Equilibrium swelling of multi-stimuli-responsive copolymer gels

Copolymer gels prepared by polymerization of thermo-responsive and anionic monomers demonstrate strong sensitivity to several triggers such as temperature, pH and ionic strength of aqueous solutions. For biomedical applications of these materials (as on-off switches in controlled drug delivery and release), fine tuning of their volume phase transition temperature (VPTT) and a sharp decay in degree of swelling upon transition from the swollen to the collapsed state are needed. These requirements are fulfilled under swelling of copolymer gels and microgels in water under acidic conditions, but are violated when tests are conducted under alkaline conditions or in aqueous solutions of salts with physiological salinity. A model is developed for equilibrium swelling of multi-stimuli-responsive copolymer gels in aqueous solutions with arbitrary pH and molar fractions of a monovalent salt. Unlike conventional approaches, the model accounts for secondary interactions between chains (hydrogen bonding) to describe the kinetics of aggregation of hydrophobic segments above VPTT. Material constants are determined by fitting experimental swelling diagrams on poly(N-isopropylacrylamide-co-sodium acrylate) gels with various molar fractions of ionic monomers. The effects of temperature, pH and molar fraction of salt on the equilibrium degree of swelling below and above VPTT are studied numerically.