundamental advancements we made with this project, we believe that we can design QDs to be the next great class of visible-light photocatalysts.

  9. Chemical Technology Division annual technical report 1989

    SciTech Connect

    Not Available

    1990-03-01

    Highlights of the Chemical Technology (CMT) Division's activities during 1989 are presented. In this period, CMT conducted research and development in the following areas: (1) electrochemical technology, including high-performance batteries (mainly lithium/iron sulfide and sodium/metal chloride), aqueous batteries (lead-acid and nickel/iron), and advanced fuel cells with molten carbonate and solid oxide electrolytes: (2) coal utilization, including the heat and seed recovery technology for coal-fired magnetohydrodynamics plants and the technology for fluidized-bed combustion; (3) methods for recovery of energy from municipal waste and techniques for treatment of hazardous organic waste; (4) nuclear technology related to a process for separating and recovering transuranic elements from nuclear waste and for producing {sup 99}Mo from low-enriched uranium targets, the recovery processes for discharged fuel and the uranium blanket in a sodium-cooled fast reactor (the Integral Fast Reactor), and waste management; and (5) physical chemistry of selected materials in environments simulating those of fission and fusion energy systems. The Division also has a program in basic chemistry research in the areas of fluid catalysis for converting small molecules to desired products; materials chemistry for superconducting oxides and associated and ordered solutions at high temperatures; interfacial processes of importance to corrosion science, high-temperature superconductivity, and catalysis; and the geochemical processes responsible for trace-element migration within the earth's crust. The Division continued to be administratively responsible for and the major user of the Analytical Chemistry Laboratory at Argonne National Laboratory (ANL).

  10. Specific inhibition of Wee1 kinase and Rad51 recombinase: A strategy to enhance the sensitivity of leukemic T-cells to ionizing radiation-induced DNA double-strand breaks

    SciTech Connect

    Havelek, Radim; Cmielova, Jana; Kralovec, Karel; Bruckova, Lenka; Bilkova, Zuzana; Fousova, Ivana; Sinkorova, Zuzana; Vavrova, Jirina; Rezacova, Martina

    2014-10-24

    Highlights: • Pre-treatment with the inhibitors increased the sensitivity of Jurkat cells to irradiation. • Combining both inhibitors together resulted in a G2 cell cycle arrest abrogation in Jurkat. • Jurkat cells pre-treated with inhibitors were positive for γH2AX foci 24 h upon irradiation. • Pre-treatment with Rad51 RI-1 had no effect on apoptosis induction in MOLT-4 cells. • When dosed together, the combination decreased MOLT-4 cell survival. - Abstract: Present-day oncology sees at least two-thirds of cancer patients receiving radiation therapy as a part of their anticancer treatment. The objectives of the current study were to investigate the effects of the small molecule inhibitors of Wee1 kinase II (681641) and Rad51 (RI-1) on cell cycle progression, DNA double-strand breaks repair and apoptosis following ionizing radiation exposure in human leukemic T-cells Jurkat and MOLT-4. Pre-treatment with the Wee1 681641 or Rad51 RI-1 inhibitor alone increased the sensitivity of Jurkat cells to irradiation, however combining both inhibitors together resulted in a further enhancement of apoptosis. Jurkat cells pre-treated with inhibitors were positive for γH2AX foci 24 h upon irradiation. MOLT-4 cells were less affected by inhibitors application prior to ionizing radiation exposure. Pre-treatment with Rad51 RI-1 had no effect on apoptosis induction; however Wee1 681641 increased ionizing radiation-induced cell death in MOLT-4 cells.

  11. New models and molecular markers in evaluation of developmental toxicity

    SciTech Connect

    Huuskonen, Hannele . E-mail: hannele.huuskonen@sttv.fi

    2005-09-01

    Mammalian and non-mammalian embryos and embryonic stem cells may be used as models in mechanistic studies and in testing embryotoxicity of compounds. In addition to conventional culture methods, genetic modifications and use of molecular markers offer significant advantages in mechanistic studies as well as in developing new test methods for embryotoxicity. Zebrafish model has been used for a long time and at present several applications are available. It is an easy vertebral non-mammalian model, whose genome is largely known and several genetic modifications are easily constructed to study gene expression or knocked down genes. Fluorescent marker proteins can be used also in zebrafish to indicate gene activation in transgenic models. Chemical genetics approach has been developed using zebrafish model. This is a new approach to screen small molecules that regulate signaling pathways. Embryonic stem cells have been used in mechanistic studies and mouse embryonic stem cell test has been validated to study embryotoxicity in vitro. This method has been improved using quantitative measurements of molecular endpoints by real-time RT-PCR or fluorescent activated cell sorting methods (FACS). Methods facilitating differentiation to several different cell types are available. We have studied preimplantation mouse embryos as a possible model for in vitro testing. In this method, superovulated and in vivo fertilized preimplantation embryos were collected at morula stage and cultured up to blastocysts. The mouse preimplantation culture test was improved by quantitative gene expression measurement using two-step real-time RT-PCR methods. New endpoints improve the tests of in vitro embryotoxicity because subjective assessments are replaced by objective measurements. In addition, automation is possible and less time is needed for analysis. Thus, high throughput screening will come possible to test large numbers of compounds.

  12. Antisense inhibition of cyclin D1 expression is equivalent to flavopiridol for radiosensitization of zebrafish embryos

    SciTech Connect

    McAleer, Mary Frances; Duffy, Kevin T.; Davidson, William R.; Kari, Gabor; Dicker, Adam P.; Rodeck, Ulrich; Wickstrom, Eric . E-mail: eric@tesla.jci.tju.edu

    2006-10-01

    Purpose: Flavopiridol, a small molecule pan-cyclin inhibitor, has been shown to enhance Radiation response of tumor cells both in vitro and in vivo. The clinical utility of flavopiridol, however, is limited by toxicity, previously attributed to pleiotropic inhibitory effects on several targets affecting multiple signal transduction pathways. Here we used zebrafish embryos to investigate radiosensitizing effects of flavopiridol in normal tissues. Methods and Materials: Zebrafish embryos at the 1- to 4-cell stage were treated with 500 nM flavopiridol or injected with 0.5 pmol antisense hydroxylprolyl-phosphono nucleic acid oligomers to reduce cyclin D1 expression, then subjected to ionizing radiation (IR) or no radiation. Results: Flavopiridol-treated embryos demonstrated a twofold increase in mortality after exposure to 40 Gy by 96 hpf and developed distinct radiation-induced defects in midline development (designated as the 'curly up' phenotype) at higher rates when compared with embryos receiving IR only. Cyclin D1-deficient embryos had virtually identical IR sensitivity profiles when compared with embryos treated with flavopiridol. This was particularly evident for the IR-induced curly up phenotype, which was greatly exacerbated by both flavopriridol and cyclin D1 downregulation. Conclusions: Treatment of zebrafish embryos with flavopiridol enhanced radiation sensitivity of zebrafish embryos to a degree that was very similar to that associated with downregulation of cyclin D1 expression. These results are consistent with the hypothesis that inhibition of cyclin D1 is sufficient to account for the radiosensitizing action of flavopiridol in the zebrafish embryo vertebrate model.

