Issue 41, 2011

Kinetics and mechanism of the [RuIII(edta)(H2O)]-mediated oxidation of cysteine by H2O2

Abstract

The kinetics and mechanism of the [RuIII(edta)(H2O)]-mediated oxidation of cysteine (RSH) by hydrogen peroxide (edta4− = ethylenediaminetetraacetate), were studied in detail as a function of both the hydrogen peroxide and cysteine concentrations at pH 5.1 and room temperature. The kinetic traces reveal clear evidence for a catalytic process in which hydrogen peroxide reacts directly with cysteine coordinated to the RuIII(edta) complex in the form of [RuIII(edta)SR]2. A parallel process in which [RuIII(edta)(H2O)] first reacts with H2O2 to produce [RuV(edta)O] and subsequently oxidizes cysteine, is orders of magnitude slower than the [RuIII(edta)(H2O)]-mediated oxidation in which cysteine rapidly coordinates to [RuIII(edta)(H2O)] prior to the reaction with H2O2. HPLC product analyses revealed the formation of cystine (RSSR) as major product along with cysteine sulfinic acid (RSO2H) in the reaction system, and established the catalytic role of [RuIII(edta)(H2O)]. Simulations were performed to account for the rather complex kinetic traces in terms of the suggested reaction mechanism. The results of the simulations support the proposed reaction mechanism that involves the oxidation of coordinated cysteine to cysteine sulfenic acid (RSOH), which subsequently rapidly reacts with H2O2 and RSH to form RSO2H and RSSR, respectively.

Graphical abstract: Kinetics and mechanism of the [RuIII(edta)(H2O)]−-mediated oxidation of cysteine by H2O2

Supplementary files

Article information

Article type
Paper
Submitted
11 Apr 2011
Accepted
04 Aug 2011
First published
15 Sep 2011

Dalton Trans., 2011,40, 10997-11004

Kinetics and mechanism of the [RuIII(edta)(H2O)]-mediated oxidation of cysteine by H2O2

D. Chatterjee, E. Ember, U. Pal, S. Ghosh and R. van Eldik, Dalton Trans., 2011, 40, 10997 DOI: 10.1039/C1DT10623F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements