Amino acid vinyl esters: a new monomer palette for degradable polycationic materialsElectronic Supplementary Information (ESI) available: GPC traces of representative poly(BAAVE) homopolymers and poly(VAc-co-BAAVE) copolymers, 1H NMR spectra of poly(BAAVE) before and after treatment with CF3COOH, Mayo-Lewis analysis of chain transfer in VAc/BGVE copolymerizations, and GPC analyses demonstrating the invariance of copolymer molecular weight distributions on treatment with HCl and CF3COOH are prese

Toward the goal of developing degradable polycationic materials with tunable backbone charge densities and hydrophilicities, we report the optimized syntheses and polymerization activities of a series of N -Boc-protected amino acid O -vinyl ester (BAAVE) monomers derived from Boc-protected glycine, alanine, valine, and proline. The homopolymerization and copolymerization behaviors of these monomers under thermally initiated conventional free radical polymerization conditions are studied. By conducting copolymerizations of ( N-tert -butoxycarbonyl)glycine vinyl ester (BGVE) with vinyl acetate (VAc) at various feed ratios and by analyzing the compositions of the resulting polymers produced at 88 C using 1,1-azobis(cyclohexane-1-carbonitrile) (V-40) initiation, we find that the reactivity ratios are r BGVE = 1.61 0.12 and r VAc = 0.82 0.07. Treatment of poly(VAc- co -BAAVE) with neat CF 3 COOH selectively unmasks the Boc-protected amine functionalities to furnish cationic poly(VAc- co -AAVECF 3 COOH) copolymers. Alternatively, treatment of these random copolymers with methanolic HCl results in the complete hydrolysis of both the Boc-protecting groups as well as the acetate esters, enabling access to well-defined, hydrophilic, polycationic amino acid ester-functionalized poly(vinyl alcohol) materials. Degradable polycationic materials with tunable backbone charge densities and variable hydrophilicities are synthesized by copolymerization of vinyl acetate and N -Boc-protected amino acid O -vinyl esters followed by post-synthetic deprotection under different conditions.