  13. Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes

    SciTech Connect

    Bang, Suhee; Lee, Yong -Min; Hong, Seungwoo; Cho, Kyung -Bin; Nishida, Yusuke; Seo, Mi Sook; Sarangi, Ritimukta; Fukuzumi, Shunichi; Nam, Wonwoo

    2014-09-14

    Redox-inactive metal ions that function as Lewis acids play pivotal roles in modulating the reactivity of oxygen-containing metal complexes and metalloenzymes, such as the oxygen-evolving complex in photosystem II and its small-molecule mimics. Here we report the synthesis and characterization of non-haem iron(III)–peroxo complexes that bind redox-inactive metal ions, (TMC)FeIII–(μ,η22-O2)–Mn+ (Mn+ = Sr2+, Ca2+, Zn2+, Lu3+, Y3+ and Sc3+; TMC, 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane). We demonstrate that the Ca2+ and Sr2+ complexes showed similar electrochemical properties and reactivities in one-electron oxidation or reduction reactions. However, the properties and reactivities of complexes formed with stronger Lewis acidities were found to be markedly different. In conclusion, complexes that contain Ca2+ or Sr2+ ions were oxidized by an electron acceptor to release O2, whereas the release of O2 did not occur for complexes that bind stronger Lewis acids. Furthermore, we discuss these results in the light of the functional role of the Ca2+ ion in the oxidation of water to dioxygen by the oxygen-evolving complex.

  14. High-Throughput Genetic Analysis and Combinatorial Chiral Separations Based on Capillary Electrophoresis

    SciTech Connect

    Wenwan Zhong

    2003-08-05

    Capillary electrophoresis (CE) offers many advantages over conventional analytical methods, such as speed, simplicity, high resolution, low cost, and small sample consumption, especially for the separation of enantiomers. However, chiral method developments still can be time consuming and tedious. They designed a comprehensive enantioseparation protocol employing neutral and sulfated cyclodextrins as chiral selectors for common basic, neutral, and acidic compounds with a 96-capillary array system. By using only four judiciously chosen separation buffers, successful enantioseparations were achieved for 49 out of 54 test compounds spanning a large variety of pKs and structures. Therefore, unknown compounds can be screened in this manner to identify optimal enantioselective conditions in just one rn. In addition to superior separation efficiency for small molecules, CE is also the most powerful technique for DNA separations. Using the same multiplexed capillary system with UV absorption detection, the sequence of a short DNA template can be acquired without any dye-labels. Two internal standards were utilized to adjust the migration time variations among capillaries, so that the four electropherograms for the A, T, C, G Sanger reactions can be aligned and base calling can be completed with a high level of confidence. the CE separation of DNA can be applied to study differential gene expression as well. Combined with pattern recognition techniques, small variations among electropherograms obtained by the separation of cDNA fragments produced from the total RNA samples of different human tissues can be revealed. These variations reflect the differences in total RNA expression among tissues. Thus, this Ce-based approach can serve as an alternative to the DNA array techniques in gene expression analysis.

  15. Solvation Free Energies of Alanine Peptides: The Effect of Flexibility

    SciTech Connect

    Kokubo, Hironori; Harris, Robert C.; Asthagiri, Dilip; Pettitt, Bernard M.

    2013-12-03

    The electrostatic (?Gel), cavity-formation (?Gvdw), and total (?G) solvation free energies for 10 alanine peptides ranging in length (n) from 1 to 10 monomers were calculated. The free energies were computed both with xed, extended conformations of the peptides and again for some of the peptides without constraints. The solvation free energies, ?Gel, ?Gvdw, and ?G, were found to be linear in n, with the slopes of the best-fit lines being gamma_el, gamma_vdw, and gamma, respectively. Both gamma_el and gamma were negative for fixed and flexible peptides, and gamma_vdw was negative for fixed peptides. That gamma_vdw was negative was surprising, as experimental data on alkanes, theoretical models, and MD computations on small molecules and model systems generally suggest that gamma_vdw should be positive. A negative gamma_vdw seemingly contradicts the notion that ?Gvdw drives the initial collapse of the protein when it folds by favoring conformations with small surface areas, but when we computed ?Gvdw for the flexible peptides, thereby allowing the peptides to assume natural ensembles of more compact conformations, gamma-vdw was positive. Because most proteins do not assume extended conformations, a ?Gvdw that increases with increasing surface area may be typical for globular proteins. An alternative hypothesis is that the collapse is driven by intramolecular interactions. We show that the intramolecular van der Waal's interaction energy is more favorable for the flexible than for the extended peptides, seemingly favoring this hypothesis, but the large fluctuations in this energy may make attributing the collapse of the peptide to this intramolecular energy difficult.

  16. CHARMM-GUI Input Generator for NAMD, GROMACS, AMBER, OpenMM, and CHARMM/OpenMM Simulations Using the CHARMM36 Additive Force Field

    DOE PAGES [OSTI]

    Lee, Jumin; Cheng, Xi; Swails, Jason M.; Yeom, Min Sun; Eastman, Peter K.; Lemkul, Justin A.; Wei, Shuai; Buckner, Joshua; Jeong, Jong Cheol; Qi, Yifei; et al

    2015-11-12

    Here we report that proper treatment of nonbonded interactions is essential for the accuracy of molecular dynamics (MD) simulations, especially in studies of lipid bilayers. The use of the CHARMM36 force field (C36 FF) in different MD simulation programs can result in disagreements with published simulations performed with CHARMM due to differences in the protocols used to treat the long-range and 1-4 nonbonded interactions. In this study, we systematically test the use of the C36 lipid FF in NAMD, GROMACS, AMBER, OpenMM, and CHARMM/OpenMM. A wide range of Lennard-Jones (LJ) cutoff schemes and integrator algorithms were tested to find themore » optimal simulation protocol to best match bilayer properties of six lipids with varying acyl chain saturation and head groups. MD simulations of a 1,2-dipalmitoyl-sn-phosphatidylcholine (DPPC) bilayer were used to obtain the optimal protocol for each program. MD simulations with all programs were found to reasonably match the DPPC bilayer properties (surface area per lipid, chain order parameters, and area compressibility modulus) obtained using the standard protocol used in CHARMM as well as from experiments. The optimal simulation protocol was then applied to the other five lipid simulations and resulted in excellent agreement between results from most simulation programs as well as with experimental data. AMBER compared least favorably with the expected membrane properties, which appears to be due to its use of the hard-truncation in the LJ potential versus a force-based switching function used to smooth the LJ potential as it approaches the cutoff distance. The optimal simulation protocol for each program has been implemented in CHARMM-GUI. This protocol is expected to be applicable to the remainder of the additive C36 FF including the proteins, nucleic acids, carbohydrates, and small molecules.« less

