Tailoring Dynamic Hydrogels by Controlling Associative Exchange Rates.

ABSTRACT: Dithioalkylidenes are a newly-developed class of conjugate acceptors that undergo thiol exchange via an associative mechanism, enabling decoupling of key material properties for sustainability, biomedical, and sensing applications. Here, we show that the exchange rate is highly sensitive to the structure of the acceptor and tunable over four orders of magnitude in aqueous environments. Cyclic acceptors exchange rapidly, from 0.95 to 15.6 M^-1s^-1, while acyclic acceptors exchange between 3.77x10^-3 and 2.17x10^-2 M^-1s^-1. Computational, spectroscopic, and structural data suggest that cyclic acceptors are more reactive than their acyclic counterparts because of resonance stabilization of the tetrahedral exchange intermediate. We p

SUBMITTER: Zhang V 

PROVIDER: S-EPMC10545375 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature