skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Fabrication of microstructured binary polymer brush “corrals” with integral pH sensing for studies of proton transport in model membrane systems

Abstract

Binary brush structures consisting of poly(cysteine methacrylate) (PCysMA) “corrals” enclosed within poly(oligoethylene glycol methyl ether methacrylate) (POEGMA) “walls” are fabricated simply and efficiently using a two-step photochemical process. First, the C–Cl bonds of 4-(chloromethyl)phenylsilane monolayers are selectively converted into carboxylic acid groups by patterned exposure to UV light through a mask and POEGMA is grown from unmodified chlorinated regions by surface-initiated atom-transfer radical polymerisation (ATRP). Incorporation of a ratiometric fluorescent pH indicator, Nile Blue 2-(methacryloyloxy)ethyl carbamate (NBC), into the polymer brushes facilitates assessment of local changes in pH using a confocal laser scanning microscope with spectral resolution capability. Moreover, the dye label acts as a radical spin trap, enabling removal of halogen end-groups from the brushes via in situ dye addition during the polymerisation process. Second, an initiator is attached to the carboxylic acid-functionalised regions formed by UV photolysis in the patterning step, enabling growth of PCysMA brushes by ATRP. Transfer of the system to THF, a poor solvent for PCysMA, causes collapse of the PCysMA brushes. At the interface between the collapsed brush and solvent, selective derivatisation of amine groups is achieved by reaction with excess glutaraldehyde, facilitating attachment of aminobutyl(nitrile triacetic acid) (NTA). The PCysMA brush collapse ismore » reversed on transfer to water, leaving it fully expanded but only functionalized at the brush–water interface. Following complexation of NTA with Ni 2+, attachment of histidine-tagged proteorhodopsin and lipid deposition, light-activated transport of protons into the brush structure is demonstrated by measuring the ratiometric response of NBC in the POEGMA walls.« less

Authors:
ORCiD logo [1];  [1];  [1];  [2];  [3];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [4]
  1. Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK
  2. Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN, UK
  3. King Saud University, Riyadh, Saudi Arabia
  4. Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK, Krebs Institute for Mechanistic Biology
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1418408
Alternate Identifier(s):
OSTI ID: 1470605
Grant/Contract Number:  
SC0001035
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 8; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; solar (fuels); photosynthesis (natural and artificial); biofuels (including algae and biomass); bio-inspired; charge transport; membrane; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Madsen, J., Ducker, R. E., Al Jaf, O., Cartron, M. L., Alswieleh, A. M., Smith, C. H., Hunter, C. N., Armes, S. P., and Leggett, G. J. Fabrication of microstructured binary polymer brush “corrals” with integral pH sensing for studies of proton transport in model membrane systems. United Kingdom: N. p., 2018. Web. doi:10.1039/C7SC04424K.
Madsen, J., Ducker, R. E., Al Jaf, O., Cartron, M. L., Alswieleh, A. M., Smith, C. H., Hunter, C. N., Armes, S. P., & Leggett, G. J. Fabrication of microstructured binary polymer brush “corrals” with integral pH sensing for studies of proton transport in model membrane systems. United Kingdom. doi:10.1039/C7SC04424K.
Madsen, J., Ducker, R. E., Al Jaf, O., Cartron, M. L., Alswieleh, A. M., Smith, C. H., Hunter, C. N., Armes, S. P., and Leggett, G. J. Mon . "Fabrication of microstructured binary polymer brush “corrals” with integral pH sensing for studies of proton transport in model membrane systems". United Kingdom. doi:10.1039/C7SC04424K.
@article{osti_1418408,
title = {Fabrication of microstructured binary polymer brush “corrals” with integral pH sensing for studies of proton transport in model membrane systems},
author = {Madsen, J. and Ducker, R. E. and Al Jaf, O. and Cartron, M. L. and Alswieleh, A. M. and Smith, C. H. and Hunter, C. N. and Armes, S. P. and Leggett, G. J.},
abstractNote = {Binary brush structures consisting of poly(cysteine methacrylate) (PCysMA) “corrals” enclosed within poly(oligoethylene glycol methyl ether methacrylate) (POEGMA) “walls” are fabricated simply and efficiently using a two-step photochemical process. First, the C–Cl bonds of 4-(chloromethyl)phenylsilane monolayers are selectively converted into carboxylic acid groups by patterned exposure to UV light through a mask and POEGMA is grown from unmodified chlorinated regions by surface-initiated atom-transfer radical polymerisation (ATRP). Incorporation of a ratiometric fluorescent pH indicator, Nile Blue 2-(methacryloyloxy)ethyl carbamate (NBC), into the polymer brushes facilitates assessment of local changes in pH using a confocal laser scanning microscope with spectral resolution capability. Moreover, the dye label acts as a radical spin trap, enabling removal of halogen end-groups from the brushes via in situ dye addition during the polymerisation process. Second, an initiator is attached to the carboxylic acid-functionalised regions formed by UV photolysis in the patterning step, enabling growth of PCysMA brushes by ATRP. Transfer of the system to THF, a poor solvent for PCysMA, causes collapse of the PCysMA brushes. At the interface between the collapsed brush and solvent, selective derivatisation of amine groups is achieved by reaction with excess glutaraldehyde, facilitating attachment of aminobutyl(nitrile triacetic acid) (NTA). The PCysMA brush collapse is reversed on transfer to water, leaving it fully expanded but only functionalized at the brush–water interface. Following complexation of NTA with Ni2+, attachment of histidine-tagged proteorhodopsin and lipid deposition, light-activated transport of protons into the brush structure is demonstrated by measuring the ratiometric response of NBC in the POEGMA walls.},
doi = {10.1039/C7SC04424K},
journal = {Chemical Science},
issn = {2041-6520},
number = 8,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/C7SC04424K

