Currently, there are three types of devices for a bioartificial pancreas; microencapsulation, an extravascular diffusion chamber, and an intravascular diffusion chamber. The purpose of the present study was to provide a new extracellular matrix hydrogel for the devices of extra- and intravascular diffusion chamber types. As the sol-gel transition of this hydrogel is reversible, refilling of islets in vivo will be possible without a severe traumatic procedure. The hydrogel was produced from a polyacrylamide derivative carrying thiol groups synthesized by radical copolymerization of acrylamide and N,N'-bis-acrylcystamine, followed by reduction of the disulfide bonds in the copolymer. This water-soluble copolymer was used to entrap hamster islets by re-formation of disulfide bonds on the copolymer to produce a hydrogel. The formed hydrogel was easily reliquefied by reduction of the disulfide crosslinks to thiols. Insulin release from the islet-entrapped hydrogel continued for more than 1 month when examined in vitro. A static glucose stimulation test for the entrapped islets exhibited an increased insulin release.

Kinetic analyses were carried out for formation of disulfide crosslinkages between thiol groups on linear polymers, poly(acrylamide‐co‐N‐acrylcysteamine) (P‐SH). Disulfide crosslinkages were formed by auto‐oxidation of pendant thiol groups or through the thiol‐disulfide exchange reaction induced by addition of disulfide compounds gluthathione. In the auto‐oxidation reaction, the rate constant for disulfide formation highly depended on pH values of the reaction mixtures and the P‐SH concentrations. Gelation rate is too slow to enclose living cells into hydrogel under physiological pH 7.4. The hydrogel formation rate can be accelerated by addition of disulfides, such as oxidized glutathione. In the later case, oxygen in the reaction mixture is not consumed. The thiol‐disulfide exchange reaction is much more suitable for the cell encapsulation than the thiol auto‐oxidation reaction. These findings give a basis for enclosure of living cells in a hydrogel. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011