  17. Catalytic Conversion of Biomass to Fuels and Chemicals Using Ionic Liquids

    SciTech Connect

    Liu, Wei; Zheng, Richard; Brown, Heather; Li, Joanne; Holladay, John; Cooper, Alan; Rao, Tony

    2012-04-13

    This project provides critical innovations and fundamental understandings that enable development of an economically-viable process for catalytic conversion of biomass (sugar) to 5-hydroxymethylfurfural (HMF). A low-cost ionic liquid (Cyphos 106) is discovered for fast conversion of fructose into HMF under moderate reaction conditions without any catalyst. HMF yield from fructose is almost 100% on the carbon molar basis. Adsorbent materials and adsorption process are invented and demonstrated for separation of 99% pure HMF product and recovery of the ionic liquid from the reaction mixtures. The adsorbent material appears very stable in repeated adsorption/regeneration cycles. Novel membrane-coated adsorbent particles are made and demonstrated to achieve excellent adsorption separation performances at low pressure drops. This is very important for a practical adsorption process because ionic liquids are known of high viscosity. Nearly 100% conversion (or dissolution) of cellulose in the catalytic ionic liquid into small molecules was observed. It is promising to produce HMF, sugars and other fermentable species directly from cellulose feedstock. However, several gaps were identified and could not be resolved in this project. Reaction and separation tests at larger scales are needed to minimize impacts of incidental errors on the mass balance and to show 99.9% ionic liquid recovery. The cellulose reaction tests were troubled with poor reproducibility. Further studies on cellulose conversion in ionic liquids under better controlled conditions are necessary to delineate reaction products, dissolution kinetics, effects of mass and heat transfer in the reactor on conversion, and separation of final reaction mixtures.

  18. Energy Landscape of Water and Ethanol on Silica Surfaces

    SciTech Connect

    Wu, Di; Guo, Xiaofeng; Sun, Hui; Navrotsky, Alexandra

    2015-06-26

    Fundamental understanding of small moleculesilica surface interactions at their interfaces is essential for the scientific, technological, and medical communities. We report direct enthalpy of adsorption (?hads) measurements for ethanol and water vapor on porous silica glass (CPG-10), in both hydroxylated and dehydroxylated (hydrophobic) forms. Results suggest a spectrum of energetics as a function of coverage, stepwise for ethanol but continuous for water. The zero-coverage enthalpy of adsorption for hydroxylated silica shows the most exothermic enthalpies for both water (-72.7 3.1 kJ/mol water) and ethanol (-78.0 1.9 kJ/mol ethanol). The water adsorption enthalpy becomes less exothermic gradually until reaching its only plateau (-20.7 2.2 kJ/mol water) reflecting water clustering on a largely hydrophobic surface, while the enthalpy of ethanol adsorption profile presents two well separated plateaus, corresponding to strong chemisorption of ethanol on adsorbate-free silica surface (-66.4 4.8 kJ/mol ethanol), and weak physisorption of ethanol on ethanol covered silica (-4.0 1.6 kJ/mol ethanol). On the other hand, dehydroxylation leads to missing watersilica interactions, whereas the number of ethanol binding sites is not impacted. The isotherms and partial molar properties of adsorption suggest that water may only bind strongly onto the silanols (which are a minor species on silica glass), whereas ethanol can interact strongly with both silanols and the hydrophobic areas of the silica surface.

  19. Inhibition of aminoacylase 3 protects rat brain cortex neuronal cells from the toxicity of 4-hydroxy-2-nonenal mercapturate and 4-hydroxy-2-nonenal

    SciTech Connect

    Tsirulnikov, Kirill; Abuladze, Natalia; Bragin, Anatol; Brain Research Institute, University of California at Los Angeles, CA 90095 ; Faull, Kym; Department of Psychiatry and Biobehavioral Sciences, University of California at Los Angeles, CA 90095; Pasarow Mass Spectrometry Laboratory, University of California at Los Angeles, CA 90095 ; Cascio, Duilio; Damoiseaux, Robert; Schibler, Matthew J.; Pushkin, Alexander

    2012-09-15

    4-Hydroxy-2-nonenal (4HNE) and acrolein (ACR) are highly reactive neurotoxic products of lipid peroxidation that are implicated in the pathogenesis and progression of Alzheimer's and Parkinson's diseases. Conjugation with glutathione (GSH) initiates the 4HNE and ACR detoxification pathway, which generates the mercapturates of 4HNE and ACR that can be excreted. Prior work has shown that the efficiency of the GSH-dependent renal detoxification of haloalkene derived mercapturates is significantly decreased upon their deacetylation because of rapid transformation of the deacetylated products into toxic compounds mediated by ?-lyase. The enzymes of the GSH-conjugation pathway and ?-lyases are expressed in the brain, and we hypothesized that a similar toxicity mechanism may be initiated in the brain by the deacetylation of 4HNE- and ACR-mercapturate. The present study was performed to identify an enzyme(s) involved in 4HNE- and ACR-mercapturate deacetylation, characterize the brain expression of this enzyme and determine whether its inhibition decreases 4HNE and 4HNE-mercapturate neurotoxicity. We demonstrated that of two candidate deacetylases, aminoacylases 1 (AA1) and 3 (AA3), only AA3 efficiently deacetylates both 4HNE- and ACR-mercapturate. AA3 was further localized to neurons and blood vessels. Using a small molecule screen we generated high-affinity AA3 inhibitors. Two of them completely protected rat brain cortex neurons expressing AA3 from the toxicity of 4HNE-mercapturate. 4HNE-cysteine (4HNE-Cys) was also neurotoxic and its toxicity was mostly prevented by a ?-lyase inhibitor, aminooxyacetate. The results suggest that the AA3 mediated deacetylation of 4HNE-mercapturate may be involved in the neurotoxicity of 4HNE.

  20. Chemical technology division: Annual technical report 1987

    SciTech Connect

    Not Available

    1988-05-01

    Highlights of the Chemical Technology (CMT) Division's activities during 1987 are presented. In this period, CMT conducted research and development in the following areas: (1) high-performance batteries--mainly lithium-alloy/metal sulfide and sodium/sulfur; (2) aqueous batteries (lead-acid, nickel/iron, etc.); (3) advanced fuel cells with molten carbonate or solid oxide electrolytes; (4) coal utilization, including the heat and seed recovery technology for coal-fired magnetohydrodynamics plants and the technology for fluidized-bed combustion; (5) methods for the electromagnetic continuous casting of steel sheet and for the purification of ferrous scrap; (6) methods for recovery of energy from municipal waste and techniques for treatment of hazardous organic waste; (7) nuclear technology related to a process for separating and recovering transuranic elements from nuclear waste, the recovery processes for discharged fuel and the uranium blanket in a sodium-cooled fast reactor, and waste management; and (8) physical chemistry of selected materials in environments simulating those of fission and fusion energy systems. The Division also has a program in basic chemistry research in the areas of fluid catalysis for converting small molecules to desired products; materials chemistry for liquids and vapors at high temperatures; interfacial processes of importance to corrosion science, high-temperature superconductivity, and catalysis; the thermochemistry of various minerals; and the geochemical processes responsible for trace-element migration within the earth's crust. The Division continued to be the major user of the technical support provided by the Analytical Chemistry Laboratory at ANL. 54 figs., 9 tabs.

