65 Search Results

The massive data generated by scientists daily serve as both a major catalyst for new discoveries and innovations, as well as a significant roadblock that restricts access to the data. Here, our paper introduces a new approach to removing Big Data barriers and democratizing access to petascale data for the broader scientific community. Our novel data fabric abstraction layer allows user-friendly querying of scientific information while hiding the complexities of dealing with file systems or cloud services. We enable FAIR (Findable, Accessible, Interoperable, and Reusable) access to datasets such as NASA’s petascale climate datasets. Our paper presents an approach tomore » managing, visualizing, and analyzing petabytes of data within a browser on equipment ranging from the top NASA supercomputer to commodity hardware like a laptop. Our novel data fabric abstraction utilizes state-of-the art progressive compression algorithms and machine-learning insights to power scalable visualization dashboards for petascale data. The result provides users with the ability to identify extreme events or trends dynamically, expanding access to scientific data and further enabling discoveries. We validate our approach by improving the ability of climate scientists to visually explore their data via three fully interactive dashboards. We further validate our approach by deploying the dashboards and simplified training materials in the classroom at a minority-serving institution. These dashboards, released in simplified form to the general public, contribute significantly to a broader push to democratize the access and use of climate data.« less

Recycling multilayer plastic films is challenged by a diversity of polymers, prompting development of new recycling methods. For the depolymerization of mixed polymers like those in multilayer films, metal-catalyzed autoxidation offers a versatile chemical recycling method to deconstruct multiple polymers to useful oxygenates. Here, we demonstrate that catalytic autoxidation is effective for depolymerizing multilayer films across diverse chemistries. We investigated conditions for a model polyethylene substrate using a Co, Mn, and Br cocatalyst system, achieving full carbon closure with oxygenated small molecules contributing up to 48 mol% carbon. Subsequently, we characterized product distributions for several common polymers used in multilayer filmsmore » using high-resolution mass spectrometry (HRMS) and developed analytical methods to quantify the resulting complex product streams. Optimized conditions for polyethylene were applied to 11 multilayer plastic films containing 10 different polymers, including films with nonpolymeric potential disrupters like aluminum foil and titanium dioxide, showing that catalytic autoxidation is effective across a broad range of polymer types and is resistant to disrupters and additives. The generation of CO₂ in these reactions overall suggests that both reaction engineering and modifications to the reaction conditions will be required to achieve higher yields of soluble oxygenated products.« less

Electrochemical CO 2 reduction reaction (CO 2 RR) catalyzed by molecular earth-abundant metal catalysts is a promising strategy to convert CO 2 into value-added products. One recent trend in this field has been focusing on the rational design of catalysts by incorporating redox-active ligands and modifying the secondary coordination sphere (SCS) to achieve efficient and selective CO 2 RR. Herein, we report a series of Co bis(bipyridine) catalysts featuring various dangling groups, such as pyridine, tertiary amine, or butyl, in the secondary coordination sphere ( Co-PyMe, Co-Py, Co-PrN, and Co-Bu ). Efficient, selective electrocatalytic CO 2 RR was achieved bymore » the complexes after the generation of triply reduced intermediate consisting of a Co I center and a dianionic ligand, producing CO as the major product and trace amount of H 2 . Strong correlations with the identity of dangling groups and turnover frequency (TOF) have been observed, in which Co-PyMe displayed the highest TOF (1086 s –1 in MeCN/H 2 O). Mechanistic studies indicated that the acceleration of CO 2 RR with pyridine-functionalized catalysts were derived from the protonation of pyridine dangling groups which participated as weak acids in the H-bonding network with exogenous proton sources, stabilizing CO 2 -bound intermediates and facilitating proton transfer. In addition, precatalytic CO 2 binding and activation at the third reduction (−2.1 V) was revealed by CV and SEC-IR studies. The resultant doubly reduced CO-bound species acted as a trapping state which inhibited CO 2 RR electrocatalysis. Regeneration of active species was accessed via reductive dissociation of CO at a more negative potential. This study highlights the combined effects of redox-active ligands and pyridine/pyridinium as SCS groups on CO 2 RR catalysis and provides design principles for future development of CO 2 RR catalysts utilizing pyridine/pyridiniums as SCS functional groups to fine-tune the catalytic activity.« less

