Surface-Confined Photopolymerization of pH-Responsive Acrylamide/Acrylate Brushes on Polymer Thin Films

Abstract

Dynamic acrylamide/acrylate polymeric brushes were synthesized at gold-plated quartz crystal surfaces. The crystals were initially coated with polystyrene-type thin films, derivatized with photolabile iniferter groups, and subsequently subjected to photoinitiated polymerization in acrylamide/acrylate monomer feeds. This surface-confined polymerization method enabled direct photocontrol over the polymerization, as followed by increased frequency responses of the crystal oscillations in a quartz crystal microbalance (QCM). The produced polymer layers were also found to be highly sensitive to external acid/base stimuli. Large oscillation frequency shifts were detected when the brushes were exposed to buffer solutions of different pH. The dynamic behavior of the resulting polymeric brushes was evaluated, and the extent of expansion and contraction of the films was monitored by the QCM setup in situ in real time. The resulting responses were rapid, and the effects were fully reversible. Low pH resulted in full contractions of the films, whereas higher pH yielded maximal expansion in order to minimize repulsion around the charged acrylate centers. The surfaces also proved to be very robust because the responsiveness was reproducible over many cycles of repeated expansion and contraction. Using ellipsometry, copolymer layers were estimated to be approximately 220 nm in a collapsed state and approximately 340 nm in the expanded state, effectively increasing the thickness of the film by 55%.

Dynamics of cyclodimerization and viscoelasticity of photo‐crosslinkable PVA

“…As indicated in other sections, this is taking advantage of the photo‐induced insolubilization and nontoxicity of PVA‐SbQ . We note that the initiator‐transfer agent‐terminator (iniferter) concept allows facile control of the polymerization reaction by means of irradiation time and intensity at room temperature …”

Photo-Click Immobilization of Carbohydrates on Polymeric Surfaces—A Quick Method to Functionalize Surfaces for Biomolecular Recognition Studies

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Multivalent Recognition of Concanavalin A by {Mo132} Glyconanocapsules—Toward Biomimetic Hybrid Multilayers

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