Biofunctional oligoN-isopropylacrylamide brushes on silicon wafer surface

J. Polym. Sci. Part A: Polym. Chem.

2015

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Novel types of dual‐functional surface‐attached polymer brushes were developed by interface‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization of 6‐azidohexylmethacrylate using the surface‐immobilized RAFT agent and the free initiator. The interface‐mediated RAFT polymerization produced silicon substrate coated with dual‐functional (azido groups from monomer and carboxylic acid groups from RAFT agent) poly(6‐azidohexylmethacrylate) [poly (AHMA)] with a grafting density as high as 0.59 chains/nm2. Dual‐functional polymer brushes can represent an attractive chemical platform to deliberately introduce other molecular units at specific sites. The azido groups of the poly(AHMA) brushes can be modified with alkyl groups via click reaction, known for their DNA hybridization, while the carboxylic acid end groups can be reacted with amine groups via amide reaction, known for their antifouling properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1696–1706

Section: Introductionmentioning

confidence: 99%

Synthesis of dual-functional poly(6-azidohexylmethacrylate) brushes by a RAFT agent carrying carboxylic acid end groups

Cimen

Yıldırım

J. Polym. Sci. Part A: Polym. Chem.

2015

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“…This variable tuning most often results from a sudden modification of the chain conformation of the brush when the external trigger is varied over a limited range. The rapid variations of properties which result from the rapidly changing chain conformation (“brush‐like” to “mushroom‐like”) make responsive polymer brushes ideally suited for applications such biosensors,6–8 microfluidic devices,9, 10 drug delivery systems,11, 12 actuation devices,13 or tunable adhesive surfaces 14, 15…”

Section: Introductionmentioning

confidence: 99%

“…[1][2][3][4][5] This variable tuning most often results from a sudden modification of the chain conformation of the brush when the external trigger is varied over a limited range. The rapid variations of properties which result from the rapidly changing chain conformation (''brush-like'' to ''mushroom-like'') make responsive polymer brushes ideally suited for applications such biosensors, [6][7][8] microfluidic devices, 9,10 drug delivery systems, 11,12 actuation devices, 13 or tunable adhesive surfaces. 14,15 Poly(N-isopropylacrylamide) [poly(NIPAM)] is one of the most studied synthetic responsive polymers, which undergoes a transition from a hydrophilic state to a hydrophobic state in water at 32 C. [16][17][18][19] Materials with surface-grafted poly(NIPAM) brushes exhibit temperature-responsive properties and have wide applications in water treatment, 20,21 drug delivery, 22 and biomedicals.…”

mentioning

confidence: 99%

RAFT‐mediated synthesis and temperature‐induced responsive properties of poly(2‐(2‐methoxyethoxy)ethyl methacrylate) brushes

Zengi̇n

Yıldırım

J. Polym. Sci. A Polym. Chem.

2012

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Well‐defined, high‐density poly(2‐(2‐methoxyethoxy)ethyl methacrylate) [poly(MEO2MA)] brushes were fabricated through a reliable strategy by the combination of self‐assembly of a monolayer of 3‐aminopropyltrimethoxy silane on silicon surface to immobilize 4‐cyano‐4‐(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid chain transfer agent and reversible addition‐fragmentation chain transfer‐mediated polymerization of MEO2MA. The whole fabrication process of the poly(MEO2MA) brushes was followed by water contact angle, grazing angle‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and atomic force microscopy. Characterization of the poly(MEO2MA) brushes, such as molecular weight and thickness determination, were measured by gel permeation chromatography and ellipsometry, and the grafting density was estimated. The temperature‐responsive property of the poly(MEO2MA) brushes was further investigated and the result verified the brush‐to‐mushroom phase transition of the poly(MEO2MA) chains from low to high temperature. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

“…Recently “living” polymerizations have been applied to grafting polymers from surfaces via “grafting‐from” technique. Among all the polymerizations for the synthesis of dense polymer brush, living radical polymerization, such as nitroxide‐mediated radical polymerization, atom‐transfer radical polymerization (ATRP), reversible addition‐fragmentation chain‐transfer (RAFT) polymerization, and single‐electron transfer‐living radical polymerization (SET‐LRP), is the most important one owing to its ease to control the thickness and the composition of the brush.…”

Section: Introductionmentioning

confidence: 99%

Stimuli‐responsive diblock copolymer brushes via combination of “click chemistry” and living radical polymerization

Demirci

Kinali-Demirci

J. Polym. Sci. Part A: Polym. Chem.

2013

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pH‐ and temperature‐responsive poly(N‐isopropylacrylamide‐block−4‐vinylbenzoic acid) (poly(NIPAAm‐b‐VBA)) diblock copolymer brushes on silicon wafers have been successfully prepared by combining click reaction, single‐electron transfer‐living radical polymerization (SET‐LRP), and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. Azide‐terminated poly(NIPAAm) brushes were obtained by SET‐LRP followed by reaction with sodium azide. A click reaction was utilized to exchange the azide end group of a poly(NIPAAm) brushes to form a surface‐immobilized macro‐RAFT agent, which was successfully chain extended via RAFT polymerization to produce poly(NIPAAm‐b‐VBA) brushes. The addition of sacrificial initiator and/or chain‐transfer agent permitted the formation of well‐defined diblock copolymer brushes and free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface. Ellipsometry, contact angle measurements, grazing angle‐Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy were used to characterize the immobilization of initiator on the silicon wafer, poly(NIPAAm) brush formation via SET‐LRP, click reaction, and poly(NIPAAm‐b‐VBA) brush formation via RAFT polymerization. The poly(NIPAAm‐b‐VBA) brushes demonstrate stimuli‐responsive behavior with respect to pH and temperature. The swollen brush thickness of poly(NIPAAm‐b‐VBA) brush increases with increasing pH, and decreases with increasing temperature. These results can provide guidance for the design of smart materials based on copolymer brushes. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2677–2685