Two-electron reduction of quinones by Enterobacter cloacae PB2 pentaerythritol tetranitrate reductase: quantitative structure-activity relationships

• Authors: Lina Misevičienė , Žilvinas Anusevičius , Jonas Šarlauskas , Richard J Harris , Nigel S Scrutton , Narimantas Čėnas
• Languages of publication: EN

Abstracts

EN

In order to clarify the poorly understood mechanisms of two-electron reduction of quinones by flavoenzymes, we examined the quinone reductase reactions of a member of a structurally distinct old yellow enzyme family, Enterobacter cloacae PB2 pentaerythritol tetranitrate reductase (PETNR). PETNR catalyzes two-electron reduction of quinones according to a 'ping-pong' scheme. A multiparameter analysis shows that the reactivity of quinones increases with an increase in their single-electron reduction potential and pKa of their semiquinones (a three-step (e-,H+,e-) hydride transfer scheme), or with an increase in their hydride-transfer potential (E7(H-)) (a single-step (H-) hydride transfer scheme), and decreases with a decrease in their van der Waals volume. However, the pH-dependence of PETNR reactivity is more consistent with a single-step hydride transfer. A comparison of X-ray data of PETNR, mammalian NAD(P)H : quinone oxidoreductase (NQO1), and Enterobacter cloacae nitroreductase, which reduce quinones in a two-electron way, and their reactivity revealed that PETNR is much less reactive, and much less sensitive to the quinone substrate steric effects than NQO1. This may be attributed to the lack of π-π stacking between quinone and the displaced aromatic amino acid in the active center, e.g., with Phe-178' in NQO1.

Keywords

EN

pentaerythritol tetranitrate reductase; reduction mechanism; electron-transfer; quinones

• Publisher: Polish Biochemical Society
• Journal: Acta Biochimica Polonica
• Year: 2007
• Volume: 54
• Issue: 2
• Pages: 379-385

Dates

published

2007

received

2007-01-16

revised

2007-03-22

accepted

2007-03-27

(unknown)

2007-06-04

Contributors

author

Lina Misevičienė

• Institute of Biochemistry, Vilnius, Lithuania

author

Žilvinas Anusevičius

• Institute of Biochemistry, Vilnius, Lithuania

author

Jonas Šarlauskas

• Institute of Biochemistry, Vilnius, Lithuania

author

Richard J Harris

• Faculty of Life Sciences, The University of Manchester, Manchester, UK

author

Nigel S Scrutton

• Faculty of Life Sciences, The University of Manchester, Manchester, UK

author

Narimantas Čėnas

• Institute of Biochemistry, Vilnius, Lithuania

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