  1. Polymer filtration systems for dilute metal ion recovery

    SciTech Connect

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1998-12-01

    Scientists at Los Alamos National Laboratory have developed a metal recovery system that meets the global treatment demands for all kinds of industrial and metal-processing streams. The Polymer Filtration (PF) System--a process that is easily operated and robust--offers metal-finishing businesses a convenient and inexpensive way to recover and recycle metal ions in-house, thus reducing materials costs, waste removal costs, and industrial liability. As a valuable economic and environmental asset, the PF System has been named a winner of a 1995 R and D 100 Award. These awards are presented annually by R and D Magazine to the one hundred most significant technical innovations of the year. The PF System is based on the use of water-soluble metal-binding polymers and on advanced ultrafiltration membranes. Customers for this technology will receive new soluble polymers, especially formulated for their waste stream, and the complete PF processing unit: a reaction reservoir, pumps, plumbing, controls, and the advanced ultrafiltration membranes, all in a skid mounted frame. Metal-bearing waste water is treated in the reaction reservoir, where the polymer binds with the metal ions under balanced acid/base conditions. The reservoir fluid is then pumped through the ultrafiltration system--a cartridge packed with ultrafiltration membranes shaped in hollow fibers. As the fluid travels inside the fiber, water and other small molecules--simple salts such as calcium and sodium, for example--pass through the porous membrane walls of the fibers and are discharged through the outlet as permeate. The polymer-bound metal, which is too large to pass through the pores, is both purified and concentrated inside the hollow fibers and is returned to the fluid reservoir for further waste water treatment.

  2. CXC Receptor 1 and 2 and Neutrophil Elastase Inhibitors Alter Radiation-induced Lung Disease in the Mouse

    SciTech Connect

    Fox, Jessica; Haston, Christina K.

    2013-01-01

    Purpose: We previously reported increased numbers of neutrophils to be associated with the development of the radiation-induced lung responses of alveolitis (pneumonitis) and fibrosis in mice. In the present study we investigated whether CXC receptor 1 and 2 antagonism with DF2156A, a small molecule inhibitor of neutrophil chemotaxis, or the neutrophil elastase inhibitor sivelestat decreases the lung response to irradiation. Methods and Materials: KK/HIJ mice received 14 Gy whole-thorax irradiation, and a subset of them received drug treatment 3 times per week from the day of irradiation until they were killed because of respiratory distress symptoms. Results: Irradiated mice receiving sivelestat survived 18% longer than did mice receiving radiation alone (73 vs 60 days for female mice, 91 vs 79 days for male mice), whereas postirradiation survival times did not differ between the group of mice receiving DF2156A and the radiation-only group. The numbers of neutrophils in lung tissue and in bronchoalveolar lavage fluid did not differ among groups of irradiated mice, but they significantly exceeded the levels in unirradiated control mice. The extent of alveolitis, assessed histologically, did not differ between irradiated mice treated with either drug and those receiving radiation alone, when assessed at the end of the experiment, but it was significantly reduced, as were the neutrophil measures, in sivelestat-treated mice at the common kill time of 60 days after irradiation. Mice treated with radiation and DF2156A developed significantly less fibrosis than did mice receiving radiation alone, and this difference was associated with decreased expression of interleukin-13 in lung tissue. Conclusions: We conclude that neutrophil elastase inhibition affects alveolitis and prolongs survival, whereas CXCR1/2 antagonism reduces radiation-induced fibrotic lung disease in mice without affecting the onset of distress.

  3. Evaluation of the pharmacokinetics and cardiotoxicity of doxorubicin in rat receiving nilotinib

    SciTech Connect

    Zhou, Zhi-yong; Wan, Li-li; Yang, Quan-jun; Han, Yong-long; Li, Yan; Yu, Qi; Guo, Cheng; Li, Xiao

    2013-10-01

    Doxorubicin (DOX) is a potent chemotherapy drug with a narrow therapeutic window. Nilotinib, a small-molecule Bcr-Abl tyrosine kinase inhibitor, was reported to reverse multidrug resistance (MDR) mediated by P-glycoprotein (P-gp) transmembrane transporters. The present study aimed to investigate nilotinib's affection on the steady-state pharmacokinetics, disposition and cardiotoxicity of DOX. A total of 24 male SpragueDawley rats were randomized into four groups (6 in each) and received the following regimens: saline, intravenous DOX (5 mg/kg) alone, and DOX co-administrated with either 20 or 40 mg/kg nilotinib. Blood was withdrawn at 12 time points till 72 h after DOX injection and the concentrations of DOX and its metabolite doxorubicinol (DOXol) in serum and cardiac tissue were assayed by LCMSMS method. To determine the cardiotoxicity, the following parameters were investigated: creatine kinase, lactate dehydrogenase, malondialdehyde, and superoxide dismutase. Histopathological examination of heart section was carried out to evaluate the extent of cardiotoxicity after treatments. The results showed that pretreatment of 40 mg/kg nilotinib increased the AUC{sub 0t} and C{sub max} of DOX and DOXol. However, their accumulation in cardiac tissue was significantly decreased when compared with the group that received DOX alone. In addition, biochemical and histopathological results showed that 40 mg/kg nilotinib reduced the cardiotoxicity induced by DOX administration. In conclusion, co-administration of nilotinib increased serum exposure, but significantly decreased the accumulation of DOX in cardiac tissue. Consistent with in vitro profile, oral dose of 40 mg/kg nilotinib significantly decreased the cardiotoxicity of DOX in rat by enhancing P-gp activity in the heart.

  4. Electrochemical Sensors and Biosensors Based on Nanomaterials and Nanostructures

    DOE PAGES [OSTI]

    Zhu, Chengzhou; Yang, Guohai; Li, He; Du, Dan; Lin, Yuehe

    2014-10-29

    We report that considerable attention has been devoted to the integration of recognition elements with electronic elements to develop electrochemical sensors and biosensors.Various electrochemical devices, such as amperometric sensors, electrochemical impedance sensors, and electrochemical luminescence sensors as well as photoelectrochemical sensors, provide wide applications in the detection of chemical and biological targets in terms of electrochemical change of electrode interfaces. Here, this review focuses on recent advances in electrochemical sensors and biosensors based on nanomaterials and nanostructures during 2013 to 2014. The aim of this effort is to provide the reader with a clear and concise view of new advancesmore » in areas ranging from electrode engineering, strategies for electrochemical signal amplification, and novel electroanalytical techniques used in the miniaturization and integration of the sensors. Moreover, the authors have attempted to highlight areas of the latest and significant development of enhanced electrochemical nanosensors and nanobiosensors that inspire broader interests across various disciplines. Electrochemical sensors for small molecules, enzyme-based biosensors, genosensors, immunosensors, and cytosensors are reviewed herein (Figure 1). Such novel advances are important for the development of electrochemical sensors that open up new avenues and methods for future research. In conclusion, we recommend readers interested in the general principles of electrochemical sensors and electrochemical methods to refer to other excellent literature for a broad scope in this area.(3, 4) However, due to the explosion of publications in this active field, we do not claim that this Review includes all of the published works in the past two years and we apologize to the authors of excellent work, which is unintentionally left out.« less

