ABSTRACT:Temperature-sensitive poly(N-isopropylacrylamide) [poly(NIPAAm)] was crosslinked with a small amount of N,N'-cystamine-bis-acrylamide which contains a disulfide linkage between two vinyl groups. The hydrogel network could be dissolved into water soluble polymer chains by the reduction of a disulfide bond to two thiol groups. The cleavage of crosslink points led to the experimental determination of the polymer molecular weight (M.) and the amount of free thiol concentration in the polymer backbone. This permitted the calculation of an average molecular weight between crosslinks (M,) which has been theoretically predicted by a Flory-Rehner equation based on either swelling or tensile experiments. The experimentally measured M, values agree well with those obtained from the swelling experiment. When the reduced poly(NIPAAm) was re-oxidized in a dilute aqueous solution, time dependent evolution of inter-and intra-molecularly disulfide linked poly(NIPAAm) species could be observed.KEY WORDS Poly(N-isopropylacrylamide) I Disulfide I Hydrogel I Lower Critical Solution Temperature I Reversible Gels I Hydrogels are crosslinked polymer chain networks that swell in aqueous or biological solution. The structure of three dimensional polymer network has been mostly characterized from its equilibrium swelling capacity in aqueous water milieu. 1 The degree of swelling for nonionic polymer hydrogels is determined by counter-balancing of mixing and elastic free energies that act in an opposite direction. 2 The most critical factor affecting the swelling property is the crosslinking density that has been more conveniently defined as an average molecular weight between crosslinks (Me). From the classical model of rubber elasticity, a Flory-Rehner equation was first introduced to estimate the Me, and later, a modified Bray-Merrill equation was developed. 3 • 4 The latter equation applies for crosslinking reactions of polymer in solid and solution states as well as the polymerization and subsequent network formation of various hydrophilic vinyl monomers in the presence of a small amount of crosslinker. The above equations were used to evaluate the theoretical calculation of Me by simply measuring the equilibrium swelling capacity of hydrogel network. Crosslinking of polymer chains such as poly(vinyl alcohol) by radiation or chemical means easily permits the calculation of Me because M" value of the polymer is known. 5 However, when vinyl monomers are used for the network formation, M" value is not available. This problem limited the use of the above equation for free radically polymerized hydrogels based on vinyl monomers such as acrylamide and 2-hydroxyethylmethacrylate. 6 Water soluble poly(N-isopropylacrylamide) [poly-(NIPAAm)] has been extensively studied for its unique coil to globular conformation change with increasing the temperature above its lower critical solution temperature (LCST). 7 -1° Crosslinked poly(NIP A Am) network that exhibits a volume phase transition at the LCST has also received much attention for i...