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Evolving Concepts About the Role of Acidosis in Ischemic Neuropathology
journal, September 1993


Peptide and protein PEGylation
journal, March 2001


In Pursuit of Zero: Polymer Brushes that Resist the Adsorption of Proteins
journal, June 2009

  • Hucknall, Angus; Rangarajan, Srinath; Chilkoti, Ashutosh
  • Advanced Materials, Vol. 21, Issue 23, p. 2441-2446
  • DOI: 10.1002/adma.200900383

Fabrication of Chemically Microstructured Polymer Brushes
journal, September 2006


Treatment of Acute Respiratory Acidosis in Chronic Obstructive Lung Disease
journal, September 1971


Cluster size regulates protein sorting in the immunological synapse
journal, July 2009

  • Hartman, N. C.; Nye, J. A.; Groves, J. T.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 31
  • DOI: 10.1073/pnas.0902621106

Integration of energy and electron transfer processes in the photosynthetic membrane of Rhodobacter sphaeroides
journal, October 2014

  • Cartron, Michaël L.; Olsen, John D.; Sener, Melih
  • Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1837, Issue 10
  • DOI: 10.1016/j.bbabio.2014.02.003

Management of Life-Threatening Acid–Base Disorders
journal, January 1998


Adaptation to hypoxia and acidosis in carcinogenesis and tumor progression
journal, October 2008


Bacterial Rhodopsin: Evidence for a New Type of Phototrophy in the Sea
journal, September 2000


Fabrication of Patterned Amine Reactivity Templates Using 4-Chloromethylphenylsiloxane Self-Assembled Monolayer Films
journal, August 1999

  • Brandow, S. L.; Chen, M. -S.; Aggarwal, R.
  • Langmuir, Vol. 15, Issue 16
  • DOI: 10.1021/la9902082

Bioreactor performance in anaerobic digestion of fruit and vegetable wastes
journal, March 2005


Electropatterning of Binary Polymer Brushes by Surface-initiated RAFT and ATRP
journal, May 2011

  • Tria, Maria Celeste R.; Advincula, Rigoberto C.
  • Macromolecular Rapid Communications, Vol. 32, Issue 13
  • DOI: 10.1002/marc.201100050

Optical properties of intrinsic silicon at 300 K
journal, January 1995

  • Green, Martin A.; Keevers, Mark J.
  • Progress in Photovoltaics: Research and Applications, Vol. 3, Issue 3
  • DOI: 10.1002/pip.4670030303

Advances in polymers for anti-biofouling surfaces
journal, January 2008

  • Krishnan, Sitaraman; Weinman, Craig J.; Ober, Christopher K.
  • Journal of Materials Chemistry, Vol. 18, Issue 29
  • DOI: 10.1039/b801491d

Critical Salt Effects in the Swelling Behavior of a Weak Polybasic Brush
journal, February 2014

  • Willott, Joshua D.; Murdoch, Timothy J.; Humphreys, Ben A.
  • Langmuir, Vol. 30, Issue 7
  • DOI: 10.1021/la4047275

Smart polymer brush nanostructures guide the self-assembly of pore-spanning lipid bilayers with integrated membrane proteins
journal, January 2014