  5. Tricyclic GyrB/ParE (TriBE) Inhibitors. A new class of broad-spectrum dual-targeting antibacterial agents

    SciTech Connect

    Tari, Leslie W.; Li, Xiaoming; Trzoss, Michael; Bensen, Daniel C.; Chen, Zhiyong; Lam, Thanh; Zhang, Junhu; Lee, Suk Joong; Hough, Grayson; Phillipson, Doug; Akers-Rodriguez, Suzanne; Cunningham, Mark L.; Kwan, Bryan P.; Nelson, Kirk J.; Castellano, Amanda; Locke, Jeff B.; Brown-Driver, Vickie; Murphy, Timothy M.; Ong, Voon S.; Pillar, Chris M.; Shinabarger, Dean L.; Nix, Jay; Lightstone, Felice C.; Wong, Sergio E.; Nguyen, Toan B.; Shaw, Karen J.; Finn, John

    2013-12-26

    Increasing resistance to every major class of antibiotics and a dearth of novel classes of antibacterial agents in development pipelines has created a dwindling reservoir of treatment options for serious bacterial infections. The bacterial type IIA topoisomerases, DNA gyrase and topoisomerase IV, are validated antibacterial drug targets with multiple prospective drug binding sites, including the catalytic site targeted by the fluoroquinolone antibiotics. Growing resistance to fluoroquinolones, frequently mediated by mutations in the drug-binding site, is increasingly limiting the utility of this antibiotic class, prompting the search for other inhibitor classes that target different sites on the topoisomerase complexes. The highly conserved ATP-binding subunits of DNA gyrase (GyrB) and topoisomerase IV (ParE) have long been recognized as excellent candidates for the development of dual-targeting antibacterial agents with broad-spectrum potential. However, to date, no natural product or small molecule inhibitors targeting these sites have succeeded in the clinic, and no inhibitors of these enzymes have yet been reported with broad-spectrum antibacterial activity encompassing the majority of Gram-negative pathogens. Using structure-based drug design (SBDD), we have created a novel dual-targeting pyrimidoindole inhibitor series with exquisite potency against GyrB and ParE enzymes from a broad range of clinically important pathogens. Inhibitors from this series demonstrate potent, broad-spectrum antibacterial activity against Gram-positive and Gram-negative pathogens of clinical importance, including fluoroquinolone resistant and multidrug resistant strains. Moreover, lead compounds have been discovered with clinical potential; they are well tolerated in animals, and efficacious in Gram-negative infection models.

  6. Structures of Human Cyctochrome P450 2E1: Insights Into the Binding of Inhibitors And Both Small Molecular Weight And Fatty Acid Substrates

    SciTech Connect

    Porubsky, P.R.; Meneely, K.M.; Scott, E.E.

    2009-05-21

    Human microsomal cytochrome P-450 2E1 (CYP2E1) monooxygenates >70 low molecular weight xenobiotic compounds, as well as much larger endogenous fatty acid signaling molecules such as arachidonic acid. In the process, CYP2E1 can generate toxic or carcinogenic compounds, as occurs with acetaminophen overdose, nitrosamines in cigarette smoke, and reactive oxygen species from uncoupled catalysis. Thus, the diverse roles that CYP2E1 has in normal physiology, toxicity, and drug metabolism are related to its ability to metabolize diverse classes of ligands, but the structural basis for this was previously unknown. Structures of human CYP2E1 have been solved to 2.2 {angstrom} for an indazole complex and 2.6 {angstrom} for a 4-methylpyrazole complex. Both inhibitors bind to the heme iron and hydrogen bond to Thr{sup 303} within the active site. Complementing its small molecular weight substrates, the hydrophobic CYP2E1 active site is the smallest yet observed for a human cytochrome P-450. The CYP2E1 active site also has two adjacent voids: one enclosed above the I helix and the other forming a channel to the protein surface. Minor repositioning of the Phe{sup 478} aromatic ring that separates the active site and access channel would allow the carboxylate of fatty acid substrates to interact with conserved {sup 216}QXXNN{sup 220} residues in the access channel while positioning the hydrocarbon terminus in the active site, consistent with experimentally observed {omega}-1 hydroxylation of saturated fatty acids. Thus, these structures provide insights into the ability of CYP2E1 to effectively bind and metabolize both small molecule substrates and fatty acids.

  7. A Thermally Stable Form of Bacterial Cocaine Esterase: A Potential Therapeutic Agent for Treatment of Cocaine Abuse

    SciTech Connect

    Brim, Remy L.; Nance, Mark R.; Youngstrom, Daniel W.; Narasimhan, Diwahar; Zhan, Chang-Guo; Tesmer, John J.G.; Sunahara, Roger K.; Woods, James H.

    2010-09-03

    Rhodococcal cocaine esterase (CocE) is an attractive potential treatment for both cocaine overdose and cocaine addiction. CocE directly degrades cocaine into inactive products, whereas traditional small-molecule approaches require blockade of the inhibitory action of cocaine on a diverse array of monoamine transporters and ion channels. The usefulness of wild-type (wt) cocaine esterase is hampered by its inactivation at 37 C. Herein, we characterize the most thermostable form of this enzyme to date, CocE-L169K/G173Q. In vitro kinetic analyses reveal that CocE-L169K/G173Q displays a half-life of 2.9 days at 37 C, which represents a 340-fold improvement over wt and is 15-fold greater than previously reported mutants. Crystallographic analyses of CocE-L169K/G173Q, determined at 1.6-{angstrom} resolution, suggest that stabilization involves enhanced domain-domain interactions involving van der Waals interactions and hydrogen bonding. In vivo rodent studies reveal that intravenous pretreatment with CocE-L169K/G173Q in mice provides protection from cocaine-induced lethality for longer time periods before cocaine administration than wt CocE. Furthermore, intravenous administration (pretreatment) of CocE-L169K/G173Q prevents self-administration of cocaine in a time-dependent manner. Termination of the in vivo effects of CoCE seems to be dependent on, but not proportional to, its clearance from plasma as its half-life is approximately 2.3 h and similar to that of wt CocE (2.2 h). Taken together these data suggest that CocE-L169K/G173Q possesses many of the properties of a biological therapeutic for treating cocaine abuse but requires additional development to improve its serum half-life.

