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Type: Journal article
Title: Substrate-independent method for growing and modulating the density of polymer brushes from surfaces by ATRP
Author: Coad, B.R.
Lu, Y.
Glattauer, V.
Meagher, L.
Citation: ACS Applied Materials and Interfaces, 2012; 4(5):2811-2823
Publisher: American Chemical Society
Issue Date: 2012
ISSN: 1944-8244
Statement of
Bryan R. Coad, Yi Lu, Veronica Glattauer, and Laurence Meagher
Abstract: We describe a method for grafting PEG-based polymer chains of variable surface density using a substrate independent approach, allowing grafting from virtually any material substrate. The approach relies upon initial coupling of a macroinitiator to plasma polymer treated surfaces. The macroinitiator is a novel random terpolymer containing ATRP initiator residues, strongly negatively charged groups, and carboxylic acid moieties that facilitate covalent surface anchoring. Surface-initiated ATRP (SI-ATRP) using polyethylene glycol methyl ether methacrylate (PEGMA) at different concentrations led to grafted surfaces of controlled thickness in either the “brush” or “mushroom” morphology, which was controlled by the abundance of initiator residues in the macroinitiator. Grafted polymer layer structure was investigated via direct interaction force measurements using colloid probe atomic force microscopy (AFM). Equilibrium, hydrated graft layer thicknesses inferred from the highly repulsive AFM force data suggest that the polymer brush graft layer contained polymer chains which were fully stretched. Since the degree of stretching resulted in layer thicknesses approaching the polymer contour length, the polymer brushes studied must be very close to maximum graft density. Grafted layers where the polymer molecules were in the mushroom regime resulted in much thinner layers but the chains had greater chain entropic freedom as indicated by strongly attractive bridging interactions between tethered chains and the silica colloid probe. Use of this experimental methodology would be suitable for preparing grafted polymer layers of a preferred density free from substrate-specific linking chemistries.
Keywords: Biomaterial interface engineering; surface-initiated ATRP; polymer brush; colloid probe microscopy; plasma polymerization; biomaterial surfaces
Description: Published: April 19, 2012
Rights: © 2012 American Chemical Society
DOI: 10.1021/am300463q
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