Coalescence of postpolymerization modification and click chemistry
Arnold, Rachelle Marie
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Using polymer science as a fundamental platform allows for a true interdisciplinary approach to create sophisticated and adaptable surfaces when combined with biology, materials science, and organic chemistry. Polymer thin films offer a wide range of possibilities to intricately design and tune the interfacial properties of specialized surfaces. Postpolymerization modification (PPM) through click reactions provides simple methods to easily create complex surfaces that bare spatially resolved chemical functionalities and incorporate very delicate components such as biomacromolecules or nanostructures. A stable, highly-reactive polymer, poly(pentafluorophenyl acrylate) (poly(PFPA)), was studied as a universal scaffold for the generation of these complex surfaces. The kinetics of the surface-initiated free radical polymerization of poly(PFPA) films were analyzed by varying the monomer concentration and the reaction time. Subsequently, the pseudo-first order reaction kinetics of aminolysis was determined via ex situ UV-vis. Patterned surfaces of PFPA and a second monomer containing a protected alkyne were produced through sequential surface-initiated free radical polymerizations. The orthogonality of the aminolysis and copper(I)-catalyzed azide-alkyne cycloaddition reactions allowed for a one-pot, self-sorting modification reaction to be performed without cross contamination. Finally, poly(PFPA) was grafted directly onto oxide substrates through covalent attachment to surface silanol functional groups. Hydrolysis and anhydride formation was observed when thermal annealing was performed in ambient conditions, but under inert conditions, no side reactions were detected. Reactive microcapillary printing on the graft to poly(PFPA) films provided two areas of distinct chemistry that could be further functionalized to yield patterns with high resolution.