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 »
- Authors:
-
- Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK
- Department of Molecular Biology and Biotechnology, University of Sheffield, Sheffield S10 2TN, UK
- King Saud University, Riyadh, Saudi Arabia
- 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)
- OSTI Identifier:
- 1418408
- Alternate Identifier(s):
- OSTI ID: 1470605
- Grant/Contract Number:
- SC0001035
- Resource Type:
- 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. https://doi.org/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. https://doi.org/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},
number = 8,
volume = 9,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
https://doi.org/10.1039/C7SC04424K
Web of Science
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