Novel temperature‐ and pH‐responsive graft copolymers composed of poly(<scp>L</scp>‐glutamic acid) and poly(<i>N</i>‐isopropylacrylamide)

Abstract

Abstract A series of novel temperature‐ and pH‐responsive graft copolymers, poly( L ‐glutamic acid)‐ g ‐poly( N ‐isopropylacrylamide), were synthesized by coupling amino‐semitelechelic poly( N ‐isopropylacrylamide) with N ‐hydroxysuccinimide‐activated poly( L ‐glutamic acid). The graft copolymers and their precursors were characterized, by ESI‐FTICR Mass Spectrum, intrinsic viscosity measurements and proton nuclear magnetic resonance ( 1 H NMR). The phase‐transition and aggregation behaviors of the graft copolymers in aqueous solutions were investigated by the turbidity measurements and dynamic laser scattering. The solution behavior of the copolymers showed dependence on both temperature and pH. The cloud point (CP) of the copolymer solution at pH 5.0–7.4 was slightly higher than that of the solution of the PNIPAM homopolymer because of the hydrophilic nature of the poly(glutamic acid) (PGA) backbone. The CP markedly decreased when the pH was lowered from 5 to 4.2, caused by the decrease in hydrophilicity of the PGA backbone. At a temperature above the lower critical solution temperature of the PNIPAM chain, the copolymers formed amphiphilic core‐shell aggregates at pH 4.5–7.4 and the particle size was reduced with decreasing pH. In contrast, larger hydrophobic aggregates were formed at pH 4.2. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4140–4150, 2008