Cobalamin-Mediated Electrocatalytic Reduction of Ethyl Chloroacetate in Dimethylformamide.
Journal
Journal of the Electrochemical Society
ISSN: 0013-4651
Titre abrégé: J Electrochem Soc
Pays: England
ID NLM: 7505603
Informations de publication
Date de publication:
May 2022
May 2022
Historique:
entrez:
11
7
2022
pubmed:
12
7
2022
medline:
12
7
2022
Statut:
ppublish
Résumé
The catalytic reduction of ethyl chloroacetate (ECA) by hydroxocobalamin (HOCbl) in dimethylformamide was studied electrochemically and spectroelectrochemically to identify initial steps in the reaction between the electrogenerated Co(I) center of cobalamin (cob(I)alamin) and ECA. Cyclic voltammograms of HOCbl in the presence of ECA show a small increase in current related to reduction of Co(II) to Co(I), and a new peak at more negative potentials related to reduction of an ethyl carboxymethyl-Cbl intermediate. The oxidation state of HOCbl during catalysis was monitored by means of spectroelectrochemical controlled-potential bulk electrolysis. Addition of ECA to electrogenerated cob(I)alamin initially generates the Co(II) form (cob(II)alamin) followed by a gradual formation of an ethyl carboxymethyl-Cbl intermediate. Controlled-potential bulk electrolysis was performed to identify products formed from catalytic reduction of ECA by electrogenerated cob(I)alamin and quantify the number of electrons transferred per molecule of ECA. Product distributions and coulometric results, together with the results of voltammograms and spectroelectrochemical controlled-potential bulk electrolysis, were interpreted to propose a reaction mechanism.
Identifiants
pubmed: 35812015
doi: 10.1149/1945-7111/ac6a13
pmc: PMC9265244
mid: NIHMS1804689
pii:
doi:
Types de publication
Journal Article
Langues
eng
Subventions
Organisme : NIGMS NIH HHS
ID : R00 GM087551
Pays : United States
Organisme : NIGMS NIH HHS
ID : R01 GM115665
Pays : United States
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