Self-association and microenvironment of random amphiphilic copolymers of sodium N-acryloyl-l-valinate and N-dodecylacrylamide in aqueous solution

The present paper reports on the syntheses and association behavior of two random copolymers of sodium N-acryloyl-l-valinate and N-dodecylacrylamide in buffered (pH 8.0) aqueous solution containing 0.1 M NaCl. Surface tension and viscosity results showed pronounced amphiphilic nature of the copolymers in aqueous solution at pH 8.0. Steady-state fluorescence studies using pyrene and N-phenyl-1-naphthylamine as probe molecules suggested microdomain formation through interpolymer association above a critical concentration called ‘critical aggregation concentration’ (CAC) as low as ca. 10−3 g L−1. The local polarity of the hydrophobic domain formed in aqueous solution was estimated from steady-state fluorescence spectra of pyrene. The microviscosity of the domains was evaluated using 1,6-diphenyl-1,3,5-hexatriene as a fluorescent probe using steady-sate fluorescence depolarization and time-resolved fluorescence method. Dynamic light scattering technique was performed over a wide range of concentration to determine hydrodynamic size of the aggregates. It was observed that both copolymers retain rather open conformation in dilute solutions having polymer concentrations less than CAC. However, with increase in concentration the intermolecular association becomes favorable towards the formation of more compact aggregates. The transmission electron microscopic images of both copolymers at a concentration above CAC revealed spherical aggregates of uniform diameter (∼50 nm).