  • Wilhelmina de Groot, G.; Demarche, Sophie; Santonicola, M. Gabriella
  • Nanoscale, Vol. 6, Issue 4
  • DOI: 10.1039/c3nr05356c

A novel fluorescent polymer brushes film as a device for ultrasensitive detection of TNT
journal, January 2013

  • Yang, Xudong; Shen, Bowen; Jiang, Yingnan
  • J. Mater. Chem. A, Vol. 1, Issue 4
  • DOI: 10.1039/C2TA00514J

Multi-component hierarchically structured polymer brushes
journal, January 2012

  • Yom, Jeannie; Lane, Sarah M.; Vaia, Richard A.
  • Soft Matter, Vol. 8, Issue 48
  • DOI: 10.1039/c2sm26277k

Controlled Micropatterning of a Si(100) Surface by Combined Nitroxide-Mediated and Atom Transfer Radical Polymerizations
journal, July 2005

  • Xu, F. J.; Song, Y.; Cheng, Z. P.
  • Macromolecules, Vol. 38, Issue 15
  • DOI: 10.1021/ma050581i

Lipid Bilayers on Polyacrylamide Brushes for Inclusion of Membrane Proteins
journal, October 2005

  • Smith, Emily A.; Coym, Jason W.; Cowell, Scott M.
  • Langmuir, Vol. 21, Issue 21
  • DOI: 10.1021/la051116h

Two-dimensional microelectrophoresis in supported lipid bilayers
journal, November 1992


Zwitterionic Poly(amino acid methacrylate) Brushes
journal, June 2014

  • Alswieleh, Abdullah M.; Cheng, Nan; Canton, Irene
  • Journal of the American Chemical Society, Vol. 136, Issue 26
  • DOI: 10.1021/ja503400r

The Growth of Bacterial Cultures
journal, October 1949


To Patterned Binary Polymer Brushes via Capillary Force Lithography and Surface-Initiated Polymerization
journal, June 2006

  • Liu, Yong; Klep, Viktor; Luzinov, Igor
  • Journal of the American Chemical Society, Vol. 128, Issue 25
  • DOI: 10.1021/ja061646f

A review of advanced small-scale parallel bioreactor technology for accelerated process development: Current state and future need
journal, November 2010

  • Bareither, Rachel; Pollard, David
  • Biotechnology Progress, Vol. 27, Issue 1
  • DOI: 10.1002/btpr.522

Functionalization of self-assembled monolayers on glass and oxidized silicon wafers by surface reactions
journal, January 2001

  • Flink, Simon; van Veggel, Frank C. J. M.; Reinhoudt, David N.
  • Journal of Physical Organic Chemistry, Vol. 14, Issue 7
  • DOI: 10.1002/poc.372

Fabrication of Biological Nanostructures by Scanning Near-Field Photolithography of Chloromethylphenylsiloxane Monolayers
journal, January 2006

  • Sun, Shuqing; Montague, Matthew; Critchley, Kevin
  • Nano Letters, Vol. 6, Issue 1
  • DOI: 10.1021/nl051804l

Natriuretic Peptides
journal, July 1998

  • Epstein, Franklin H.; Levin, Ellis R.; Gardner, David G.
  • New England Journal of Medicine, Vol. 339, Issue 5
  • DOI: 10.1056/NEJM199807303390507

The Activity Ratio of Zwitterions and Uncharged Molecules in Ampholyte Solutions. The Dissociation Constants of Amino Acid Esters
journal, June 1933

  • Edsall, John T.; Blanchard, Muriel H.
  • Journal of the American Chemical Society, Vol. 55, Issue 6
  • DOI: 10.1021/ja01333a019

Fabrication of Chemically Tethered Binary Polymer-Brush Pattern through Two-Step Surface-Initiated Atomic-Transfer Radical Polymerization
journal, December 2004

  • Zhou, Feng; Jiang, Lei; Liu, Weimin
  • Macromolecular Rapid Communications, Vol. 25, Issue 23
  • DOI: 10.1002/marc.200400397

Synthesis and optimization of fluorescent poly( N- isopropyl acrylamide)-coated surfaces by atom transfer radical polymerization for cell culture and detachment
journal, March 2015

  • Cooperstein, Marta A.; Bluestein, Blake M.; Canavan, Heather E.
  • Biointerphases, Vol. 10, Issue 1
  • DOI: 10.1116/1.4894530

Dual Excitation Ratiometric Fluorescent pH Sensor for Noninvasive Bioprocess Monitoring: Development and Application
journal, October 2002