  8. Bio-distribution and metabolic paths of silica coated CdSeS quantum dots

    SciTech Connect

    Chen Zhen; Chen Hu; Meng Huan; Xing Gengmei Gao Xueyun; Sun Baoyun; Shi Xiaoli; Yuan Hui; Zhang Chengcheng; Liu Ru; Zhao Feng

    2008-08-01

    With the rapid development of quantum dot (QD) technology, water-soluble QDs have the prospect of being used as a biological probe for specific diagnoses, but their biological behaviors in vivo are little known. Our recent in vivo studies concentrated on the bio-kinetics of QDs coated by hydroxyl group modified silica networks (the QDs are 21.3 {+-} 2.0 nm in diameter and have maximal emission at 570 nm). Male ICR mice were intravenously given the water-soluble QDs with a single dose of 5 nmol/mouse. Inductively coupled plasma-mass spectrometry was used to measure the {sup 111}Cd content to indicate the concentration of QDs in plasma, organs, and excretion samples collected at predetermined time intervals. Meanwhile, the distribution and aggregation state of QDs in tissues were also investigated by pathological examination and differential centrifugation. The plasma half-life and clearance of QDs were 19.8 {+-} 3.2 h and 57.3 {+-} 9.2 ml/h/kg, respectively. The liver and kidney were the main target organs for QDs. The QDs metabolized in three paths depending on their distinct aggregated states in vivo. A fraction of free QDs, maintaining their original form, could be filtered by glomerular capillaries and excreted via urine as small molecules within five days. Most QDs bound to protein and aggregated into larger particles that were metabolized in the liver and excreted via feces in vivo. After five days, 8.6% of the injected dose of aggregated QDs still remained in hepatic tissue and it was difficult for this fraction to clear.

  9. Comprehensive mechanisms for combustion chemistry: Experiment, modeling, and sensitivity analysis

    SciTech Connect

    Dryer, F.L.; Yetter, R.A.

    1993-12-01

    This research program is an integrated experimental/numerical effort to study pyrolysis and oxidation reactions and mechanisms for small-molecule hydrocarbon structures under conditions representative of combustion environments. The experimental aspects of the work are conducted in large diameter flow reactors, at pressures from one to twenty atmospheres, temperatures from 550 K to 1200 K, and with observed reaction times from 10{sup {minus}2} to 5 seconds. Gas sampling of stable reactant, intermediate, and product species concentrations provides not only substantial definition of the phenomenology of reaction mechanisms, but a significantly constrained set of kinetic information with negligible diffusive coupling. Analytical techniques used for detecting hydrocarbons and carbon oxides include gas chromatography (GC), and gas infrared (NDIR) and FTIR methods are utilized for continuous on-line sample detection of light absorption measurements of OH have also been performed in an atmospheric pressure flow reactor (APFR), and a variable pressure flow (VPFR) reactor is presently being instrumented to perform optical measurements of radicals and highly reactive molecular intermediates. The numerical aspects of the work utilize zero and one-dimensional pre-mixed, detailed kinetic studies, including path, elemental gradient sensitivity, and feature sensitivity analyses. The program emphasizes the use of hierarchical mechanistic construction to understand and develop detailed kinetic mechanisms. Numerical studies are utilized for guiding experimental parameter selections, for interpreting observations, for extending the predictive range of mechanism constructs, and to study the effects of diffusive transport coupling on reaction behavior in flames. Modeling using well defined and validated mechanisms for the CO/H{sub 2}/oxidant systems.

  10. Tricyclic GyrB/ParE (TriBE) Inhibitors. A new class of broad-spectrum dual-targeting antibacterial agents

    DOE PAGES [OSTI]

    Tari, Leslie W.; Li, Xiaoming; Trzoss, Michael; Bensen, Daniel C.; Chen, Zhiyong; Lam, Thanh; Zhang, Junhu; Lee, Suk Joong; Hough, Grayson; Phillipson, Doug; et al

    2013-12-26

    Increasing resistance to every major class of antibiotics and a dearth of novel classes of antibacterial agents in development pipelines has created a dwindling reservoir of treatment options for serious bacterial infections. The bacterial type IIA topoisomerases, DNA gyrase and topoisomerase IV, are validated antibacterial drug targets with multiple prospective drug binding sites, including the catalytic site targeted by the fluoroquinolone antibiotics. Growing resistance to fluoroquinolones, frequently mediated by mutations in the drug-binding site, is increasingly limiting the utility of this antibiotic class, prompting the search for other inhibitor classes that target different sites on the topoisomerase complexes. The highlymore » conserved ATP-binding subunits of DNA gyrase (GyrB) and topoisomerase IV (ParE) have long been recognized as excellent candidates for the development of dual-targeting antibacterial agents with broad-spectrum potential. However, to date, no natural product or small molecule inhibitors targeting these sites have succeeded in the clinic, and no inhibitors of these enzymes have yet been reported with broad-spectrum antibacterial activity encompassing the majority of Gram-negative pathogens. Using structure-based drug design (SBDD), we have created a novel dual-targeting pyrimidoindole inhibitor series with exquisite potency against GyrB and ParE enzymes from a broad range of clinically important pathogens. Inhibitors from this series demonstrate potent, broad-spectrum antibacterial activity against Gram-positive and Gram-negative pathogens of clinical importance, including fluoroquinolone resistant and multidrug resistant strains. Moreover, lead compounds have been discovered with clinical potential; they are well tolerated in animals, and efficacious in Gram-negative infection models.« less

  11. Dynamics-based selective 2D {sup 1}H/{sup 1}H chemical shift correlation spectroscopy under ultrafast MAS conditions

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-05-28

    Dynamics plays important roles in determining the physical, chemical, and functional properties of a variety of chemical and biological materials. However, a material (such as a polymer) generally has mobile and rigid regions in order to have high strength and toughness at the same time. Therefore, it is difficult to measure the role of mobile phase without being affected by the rigid components. Herein, we propose a highly sensitive solid-state NMR approach that utilizes a dipolar-coupling based filter (composed of 12 equally spaced 90° RF pulses) to selectively measure the correlation of {sup 1}H chemical shifts from the mobile regions of a material. It is interesting to find that the rotor-synchronized dipolar filter strength decreases with increasing inter-pulse delay between the 90° pulses, whereas the dipolar filter strength increases with increasing inter-pulse delay under static conditions. In this study, we also demonstrate the unique advantages of proton-detection under ultrafast magic-angle-spinning conditions to enhance the spectral resolution and sensitivity for studies on small molecules as well as multi-phase polymers. Our results further demonstrate the use of finite-pulse radio-frequency driven recoupling pulse sequence to efficiently recouple weak proton-proton dipolar couplings in the dynamic regions of a molecule and to facilitate the fast acquisition of {sup 1}H/{sup 1}H correlation spectrum compared to the traditional 2D NOESY (Nuclear Overhauser effect spectroscopy) experiment. We believe that the proposed approach is beneficial to study mobile components in multi-phase systems, such as block copolymers, polymer blends, nanocomposites, heterogeneous amyloid mixture of oligomers and fibers, and other materials.