The next generation of nuclear and particle physics rare-event search experiments demand structural materials combining ultra-low levels of radioactive contamination with exceptional mechanical strength. Here, this study evaluates chemical vapor deposition (CVD) nickel as a low radioactive background candidate structural material for such applications. Manufacturer-supplied CVD Ni grown on aluminum substrates was assayed via inductively coupled plasma mass spectrometry (ICP-MS) employing isotope-dilution. These material assays produced measured bulk concentration of ²³²Th, ²³⁸U, and ^natK at the levels of ~70 ppq, ≲100 ppq, and ~900 ppt, respectively, which is the lowest reported in nickel. Surface-etch profiling uncovered higher concentrations of thesemore » contaminants extending ~10 μm beneath the surface, likely associated with the aluminum growth substrate. Additionally, the CVD Ni underwent tensile testing alongside standard Ni samples. CVD Ni exhibited a planar tensile strength of ~600 MPa, significantly surpassing standard nickel. However, heat treatment was found to reduce the tensile strength to levels comparable to standard Ni, with implications for high-temperature weld joining methods. The results reported are compared to the one other well documented usage of CVD Ni in a low radioactive background physics research experiment and a discussion is provided on how the currently reported results may arise from changes in CVD fabrication or testing process. These results establish CVD Ni as a promising low-radioactivity structural material, while outlining the need for further development in surface cleaning and weld-joining techniques to fully realize its potential in large-scale, low radioactive background rare-event search experiments.« less

Lifetimes of photoexcited charge transfer (CT) states in transition metal chromophores are influenced by low-lying ligand field (LF) excited states, especially for 3d metal complexes. To manipulate interactions between LF and CT states, it is important to be able to control LF excited state energies using tunable synthetic variables. In this report, we use Fe 2p3d L₃-edge resonant inelastic X-ray scattering (RIXS) to measure LF excited state energies of three homoleptic iron chromophores coordinated by strong-field N-heterocyclic carbenes (NHCs). We investigate the effect of oxidation state and ligand scaffold on LF energies and covalency parameters. A cyclometalated bis(NHC) ligand affordsmore » both high LF excited state energies (and thus high 10 Dq) as well as high metal–ligand covalency compared to other iron complexes with very strong-field ligands. However, for the set of complexes investigated, we do not observe meaningful correlation between the LF excited state energies and the CT excited state lifetimes. These results illustrate that targeting long-lived CT excited states necessitates control of multiple molecular excited state properties, with destabilization of the LF excited state energies proving necessary, but insufficient, to control the CT excited state lifetime in Fe carbene complexes.« less

The ultrafast excited state pathways and dynamics of Ni^II-bipyridine complexes influence the yield of photochemical processes involved in their catalytic cross-coupling reactions. Here we present ultrafast Ni Kβ X-ray emission spectroscopy (XES) and X-ray solution scattering (XSS) of a Ni^II-bipyridine aryl halide complex, [Ni(^t‑Bubpy)(o-tol)Br], to quantify the excited state population dynamics and structural changes of the precatalyst. Due to the local spin-sensitivity of XES, the population dynamics of metal-to-ligand charge transfer (MLCT) and metalcentered (MC) excited states is established. A rapid ground state recovery pathway is newly identified, representing a significant deactivation pathway during photocatalysis. Furthermore, the pseudotetrahedral structure ofmore » the long-lived MC excited state is unambiguously identified and refined by XSS. The results advance our understanding of the ultrafast relaxation mechanisms that impact the photocatalytic mechanism and yield for Ni^II-bipyridine aryl halide cross-coupling catalysts.« less

The removal of dyes from coloured textile waste represents a sustainable approach to textile recycling, enabling the recovery of valuable chemical, and material resources that would otherwise be discarded. Up to 40% of the greenhouse gas emissions from textiles originate from dye production, making efficient recycling of dyes a major opportunity for curbing emissions and minimizing waste in both textile manufacturing and recycling. Here, in this study, we demonstrate a process for the extraction, purification, and reuse of mixed dyes from polyester textiles using bio-based, non-hazardous solvents selected on the basis of computational predictions for polyester and dye solubilities. Extractedmore » dyes are purified to individual compounds using counter-current chromatography and analysed via liquid chromatography-mass spectrometry. Post-extraction characterization of the extracted dyes and polymer substrate confirms dye colour retention and polyester fabric property preservation. Dye recycling is demonstrated by redyeing colour-free fabrics with the recovered dyes. We further show a potential process configuration for dye removal using a flow-through reactor packed with a textile substrate. The proposed dye removal process produces reusable, recyclable dyes, and dye-free fabrics, thus facilitating textile recycling.« less

