Mechanisms of Degradation for Polydisulfides: Main Chain Scission, Self-Immolation, Or Chain Transfer Depolymerization.

Organic polydisulfides hold immense potential for the design of recyclable materials. Of these, polymers based on lipoic acid are attractive, as they are based on a natural, renewable resource. Herein, we demonstrate that reductive degradation of lipoic acid polydisulfides is a rapid process whereby the quantity of added initiator relative to the polymer content defines the mechanism of polymer degradation, through the main chain scission, self-immolation, or "chain transfer" depolymerization.

Chemical zymogens for the protein cysteinome.

We present three classes of chemical zymogens established around the protein cysteinome. In each case, the cysteine thiol group was converted into a mixed disulfide: with a small molecule, a non-degradable polymer, or with a fast-depolymerizing fuse polymer (Z). The latter was a polydisulfide based on naturally occurring molecule, lipoic acid.