  • Kermis, H. R.; Kostov, Y.; Harms, P.
  • Biotechnology Progress, Vol. 18, Issue 5
  • DOI: 10.1021/bp0255560

Concentrating Membrane Proteins Using Asymmetric Traps and AC Electric Fields
journal, May 2011

  • Cheetham, Matthew R.; Bramble, Jonathan P.; McMillan, Duncan G. G.
  • Journal of the American Chemical Society, Vol. 133, Issue 17
  • DOI: 10.1021/ja2007615

Nile Blue-Based Nanosized pH Sensors for Simultaneous Far-Red and Near-Infrared Live Bioimaging
journal, September 2013

  • Madsen, Jeppe; Canton, Irene; Warren, Nicholas J.
  • Journal of the American Chemical Society, Vol. 135, Issue 39
  • DOI: 10.1021/ja407380t

Direct Imaging of Protein Organization in an Intact Bacterial Organelle Using High-Resolution Atomic Force Microscopy
journal, November 2016


Micrometre and nanometre scale patterning of binary polymer brushes, supported lipid bilayers and proteins
journal, January 2017

  • Johnson, Alexander; Madsen, Jeppe; Chapman, Paul
  • Chemical Science, Vol. 8, Issue 6
  • DOI: 10.1039/C7SC00289K

Bond Dissociation Energies of the N−H Bond and Rate Constants for the Reaction with Alkyl, Alkoxyl, and Peroxyl Radicals of Phenothiazines and Related Compounds
journal, December 1999

  • Lucarini, Marco; Pedrielli, Pamela; Pedulli, Gian Franco
  • Journal of the American Chemical Society, Vol. 121, Issue 49
  • DOI: 10.1021/ja992904u

Spatial Control over Cross-Linking Dictates the pH-Responsive Behavior of Poly(2-( tert -butylamino)ethyl methacrylate) Brushes
journal, January 2014

  • Alswieleh, Abdullah M.; Cheng, Nan; Leggett, Graham J.
  • Langmuir, Vol. 30, Issue 5
  • DOI: 10.1021/la403666y

Surface-Initiated Polymer Brushes in the Biomedical Field: Applications in Membrane Science, Biosensing, Cell Culture, Regenerative Medicine and Antibacterial Coatings
journal, October 2014

  • Krishnamoorthy, Mahentha; Hakobyan, Shoghik; Ramstedt, Madeleine
  • Chemical Reviews, Vol. 114, Issue 21
  • DOI: 10.1021/cr500252u

Polymer brushes via surface-initiated polymerizations
journal, January 2004

  • Edmondson, Steve; Osborne, Vicky L.; Huck, Wilhelm T. S.
  • Chemical Society Reviews, Vol. 33, Issue 1
  • DOI: 10.1039/b210143m

Stratified Polymer Brushes from Microcontact Printing of Polydopamine Initiator on Polymer Brush Surfaces
journal, March 2014

  • Wei, Qiangbing; Yu, Bo; Wang, Xiaolong
  • Macromolecular Rapid Communications, Vol. 35, Issue 11
  • DOI: 10.1002/marc.201400052

A Self-Assembled Monolayer for the Binding and Study of Histidine-Tagged Proteins by Surface Plasmon Resonance
journal, January 1996

  • Sigal, George B.; Bamdad, Cynthia; Barberis, Alcide
  • Analytical Chemistry, Vol. 68, Issue 3
  • DOI: 10.1021/ac9504023

Multicomponent Polymer Brushes
journal, December 2006

  • Zhou, Feng; Zheng, Zijian; Yu, Bo
  • Journal of the American Chemical Society, Vol. 128, Issue 50
  • DOI: 10.1021/ja0654377

Fluorescent monomers as building blocks for dye labeled polymers: synthesis and application in energy conversion, biolabeling and sensors
journal, January 2013

  • Breul, Alexander M.; Hager, Martin D.; Schubert, Ulrich S.
  • Chemical Society Reviews, Vol. 42, Issue 12
  • DOI: 10.1039/c3cs35478d

Nano-Anemones: Stimulus-Responsive Copolymer-Micelle Surfaces
journal, October 2004

  • Webber, G. B.; Wanless, E. J.; Armes, S. P.
  • Advanced Materials, Vol. 16, Issue 20
  • DOI: 10.1002/adma.200400086

Fluorescent Indicators for Intracellular pH
journal, May 2010

  • Han, Junyan; Burgess, Kevin
  • Chemical Reviews, Vol. 110, Issue 5
  • DOI: 10.1021/cr900249z

