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Incorporation of molybdenum in rubredoxin: models for mononuclear molybdenum enzymes

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Abstract

Molybdenum is found in the active site of enzymes usually coordinated by one or two pyranopterin molecules. Here, we mimic an enzyme with a mononuclear molybdenum-bis pyranopterin center by incorporating molybdenum in rubredoxin. In the molybdenum-substituted rubredoxin, the metal ion is coordinated by four sulfurs from conserved cysteine residues of the apo-rubredoxin and two other exogenous ligands, oxygen and thiol, forming a Mo(VI)-(S-Cys)4(O)(X) complex, where X represents –OH or –SR. The rubredoxin molybdenum center is stabilized in a Mo(VI) oxidation state, but can be reduced to Mo(IV) via Mo(V) by dithionite, being a suitable model for the spectroscopic properties of resting and reduced forms of molybdenum-bis pyranopterin-containing enzymes. Preliminary experiments indicate that the molybdenum site built in rubredoxin can promote oxo transfer reactions, as exemplified with the oxidation of arsenite to arsenate.

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Abbreviations

apo-Rd:

Apo-rubredoxin

β-ME:

β-Mercaptoethanol

BSO:

Biotin sulfoxide

CT:

Charge transfer

CV:

Cyclic voltammetry

DMSOR:

Dimethylsulfoxide reductase

DTT:

Dithiothreitol

DPV:

Differential pulsed voltammetry

Fe-Rd:

Iron-containing rubredoxin

GC:

Glassy carbon

hSO:

Human sulfite oxidase

M:

Metal

Mo-bis PGD:

Molybdenum-bis pyranopterin guanosine dinucleotide-containing enzyme

Mo-Rd:

Molybdenum-substituted rubredoxin

PGE:

Pyrolytic graphite electrode

NHE:

Normal hydrogen electrode

RR:

Resonance Raman

Rd:

Rubredoxin

TCA:

Trichloroacetic acid

TFET:

2,2,2-Trifluoroethanethiol

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Acknowledgments

We acknowledge Fundação para a Ciência e Tecnologia (FCT) for the financial support Granted to REQUIMTE (PEst-C/EQB/LA0006/2013) and UCIBIO-REQUIMTE (UID/Multi/04378/2013), BKM (SFRH/BPD/63066/2009) and SRP (FCT-ANR/BBB-MET0023/2012). NMR data were collected on 400-MHz spectrometer that is part of the National NMR Network, also supported by FCT (RECI/BBB-BQB/0230/2012).

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Authors and Affiliations

  1. UCIBIO, REQUIMTE, Departamento Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516, Caparica, Portugal

    Biplab K. Maiti, Luisa B. Maia, Célia M. Silveira, Cintia Carreira, Marta S. P. Carepo, Raquel Grazina, Isabel Moura, Sofia R. Pauleta & José J. G. Moura

  2. Instituto de Tecnologia Química e Biológica, Universidade Nova de Lisboa, 2780-157, Oeiras, Portugal

    Célia M. Silveira & Smilja Todorovic

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  1. Biplab K. Maiti
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  2. Luisa B. Maia
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  3. Célia M. Silveira
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  10. José J. G. Moura
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Correspondence to José J. G. Moura.

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Maiti, B.K., Maia, L.B., Silveira, C.M. et al. Incorporation of molybdenum in rubredoxin: models for mononuclear molybdenum enzymes. J Biol Inorg Chem 20, 821–829 (2015). https://doi.org/10.1007/s00775-015-1268-0

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