A hydrogen-bonded layer-by-layer (LbL) technique was used to build multilayers of neutral, temperature-responsive polymers such as poly(N-isopropylacrylamide) (PNIPAM), poly(N-vinylcaprolactam) (PVCL), poly(vinyl methyl ether) (PVME), or poly(acrylamide) (PAAm) with a polycarboxylic acid such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), or poly(ethacrylic acid) (PEAA). For all multilayers involving temperature-responsive polymers, the temperature used during or after self-assembly had a significant effect on film stability with pH changes. The proximity of the self-assembly or post-self-assembly temperature to the critical temperature of phase separation of a neutral polymer from solution resulted in a higher pH stability of multilayers. However, for polymers with a lower critical solution temperature (LCST) such as PNIPAM, PVCL, or PVME within PNIPAM/PMAA, PVCL/PMAA, or PVME/PMAA multilayers, the critical pH of film disintegration (pH(crit)) increased in the temperature range from 10 to 37 degrees C, whereas for polymer films with an upper critical solution temperature (UCST), such as PAAm within PAAm/PMAA, the film showed the opposite trend. Using a hydrogen-bonded polyvinylpyrrolidone (PVPON)/PMAA system, which is not responsive to temperature changes, we constructed hybrid films with lower [PNIPAM/PMAA](n) and higher [PVPON/PMAA](m) strata and obtained free-floating [PVPON/PMAA](m) films by temperature-triggered dissolution of the PNIPAM/PMAA layers at a constant pH value. The kinetics of [PVPON/PMAA](m) film release was strongly dependent on the number of bilayers within the PNIPAM/PMAA stratum, indicating significant interpenetration between PNIPAM/PMAA and PVPON/PMAA bilayers. Importantly, the use of PEAA instead of PAA or PMAA in film assembly enabled the construction of hydrogen-bonded LbL films that can be released by applying temperature as a trigger at near-physiological pH values. This feature makes such release layers attractive candidates for future tissue engineering applications.