Fabrication of Complex Three-Dimensional Polymer Brush Nanostructures through Light-Mediated Living Radical Polymerization
journal, June 2013

  • Poelma, Justin E.; Fors, Brett P.; Meyers, Gregory F.
  • Angewandte Chemie International Edition, Vol. 52, Issue 27
  • DOI: 10.1002/anie.201301845

Reversible Oriented Surface Immobilization of Functional Proteins on Oxide Surfaces
journal, June 1997

  • Schmid, Evelyne L.; Keller, Thomas A.; Dienes, Zoltan
  • Analytical Chemistry, Vol. 69, Issue 11
  • DOI: 10.1021/ac9700033

Evaluating Nanoparticle Sensor Design for Intracellular pH Measurements
journal, July 2011

  • Benjaminsen, Rikke V.; Sun, Honghao; Henriksen, Jonas R.
  • ACS Nano, Vol. 5, Issue 7
  • DOI: 10.1021/nn201643f

Copper(i) mediated radical polymerisation of uridine and adenosine monomers on a silica support
journal, January 2000

  • Marsh, Andrew; Khan, Afzal; Garcia, Margarita
  • Chemical Communications, Issue 21
  • DOI: 10.1039/b005832g

Controlling Two-Dimensional Tethered Vesicle Motion Using an Electric Field:  Interplay of Electrophoresis and Electro-Osmosis
journal, February 2006

  • Yoshina-Ishii, Chiaki; Boxer, Steven G.
  • Langmuir, Vol. 22, Issue 5
  • DOI: 10.1021/la0526277

New Poly(amino acid methacrylate) Brush Supports the Formation of Well-Defined Lipid Membranes
journal, March 2015

  • Blakeston, Anita C.; Alswieleh, Abdullah M.; Heath, George R.
  • Langmuir, Vol. 31, Issue 12
  • DOI: 10.1021/la504163s

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH
journal, January 2015

  • Yin, Jun; Hu, Ying; Yoon, Juyoung
  • Chemical Society Reviews, Vol. 44, Issue 14
  • DOI: 10.1039/C4CS00275J

An overview of nanoparticles commonly used in fluorescent bioimaging
journal, January 2015


Controlled/living radical polymerization: Features, developments, and perspectives
journal, January 2007


Simple, Direct Routes to Polymer Brush Traps and Nanostructures for Studies of Diffusional Transport in Supported Lipid Bilayers
journal, April 2017


Regulation of cytoplasmic pH in phagocytic cell function and dysfunction
journal, June 1991


A Nanogel for Ratiometric Fluorescent Sensing of Intracellular pH Values
journal, May 2010

  • Peng, Hong-shang; Stolwijk, Judith A.; Sun, Li-Ning
  • Angewandte Chemie International Edition, Vol. 49, Issue 25
  • DOI: 10.1002/anie.200906926

Postpolymerization Modification of Poly(glycidyl methacrylate) Brushes: An XPS Depth-Profiling Study
journal, July 2013

  • Barbey, Raphael; Laporte, Vincent; Alnabulsi, Saad
  • Macromolecules, Vol. 46, Issue 15
  • DOI: 10.1021/ma400819a

Fluorescence interference-contrast microscopy on oxidized silicon using a monomolecular dye layer
journal, September 1996

  • Lambacher, Armin; Fromherz, Peter
  • Applied Physics A Materials Science & Processing, Vol. 63, Issue 3
  • DOI: 10.1007/BF01567871

Augmenting light coverage for photosynthesis through YFP-enhanced charge separation at the Rhodobacter sphaeroides reaction centre
journal, January 2017

  • Grayson, Katie J.; Faries, Kaitlyn M.; Huang, Xia
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms13972

Surface modification of polymeric materials by plasma immersion ion implantation
journal, August 2005

  • Fu, Ricky K. Y.; Cheung, I. T. L.; Mei, Y. F.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 237, Issue 1-2
  • DOI: 10.1016/j.nimb.2005.05.029

pH-Responsive Fluorescent Molecular Bottlebrushes Prepared by Atom Transfer Radical Polymerization
journal, August 2011

  • Nese, Alper; Lebedeva, Natalia V.; Sherwood, Gizelle
  • Macromolecules, Vol. 44, Issue 15
  • DOI: 10.1021/ma201045c

High resolution X-ray photoelectron spectroscopy of l-cysteine self-assembled films
journal, January 2004

  • Cavalleri, O.; Gonella, G.; Terreni, S.
  • Physical Chemistry Chemical Physics, Vol. 6, Issue 15
  • DOI: 10.1039/b405516k