One-megadalton metalloenzyme complex in Geobacter metallireducens involved in benzene ring reduction beyond the biological redox window

Huwiler, Simona G. and Loffler, Claudia and Anselmann, Sebastian E. L. and Stark, Hans-Joachim and von Bergen, Martin and Flechsler, Jennifer and Rachel, Reinhard and Boll, Matthias (2019) One-megadalton metalloenzyme complex in Geobacter metallireducens involved in benzene ring reduction beyond the biological redox window. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 116 (6). pp. 2259-2264. ISSN 0027-8424,

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Abstract

Reversible biological electron transfer usually occurs between redox couples at standard redox potentials ranging from +0.8 to -0.5 V. Dearomatizing benzoyl-CoA reductases (BCRs), key enzymes of the globally relevant microbial degradation of aromatic compounds at anoxic sites, catalyze a biological Birch reduction beyond the negative limit of this redox window. The structurally characterized BamBC subunits of class II BCRs accomplish benzene ring reduction at an active-site tungsten cofactor; however, the mechanism and components involved in the energetic coupling of endergonic benzene ring reduction have remained hypothetical. We present a 1-MDa, membrane-associated, Bam[(BC) 2DEFGHI] 2 complex from the anaerobic bacterium Geobacter metallireducens harboring 4 tungsten, 4 zinc, 2 selenocysteines, 6 FAD, and >50 FeS cofactors. The results suggest that class II BCRs catalyze electron transfer to the aromatic ring, yielding a cyclic 1,5-dienoyl-CoA via two flavin-based electron bifurcation events. This work expands our knowledge of energetic couplings in biology by high-molecular-mass electron bifurcating machineries.

Item Type: Article
Uncontrolled Keywords: AROMATIC-COMPOUNDS; BENZOYL-COENZYME; HETERODISULFIDE REDUCTASE; ELECTRON BIFURCATION; THAUERA-AROMATICA; DEGRADATION; METABOLISM; FERREDOXIN; PROTEINS; CLUSTERS; metalloenzyme; electron bifurcation; electron transfer; aromatic compound; membrane protein complex
Subjects: 500 Science > 570 Life sciences
Divisions: Biology, Preclinical Medicine > Institut für Biochemie, Genetik und Mikrobiologie
Biology, Preclinical Medicine > Institut für Biochemie, Genetik und Mikrobiologie > Lehrstuhl für Mikrobiologie (Archaeenzentrum)
Biology, Preclinical Medicine > Institut für Biochemie, Genetik und Mikrobiologie > Lehrstuhl für Mikrobiologie (Archaeenzentrum) > Prof. Dr. Reinhard Rachel
Depositing User: Dr. Gernot Deinzer
Date Deposited: 17 Apr 2020 11:42
Last Modified: 17 Apr 2020 11:42
URI: https://pred.uni-regensburg.de/id/eprint/27565

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