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2007 | 54 | 2 | 379-385
Article title

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

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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.
Publisher

Year
Volume
54
Issue
2
Pages
379-385
Physical description
Dates
published
2007
received
2007-01-16
revised
2007-03-22
accepted
2007-03-27
(unknown)
2007-06-04
Contributors
  • Institute of Biochemistry, Vilnius, Lithuania
  • Institute of Biochemistry, Vilnius, Lithuania
  • Institute of Biochemistry, Vilnius, Lithuania
  • Faculty of Life Sciences, The University of Manchester, Manchester, UK
  • Faculty of Life Sciences, The University of Manchester, Manchester, UK
  • Institute of Biochemistry, Vilnius, Lithuania
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Document Type
Publication order reference
Identifiers
YADDA identifier
bwmeta1.element.bwnjournal-article-abpv54p379kz
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