Temperature-induced swelling and small molecule release with hydrogen-bonded multilayers of block copolymer micelles

We report on reversible temperature-triggered swelling transitions in hydrogen-bonded multilayer films of a polycarboxylic acid and stimuli-responsive block copolymer micelles (BCMs). A neutral hydrogen-bonding temperature-responsive diblock copolymer, poly(N-vinylpyrrolidone)-b-poly(N-isopropylacrylamide) (PVPON-b-PNIPAM), was synthesized by macromolecular design via the interchange of xanthates (MADIX). The block copolymer exhibited reversible micellization, forming PNIPAM-core micelles with PVPON coronae in 0.01 M buffer solutions at temperatures higher than 34 degrees C, or in solutions with high salt concentrations (C(NaCl) > 0.4 M) at 20 degrees C. The PVPON-b-PNIPAM BCMs were then assembled with poly(methacrylic acid) (PMAA) at acidic pH and higher temperature using the layer-by-layer (LbL) technique. Within the hydrogen-bonded multilayer, BCMs were stabilized through hydrogen bonding between PVPON and PMAA units and, unlike in solution, did not dissociate into unimers in low-salt solution at T < 34 degrees C. Instead, PVPON-b-PNIPAM BCMs reversibly swelled within film in response to temperature- or salt-concentration variations, reflecting collapse and dissolution of the BCM PNIPAM cores. The capacity of BCM/PMAA films to retain hydrophobic molecules was also dramatically dependent on temperature and/or ionic strength. The characteristic release time of pyrene from a [BCM/PMAA](10) film decreased from 80 to 10 min upon a decrease in temperature from 37 to 20 degrees C. In addition, at 20 degrees C, ionic strength was also capable of controlling the collapse of PNIPAM micellar cores and the subsequent film swelling and pyrene release rate. Incorporation of stimuli-responsive BCM micelles within LbL films opens new opportunities in designing nanoscale films capable of controlling molecular swelling, transport, and diffusion in response to environmental stimuli.