We study the sensitivity of nEXO to solar neutrino charged-current interactions, 𝜈_𝑒 +¹³⁶Xe → ¹³⁶Cs*+𝑒⁻, as well as analogous interactions predicted by models of fermionic dark matter. Due to the recently observed low-lying isomeric states of ¹³⁶Cs, these interactions will create a time-delayed coincident signal observable in the scintillation channel. Here we develop a detailed Monte Carlo simulation of scintillation emission, propagation, and detection in the nEXO detector to model these signals under different assumptions about the timing resolution of the photosensor readout. We show this correlated signal can be used to achieve background discrimination on the order of 10⁻⁹,more » enabling nEXO to make background-free measurements of solar neutrinos above the reaction threshold of 0.668 MeV. We project that nEXO could measure the flux of neutrinos from the carbon-nitrogen-oxygen cycle with a statistical uncertainty of 25%, thus contributing a novel and competitive measurement toward addressing the solar metallicity problem. Additionally, nEXO could measure the mean energy of the ⁷Be neutrinos with a precision of 𝜎 ≤ 1.5 keV and could determine the survival probability of ⁷Be and pep solar 𝜈𝑒 with precision comparable to the state of the art. These quantities are sensitive to the Sun’s core temperature and to nonstandard neutrino interactions, respectively. Here, the strong background suppression would allow nEXO to search for charged-current interactions of fermionic dark matter in the mass range 𝑚_𝜒 = 0.668–7 MeV with a sensitivity up to three orders of magnitude better than current limits.« less

Polyamides, such as nylons, are often used in multi-component materials, like textiles and packaging, and are accompanied with unique recycling challenges. Recently, autoxidation and bioconversion has emerged as a tandem approach for the conversion of mixed plastics waste to single products, however the fate of polyamides in these processes is unknown. Here, we optimized the autoxidation of nylon-6 and nylon-6,6 depolymerization, achieving >92 mol% nitrogen recovery from both substrates, predominantly as acetamide, and 20–27 mol% carbon recovery (not including acetamide). Experiments with ¹³C-labeled acetic acid demonstrated that the carbon in acetamide was solvent derived. Autoxidation of mixed nylon-6 and poly(ethylenemore » terephthalate) (PET) post-consumer fibers resulted in similar carbon and nitrogen recoveries from nylon, while PET was depolymerized to terephthalic acid (TPA) at >65 C-mol% recovery. Next, we engineered Pseudomonas putida KT2440 to utilize acetamide as the sole carbon and nitrogen source for growth through the constitutive expression of genes encoding amidase enzymes, including a native amidase (PP_0613) shown to be active on C₂–C₄ amides. Heterologous chromosomal expression of amiE, encoding the amidase from P. aeruginosa, was found to be superior to PP_0613 constitutive expression in genome integrated strains. Prior engineering to enable TPA conversion to β-ketoadipate pathway intermediate protocatechuate was leveraged and combined with deletion of pcaD to produce muconolactone as a product. Finally, a stacked strain engineered for conversion of acetamide, TPA, and DCAs was evaluated on the reaction product from autoxidation of mixed post-consumer nylon and PET fibers without any supplemental nitrogen, achieving quantitative yields in the presence of supplemental carbon.« less

Rare event searches such as neutrinoless double beta decay and Weakly Interacting Massive Particle detection require ultra-low background detectors. Radon contamination is a significant challenge for these experiments, which employ highly sensitive radon assay techniques to identify and select low-emission materials. This work presents the development of ultra-sensitive electrostatic chamber (ESC) instruments designed to measure radon emanation in a recirculating gas loop, for future lower background experiments. Unlike traditional methods that separate emanation and detection steps, this system allows continuous radon transport and detection. This is made possible with a custom-built recirculation pump. A Python-based analysis framework, PyDAn, was developedmore » to process and fit time-dependent radon decay data. Radon emanation rates are given for various materials measured with this instrument. A radon source of known activity provides an absolute calibration, enabling statistically-limited minimal detectable activities of 20 µBq. These devices are powerful tools for screening materials in the development of low-background particle physics experiments.« less