Mechanism and Chemoselectivity for HOCl-Mediated Oxidation of Zinc-Bound Thiolates.

Lindsay ZumwaltArden PerkinsO Maduka Ogba

Published in: Chemphyschem : a European journal of chemical physics and physical chemistry (2020)

Quantum mechanical calculations reveal the preferred mechanism and origins of chemoselectivity for HOCl-mediated oxidation of zinc-bound thiolates implicated in bacterial redox sensing. Distortion/interaction models show that minimizing geometric distortion at the zinc complex during the rate-limiting nucleophilic substitution step controls the mechanistic preference for OH over Cl transfer with HOCl and the chemoselectivity for HOCl over H2 O2 .

Keyphrases

oxide nanoparticles
molecular dynamics
electron transfer
hydrogen peroxide
density functional theory
molecular dynamics simulations
single cell
monte carlo
gene expression