Madsen, J., Ducker, R.E., Al Jaf, O. et al. (6 more authors) (2018) Fabrication of microstructured binary polymer brush “corrals” with integral pH sensing for studies of proton transport in model membrane systems. Chemical Science, 9. pp. 2238-2251. ISSN 2041-6520
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 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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | Open Access Article. Published on 15 January 2018. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Funding Information: | Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL (EPSRC) EP/I012060/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 13 Mar 2018 11:31 |
Last Modified: | 14 Jan 2020 14:29 |
Published Version: | https://doi.org/10.1039/c7sc04424k |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Refereed: | Yes |
Identification Number: | 10.1039/c7sc04424k |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:128451 |