Improving the Stability in Aqueous Media of Polymer Brushes Grafted from Silicon Oxide Substrates by Surface‐Initiated Atom Transfer Radical Polymerization

Paripovic, Dusko; Klok, Harm‐Anton

doi:10.1002/macp.201000729

Cited by 78 publications

(106 citation statements)

References 26 publications

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“…36 A subsequent study reported that covering the ATRP initiator modified substrate with a thin layer of a hydrophobic polymer prior to reinitiating ATRP with methacrylic acid resulted in robust hydrophilic polymer brushes. 37 These results are consistent with hydrolytic bond cleavage at the brush−substrate interface (presumably the Si− O bond that links the organosilane modified ATRP initiator to the silicon substrate and/or the amide bond that connects the ATRP initiating group with the aminopropyl trialkoxysilane anchoring moiety), which is facilitated by the solvent-induced stretching of the surface-grafted polymer chains (and hence a "mechanochemical(ly-facilitated)" process). The findings discussed above were preceded by a paper by Deng and Zhu, who reported the degrafting of hyperbranched polyglycerols that were prepared via SIP from gold substrates.…”

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confidence: 79%

Expanding the Polymer Mechanochemistry Toolbox through Surface-Initiated Polymerization

Klok

Genzer

2015

ACS Macro Lett.

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Surface-initiated polymerizations represent a versatile toolbox to generate densely grafted assemblies of chain end-tethered polymers. At sufficiently short interchain distances, surface-grafted polymers are forced into an extended chain conformation, which forms the basis of several unique properties, including their ability to withstand efficiently biofouling or to act as low friction coatings. While the effect on materials properties is well-established, only relatively recently first reports have appeared describing that chain stretching in surface-grafted polymer films also impacts chemical stability/reactivity. This Viewpoint presents surface-initiated polymerization as an alternative polymer mechanochemical tool. The absence of an external force field to induce chain elongation and the possibility to modulate chain stretching by varying brush molecular weight and grafting density, in conjunction with electrostatic interactions and nanoinclusions that may be present inside the polymeric grafts, make surface-initiated polymerization an attractive tool to both study and understand the effects of polymer chain conformation on the stability/ reactivity of surface-grafted polymers.

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confidence: 79%

Expanding the Polymer Mechanochemistry Toolbox through Surface-Initiated Polymerization

Klok

Genzer

2015

ACS Macro Lett.

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“…These cylindrical brushes consisted of pHOEGMA chains with a methacrylate backbone and OEG side chains. The dense low-fouling brushes of pHOEGMA have been grown from gold [65,68,94,156,160,161], silica and/or silicon [151,162,163], TiO 2 [164], polymeric nanocapsules [154], and a variety of polymer surfaces [10,155].…”

Section: Brushes Of Polymers With Oligo(ethylene Glycol) Side Chainsmentioning

confidence: 99%

Functionalizable low-fouling coatings for label-free biosensing in complex biological media: advances and applications

2015

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This review focuses on recent advances in the development of functionalizable antifouling coatings and their applications in label-free optical biosensors. Approaches to the development of antifouling coatings, ranging from self-assembled monolayers and PEG derivatives to ultra-low-fouling polymer brushes, are reviewed. Methods of preparation and characterization of antifouling coatings and the functionalization of antifouling coatings with bioreceptors are reviewed, and the effect of functionalization on the fouling properties of biofunctional coating is discussed. Special attention is given to biofunctional coatings for label-free bioanalysis of blood plasma and serum for medical diagnostics.

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“…[4] Thedegrafting of hydrophilic polymer brushes from silicon oxide surfaces in aqueous media has been attributed to as welling-induced stretching of the surface-anchored polymer chains and ac oncomitant amplification of the tension that acts on the siloxane and ester/amide bonds that anchor the chains to the surface. Foranumber of hydrophilic polymer brushes grown via surface-initiated atom transfer radical polymerization (SI-ATRP) from silicon oxide substrates modified with organosilane functionalized ester or amide based ATRP initiators,incubation in aqueous media results in detachment (degrafting) of the surface-anchored polymer chains.…”

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Swelling‐Induced Chain Stretching Enhances Hydrolytic Degrafting of Hydrophobic Polymer Brushes in Organic Media

Wang

Klok

2019

Angew Chem Int Ed

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Hydrophilic polymer brushes grown via surfaceinitiated polymerization from silicon oxide surfaces can detach or degraft in aqueous media. Degrafting of these chain endtethered polymers is believed to involve hydrolysis of bonds at the polymer-substrate interface.Degrafting so far has not been reported for hydrophobic polymer brushes in non-aqueous media. This study has investigated the degrafting and swelling properties of poly(tert-butyl methacrylate) (PtBMA) brushes in different water-miscible,organic solvents,viz. DMF,acetone and THF.Inthe presence of asufficient quantity of water in the organic solvent, degrafting was also observed for PtBMA brushes.M ore importantly,h owever,t he rate of degrafting depended on the nature of the organic solvent and the apparent initial rate constant of the degrafting reaction was found to correlate with the swelling ratio of the polymer brush in the different solvents.T his correlation is first, direct evidence in support of the hypothesis that degrafting is facilitated by atension that acts on the bond(s) that tether the polymer chains to the surface and whichi sa mplified upon swelling of the polymer brush.Scheme 1. Preparation of PtBMA brushes via SI-ATRP.

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Improving the Stability in Aqueous Media of Polymer Brushes Grafted from Silicon Oxide Substrates by Surface‐Initiated Atom Transfer Radical Polymerization

Cited by 78 publications

References 26 publications

Expanding the Polymer Mechanochemistry Toolbox through Surface-Initiated Polymerization

Expanding the Polymer Mechanochemistry Toolbox through Surface-Initiated Polymerization

Functionalizable low-fouling coatings for label-free biosensing in complex biological media: advances and applications

Swelling‐Induced Chain Stretching Enhances Hydrolytic Degrafting of Hydrophobic Polymer Brushes in Organic Media

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