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Synthesis, preparation, and conformation of stimulus-responsive end-grafted poly(methacrylic acid-g-ethylene glycol) layers
Journal article

Synthesis, preparation, and conformation of stimulus-responsive end-grafted poly(methacrylic acid-g-ethylene glycol) layers

Miao Ye, Dong Zhang, Lin Han, Jonathon Tejada and Christine Ortiz
Soft matter, v 2(3), pp 243-256
07 Mar 2006
PMID: 32646151

Abstract

Here we report the formation of stimulus-responsive chemically end-grafted 'brush-brushes' by synthesizing, mono thiol(end)-functionalized poly(methacrylic acid-g-ethylene glycol) or poly(MAA-g-EG) comb-type graft copolymers via a combination of protecting group chemistry and atom transfer radical polymerization using the initiator 2-(2,4-dinitrophenylthio)ethyl 2-bromo-2-methyl propionate. The polymers were synthesized with three different molecular weights (15 k, 17 k and 27 k), PEG side chain graft densities (EG/MAA mole ratio = 2.,0.4 and 1.9, respectively), and a PEG molecular weight = 1100 and then chemically end-grafted to gold substrates via chemisorption, resulting in molecular separation distances of -3-4 nm. pH-Dependent swelling was confirmed to take place gradually above pH 4-5 and quantified by heights measured by contact mode AFM imaging of microcontact printed (.tCP) samples. Swelling factors (maximum height/minimum height) were fairly large (3.6-7.3) and a decrease in molecular weight by 2 x and side chain graft density by 4 x resulted in a decrease in swelling factor by -2 x . Layer height versus normal force for all three polymers measured by contact mode atomic force microscope imaging on p,CP samples at pH 9 showed a nonlinearly decreasing relationship and complete compression - < 2 nm for forces > 10 nN. At pH 4, all polymer layers were largely collapsed (heights - < 4 nm) and incompressible (i.e., heights were independent of normal force).

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Web of Science research areas
Chemistry, Physical
Materials Science, Multidisciplinary
Physics, Multidisciplinary
Polymer Science
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