Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes
An iodide-terminated polymer (Polymer-I) is converted to a thiol-terminated polymer (Polymer-SH) using HSCH2CH2SH in a remarkably short time (10 min). Polymer-SH is further converted to a pyridyl disulfide-terminated polymer (Polymer-SS-Py). The hetero-coupling of Polymer-SH and Polymer-SS-Py is suc...
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sg-ntu-dr.10356-1536022023-02-28T19:52:59Z Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes Sim, Xuan Ming Chen, Chen Goto, Atsushi School of Physical and Mathematical Sciences Division of Chemistry and Biological Chemistry Science::Chemistry::Organic chemistry::Polymers Polymer Brush Rewritable Surface An iodide-terminated polymer (Polymer-I) is converted to a thiol-terminated polymer (Polymer-SH) using HSCH2CH2SH in a remarkably short time (10 min). Polymer-SH is further converted to a pyridyl disulfide-terminated polymer (Polymer-SS-Py). The hetero-coupling of Polymer-SH and Polymer-SS-Py is successfully achieved to quantitatively generate a polymer disulfide (Polymer-SS-Polymer). Exploiting this efficient hetero-coupling technique, Polymer-SH is attached (grafted) on a Py-SS-immobilized surface to generate a polymer brush via a disulfide (-SS-) linkage (writing process). The -SS- linkage is cleaved by the treatment with dithiothreitol (DTT) to detach the polymer from the surface (erasing process). Subsequently, another Polymer-SH is attached on the surface to generate another polymer brush (rewriting process). Thus, a writable, erasable, and rewritable polymer brush surface is achieved. Hydrophilic, hydrophobic, and super-hydrophobic polymers (Polymer-SH) are attached on the surface, tailoring the surface wettability in the writing-erasing-rewriting cycles. Polymer-SH is also attached on a chain-end Py-SS-functionalized polymer brush surface, generating a rewritable block copolymer brush surface. A patterned block copolymer brush surface is also obtained using photo-irradiation and a photo-mask in the erasing process. The metal-free synthetic procedure, accessibility to patterned brushes, and switchable surface properties via the writing-erasing-rewriting process are attractive features of the present approach. Ministry of Education (MOE) National Research Foundation (NRF) Accepted version This work was supported by National Research Foundation (NRF) Investigatorship in Singapore (NRF-NRFI05-2019-0001) and Academic Research Fund (AcRF) Tier 2 from Ministry of Education in Singapore (MOE2017-T2-1-018). 2021-12-12T09:21:10Z 2021-12-12T09:21:10Z 2021 Journal Article Sim, X. M., Chen, C. & Goto, A. (2021). Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes. ACS Applied Materials & Interfaces, 13(20), 24183-24193. https://dx.doi.org/10.1021/acsami.1c07195 1944-8244 https://hdl.handle.net/10356/153602 10.1021/acsami.1c07195 33982564 2-s2.0-85106383907 20 13 24183 24193 en NRF-NRFI05-2019-0001 MOE2017-T2-1-018 ACS Applied Materials & Interfaces This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acsami.1c07195. application/pdf |
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Science::Chemistry::Organic chemistry::Polymers Polymer Brush Rewritable Surface Sim, Xuan Ming Chen, Chen Goto, Atsushi Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes |
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An iodide-terminated polymer (Polymer-I) is converted to a thiol-terminated polymer (Polymer-SH) using HSCH2CH2SH in a remarkably short time (10 min). Polymer-SH is further converted to a pyridyl disulfide-terminated polymer (Polymer-SS-Py). The hetero-coupling of Polymer-SH and Polymer-SS-Py is successfully achieved to quantitatively generate a polymer disulfide (Polymer-SS-Polymer). Exploiting this efficient hetero-coupling technique, Polymer-SH is attached (grafted) on a Py-SS-immobilized surface to generate a polymer brush via a disulfide (-SS-) linkage (writing process). The -SS- linkage is cleaved by the treatment with dithiothreitol (DTT) to detach the polymer from the surface (erasing process). Subsequently, another Polymer-SH is attached on the surface to generate another polymer brush (rewriting process). Thus, a writable, erasable, and rewritable polymer brush surface is achieved. Hydrophilic, hydrophobic, and super-hydrophobic polymers (Polymer-SH) are attached on the surface, tailoring the surface wettability in the writing-erasing-rewriting cycles. Polymer-SH is also attached on a chain-end Py-SS-functionalized polymer brush surface, generating a rewritable block copolymer brush surface. A patterned block copolymer brush surface is also obtained using photo-irradiation and a photo-mask in the erasing process. The metal-free synthetic procedure, accessibility to patterned brushes, and switchable surface properties via the writing-erasing-rewriting process are attractive features of the present approach. |
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School of Physical and Mathematical Sciences |
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School of Physical and Mathematical Sciences Sim, Xuan Ming Chen, Chen Goto, Atsushi |
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Article |
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Sim, Xuan Ming Chen, Chen Goto, Atsushi |
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Sim, Xuan Ming |
title |
Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes |
title_short |
Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes |
title_full |
Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes |
title_fullStr |
Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes |
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Polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes |
title_sort |
polymer coupling via hetero-disulfide exchange and its applications to rewritable polymer brushes |
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2021 |
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https://hdl.handle.net/10356/153602 |
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