  12. Multi-scaled normal mode analysis method for dynamics simulation of protein-membrane complexes: A case study of potassium channel gating motion correlations

    SciTech Connect

    Wu, Xiaokun; Han, Min; Ming, Dengming

    2015-10-07

    Membrane proteins play critically important roles in many cellular activities such as ions and small molecule transportation, signal recognition, and transduction. In order to fulfill their functions, these proteins must be placed in different membrane environments and a variety of protein-lipid interactions may affect the behavior of these proteins. One of the key effects of protein-lipid interactions is their ability to change the dynamics status of membrane proteins, thus adjusting their functions. Here, we present a multi-scaled normal mode analysis (mNMA) method to study the dynamics perturbation to the membrane proteins imposed by lipid bi-layer membrane fluctuations. In mNMA, channel proteins are simulated at all-atom level while the membrane is described with a coarse-grained model. mNMA calculations clearly show that channel gating motion can tightly couple with a variety of membrane deformations, including bending and twisting. We then examined bi-channel systems where two channels were separated with different distances. From mNMA calculations, we observed both positive and negative gating correlations between two neighboring channels, and the correlation has a maximum as the channel center-to-center distance is close to 2.5 times of their diameter. This distance is larger than recently found maximum attraction distance between two proteins embedded in membrane which is 1.5 times of the protein size, indicating that membrane fluctuation might impose collective motions among proteins within a larger area. The hybrid resolution feature in mNMA provides atomic dynamics information for key components in the system without costing much computer resource. We expect it to be a conventional simulation tool for ordinary laboratories to study the dynamics of very complicated biological assemblies. The source code is available upon request to the authors.

  13. Targeting ceramide metabolic pathway induces apoptosis in human breast cancer cell lines

    SciTech Connect

    Vethakanraj, Helen Shiphrah; Babu, Thabraz Ahmed; Sudarsanan, Ganesh Babu; Duraisamy, Prabhu Kumar; Ashok Kumar, Sekar

    2015-08-28

    The sphingolipid ceramide is a pro apoptotic molecule of ceramide metabolic pathway and is hydrolyzed to proliferative metabolite, sphingosine 1 phosphate by the action of acid ceramidase. Being upregulated in the tumors of breast, acid ceramidase acts as a potential target for breast cancer therapy. We aimed at targeting this enzyme with a small molecule acid ceramidase inhibitor, Ceranib 2 in human breast cancer cell lines MCF 7 and MDA MB 231. Ceranib 2 effectively inhibited the growth of both the cell lines in dose and time dependant manner. Morphological apoptotic hallmarks such as chromatin condensation, fragmented chromatin were observed in AO/EtBr staining. Moreover, ladder pattern of fragmented DNA observed in DNA gel electrophoresis proved the apoptotic activity of Ceranib 2 in breast cancer cell lines. The apoptotic events were associated with significant increase in the expression of pro-apoptotic genes (Bad, Bax and Bid) and down regulation of anti-apoptotic gene (Bcl 2). Interestingly, increase in sub G1 population of cell cycle phase analysis and elevated Annexin V positive cells after Ceranib 2 treatment substantiated its apoptotic activity in MCF 7 and MDA MB 231 cell lines. Thus, we report Ceranib 2 as a potent therapeutic agent against both ER{sup +} and ER{sup −} breast cancer cell lines. - Highlights: • Acid Ceramidase inhibitor, Ceranib 2 induced apoptosis in Breast cancer cell lines (MCF 7 and MDA MB 231 cell lines). • Apoptosis is mediated by DNA fragmentation and cell cycle arrest. • Ceranib 2 upregulated the expression of pro-apoptotic genes and down regulated anti-apoptotic gene expression. • More potent compared to the standard drug Tamoxifen.

  14. Summary report : universal fuel processor.

    SciTech Connect

    Coker, Eric Nicholas; Rice, Steven F.; Kemp, Richard Alan; Stewart, Constantine A.; Miller, James Edward; Cornelius, Christopher James; Staiger, Chad Lynn; Pickett, Lyle M.

    2008-01-01

    The United States produces only about 1/3 of the more than 20 million barrels of petroleum that it consumes daily. Oil imports into the country are roughly equivalent to the amount consumed in the transportation sector. Hence the nation in general, and the transportation sector in particular, is vulnerable to supply disruptions and price shocks. The situation is anticipated to worsen as the competition for limited global supplies increases and oil-rich nations become increasingly willing to manipulate the markets for this resource as a means to achieve political ends. The goal of this project was the development and improvement of technologies and the knowledge base necessary to produce and qualify a universal fuel from diverse feedstocks readily available in North America and elsewhere (e.g. petroleum, natural gas, coal, biomass) as a prudent and positive step towards mitigating this vulnerability. Three major focus areas, feedstock transformation, fuel formulation, and fuel characterization, were identified and each was addressed. The specific activities summarized herein were identified in consultation with industry to set the stage for collaboration. Two activities were undertaken in the area of feedstock transformation. The first activity focused on understanding the chemistry and operation of autothermal reforming, with an emphasis on understanding, and therefore preventing, soot formation. The second activity was focused on improving the economics of oxygen production, particularly for smaller operations, by integrating membrane separations with pressure swing adsorption. In the fuel formulation area, the chemistry of converting small molecules readily produced from syngas directly to fuels was examined. Consistent with the advice from industry, this activity avoided working on improving known approaches, giving it an exploratory flavor. Finally, the fuel characterization task focused on providing a direct and quantifiable comparison of diesel fuel and JP-8.

  15. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    SciTech Connect

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  16. Comprehensive Mechanisms for Combustion Chemistry: An Experimental and Numerical Study with Emphasis on Applied Sensitivity Analysis

    SciTech Connect

    Dryer, Frederick L.

    2009-04-10

    This project was an integrated experimental/numerical effort to study pyrolysis and oxidation reactions and mechanisms for small-molecule hydrocarbon structures under conditions representative of combustion environments. The experimental aspects of the work were conducted in large-diameter flow reactors, at 0.3 to 18 atm pressure, 500 to 1100 K temperature, and 10-2 to 2 seconds reaction time. Experiments were also conducted to determine reference laminar flame speeds using a premixed laminar stagnation flame experiment and particle image velocimetry, as well as pressurized bomb experiments. Flow reactor data for oxidation experiments include: (1)adiabatic/isothermal species time-histories of a reaction under fixed initial pressure, temperature, and composition; to determine the species present after a fixed reaction time, initial pressure; (2)species distributions with varying initial reaction temperature; (3)perturbations of a well-defined reaction systems (e.g. CO/H2/O2 or H2/O2)by the addition of small amounts of an additive species. Radical scavenging techniques are applied to determine unimolecular decomposition rates from pyrolysis experiments. Laminar flame speed measurements are determined as a function of equivalence ratio, dilution, and unburned gas temperature at 1 atm pressure. Hierarchical, comprehensive mechanistic construction methods were applied to develop detailed kinetic mechanisms which describe the measurements and literature kinetic data. Modeling using well-defined and validated mechanisms for the CO/H2/Oxidant systems and perturbations of oxidation experiments by small amounts of additives were also used to derive absolute reaction rates and to investigate the compatibility of published elementary kinetic and thermochemical information. Numerical tools were developed and applied to assess the importance of individual elementary reactions to the predictive performance of the

