Chlorinations catalyzed by chloroperoxidase occur via diffusible intermediate(s) and the reaction components play multiple roles in the overall process.

摘要: The chlorination mechanism of the fungal enzyme chloroperoxidase (CPO) has been debated for (1) active site and (2) diffusible species mediated chlorination. Based upon conversion approximately 35 different substrates belonging to reactive groups, it was found that substrate dimensions topography had no pronounced effect on rates CPO reaction. Epoxidation indene dependent its concentration where as not. Also, effective seen in mixture could not be epoxidized or sulfoxidized. Some insoluble certain molecules exceeded were chlorinated at comparable required CPO's more natural substrate, monochlorodimedone. By terminating enzymatic reaction with an ligand (azide), amount correlated mixture. preferential utilization a earlier attributed site, is due specificity afforded by environment. It medium components peroxide, chloride hydronium ions affected through varying roles non-enzymatic process. Besides these experimental evidences, key mechanistic kinetic arguments are presented infer final chlorine transfer occurs outside via species.