  17. The structure and reactivity of adsorbates on stepped Rh and Pt surfaces investigated by LEED, HREELS, TPD, XPS and STM

    SciTech Connect

    Batteas, J.D. |

    1995-06-01

    Defects on surfaces such as steps play an important role in surface chemistry. In order to obtain an understanding of the influence of steps in surface chemical reactions, the structure and reactivity of small molecules (O{sub 2}, CO, H{sub 2}S, and C{sub 2}H{sub 4}) on atomically stepped surfaces of RH and Pt have been investigated. The detailed structures of CO and oxygen bonded to the Rh(110) surface were determined. The CO molecules bond near the short bridge sites with the CO molecular axis tilted approximately 24{degree} from the surface normal. Oxygen atoms are bound asymmetrically in the 3-fold fcc hollow-sites to the (111) facets of the steps. The interactions of CO and oxygen on the Rh(311) surface were examined. The reaction of CO with the ordered phases of O shows two distinct reaction channels, a low temperature reaction limited channel (200 K) and a high temperature diffusion limited channel (350 K). Models of the reaction geometry and dynamics are proposed. The thermal decomposition of ethylene was examined on the Rh(311) surface. The stable decomposition species (C{sub 2}H, CH and C{sub 2}) are formed near 300 K, approximately 100 K lower on the stepped Rh(311) than on the flatter Rh(111) surface. The formation of these species at lower temperatures is attributed to the stepped nature of the surface. Finally, in situ STM was used to examine surface structural changes of a stepped Pt(111) crystal under coadsorption of sulfur and CO. This is the first direct evidence for a new mechanism by which a surface covered with an unreactive, strongly chemisorbed overlayer can form new sites, for bonding and reactions to occur, by massive surface restructuring at the step edges. This new surface phenomenon answers some of the puzzles of metal surface catalysis and its implications are described. 278 refs.

  18. Development of peptoid-based ligands for the removal of cadmium from biological media

    SciTech Connect

    Knight, Abigail S.; Zhou, Effie Y.; Francis, Matthew B.

    2015-05-14

    Cadmium poisoning poses a serious health concern due to cadmium's increasing industrial use, yet there is currently no recommended treatment. The selective coordination of cadmium in a biological environmenti.e. in the presence of serum ions, small molecules, and proteinsis a difficult task. To address this challenge, a combinatorial library of peptoid-based ligands has been evaluated to identify structures that selectively bind to cadmium in human serum with minimal chelation of essential metal ions. Eighteen unique ligands were identified in this screening procedure, and the binding affinity of each was measured using metal titrations monitored by UV-vis spectroscopy. To evaluate the significance of each chelating moiety, sequence rearrangements and substitutions were examined. Analysis of a metalligand complex by NMR spectroscopy highlighted the importance of particular residues. Depletion experiments were performed in serum mimetics and human serum with exogenously added cadmium. These depletion experiments were used to compare and demonstrate the ability of these peptoids to remove cadmium from blood-like mixtures. In one of these depletion experiments, the peptoid sequence was able to deplete the cadmium to a level comparable to the reported acute toxicity limit. Evaluation of the metal selectivity in buffered solution and in human serum was performed to verify minimal off-target binding. These studies highlight a screening platform for the identification of metalligands that are capable of binding in a complex environment. They additionally demonstrate the potential utility of biologically-compatible ligands for the treatment of heavy metal poisoning.

  19. The PD-1/PD-L1 complex resembles the antigen-binding Fv domains of antibodies and T cell receptors

    SciTech Connect

    Lin, David Yin-wei; Tanaka, Yoshimasa; Iwasaki, Masashi; Gittis, Apostolos G.; Su, Hua-Poo; Mikami, Bunzo; Okazaki, Taku; Honjo, Tasuku; Minato, Nagahiro; Garboczi, David N. (NIH); (Kyoto)

    2008-07-29

    Signaling through the programmed death 1 (PD-1) inhibitory receptor upon binding its ligand, PD-L1, suppresses immune responses against autoantigens and tumors and plays an important role in the maintenance of peripheral immune tolerance. Release from PD-1 inhibitory signaling revives 'exhausted' virus-specific T cells in chronic viral infections. Here we present the crystal structure of murine PD-1 in complex with human PD-L1. PD-1 and PD-L1 interact through the conserved front and side of their Ig variable (IgV) domains, as do the IgV domains of antibodies and T cell receptors. This places the loops at the ends of the IgV domains on the same side of the PD-1/PD-L1 complex, forming a surface that is similar to the antigen-binding surface of antibodies and T cell receptors. Mapping conserved residues allowed the identification of residues that are important in forming the PD-1/PD-L1 interface. Based on the structure, we show that some reported loss-of-binding mutations involve the PD-1/PD-L1 interaction but that others compromise protein folding. The PD-1/PD-L1 interaction described here may be blocked by antibodies or by designed small-molecule drugs to lower inhibitory signaling that results in a stronger immune response. The immune receptor-like loops offer a new surface for further study and potentially the design of molecules that would affect PD-1/PD-L1 complex formation and thereby modulate the immune response.

  20. Electrochemical Sensors and Biosensors Based on Nanomaterials and Nanostructures

    SciTech Connect

    Zhu, Chengzhou; Yang, Guohai; Li, He; Du, Dan; Lin, Yuehe

    2014-10-29

    We report that considerable attention has been devoted to the integration of recognition elements with electronic elements to develop electrochemical sensors and biosensors.Various electrochemical devices, such as amperometric sensors, electrochemical impedance sensors, and electrochemical luminescence sensors as well as photoelectrochemical sensors, provide wide applications in the detection of chemical and biological targets in terms of electrochemical change of electrode interfaces. Here, this review focuses on recent advances in electrochemical sensors and biosensors based on nanomaterials and nanostructures during 2013 to 2014. The aim of this effort is to provide the reader with a clear and concise view of new advances in areas ranging from electrode engineering, strategies for electrochemical signal amplification, and novel electroanalytical techniques used in the miniaturization and integration of the sensors. Moreover, the authors have attempted to highlight areas of the latest and significant development of enhanced electrochemical nanosensors and nanobiosensors that inspire broader interests across various disciplines. Electrochemical sensors for small molecules, enzyme-based biosensors, genosensors, immunosensors, and cytosensors are reviewed herein (Figure 1). Such novel advances are important for the development of electrochemical sensors that open up new avenues and methods for future research. In conclusion, we recommend readers interested in the general principles of electrochemical sensors and electrochemical methods to refer to other excellent literature for a broad scope in this area.(3, 4) However, due to the explosion of publications in this active field, we do not claim that this Review includes all of the published works in the past two years and we apologize to the authors of excellent work, which is unintentionally left out.