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Production of Dioxygen in the Dark: Dismutases of Oxyanions

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Sustaining Life on Planet Earth: Metalloenzymes Mastering Dioxygen and Other Chewy Gases

Part of the book series: Metal Ions in Life Sciences ((MILS,volume 15))

Abstract

O2-generating reactions are exceedingly rare in biology and difficult to mimic synthetically. Perchlorate-respiring bacteria enzymatically detoxify chlorite (ClO −2 ), the end product of the perchlorate (ClO −4 ) respiratory pathway, by rapidly converting it to dioxygen (O2) and chloride (Cl−). This reaction is catalyzed by a heme-containing protein, called chlorite dismutase (Cld), which bears no structural or sequence relationships with known peroxidases or other heme proteins and is part of a large family of proteins with more than one biochemical function. The original assumptions from the 1990s that perchlorate is not a natural product and that perchlorate respiration might be confined to a taxonomically narrow group of species have been called into question, as have the roles of perchlorate respiration and Cld-mediated reactions in the global biogeochemical cycle of chlorine. In this chapter, the chemistry and biochemistry of Cld-mediated O2 generation, as well as the biological and geochemical context of this extraordinary reaction, are described.

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Acknowledgments

Support for this work from the National Institutes of Health, National Institute for General Medical Sciences is gratefully acknowledged (GM090260), as are the scientific and intellectual contributions of laboratory members past and present.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, 59717, USA

    Jennifer L. DuBois & Sunil Ojha

Authors
  1. Jennifer L. DuBois
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  2. Sunil Ojha
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Correspondence to Jennifer L. DuBois .

Editor information

Editors and Affiliations

  1. Fachbereich Biologie, Universita¨t Konstanz, Konstanz, Germany

    Peter M. H Kroneck

  2. Facultad de Química Departamento de Química Inorganica y Nuc, Universidad Nacional Autónoma de México, Ciudad de México, Distrito Federal, Mexico

    Martha E. Sosa Torres

Abbreviations and Definitions

Abbreviations and Definitions

Cld:

chlorite dismutase

ClO– :

hypochlorite

ClO2 :

chlorine dioxide

ClO −2 :

chlorite

ClO −3 :

chlorate

ClO −4 :

perchlorate

Clr:

chlorate reductase

Compound 0:

Fe(III)-anion complex

Compound I:

Fe(IV)porphyrin cation radical

Compound II:

Fe(IV)=O or Fe(IV)–OH

DaCld:

Dechloromonas aromatica chlorite dismutase

DMSO:

dimethylsulfoxide

DyP:

dye-decoloring peroxidase

HClO:

hypochlorous acid

HRP:

horseradish peroxidase

MCD:

monochlorodimedone

MGD:

molybdopterin guanine dinucleotide

Nar:

nitrate reductase

NHE:

normal hydrogen electrode

NPRB:

non-perchlorate-respiring bacteria

NwCld:

Nitrospira winogradskyi chlorite dismutase

ONOO− :

peroxynitrite

OTf:

triflate

Pcr:

perchlorate reductase

(per)chlorate:

chlorate and/or perchlorate

PRB:

perchlorate-respiring bacteria

PSII:

Photosystem II

Ser:

selenate reductase

TDMImP:

tetrakis-5,10,15,20-(N,N-dimethylimidazolium)porphyrinato

TF4TMAP:

5,10,15,20-tetrakis(tetrafluro-N,N,N-trimethylanilinium)porphyrinato

WCL:

wet chemistry laboratory

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DuBois, J.L., Ojha, S. (2015). Production of Dioxygen in the Dark: Dismutases of Oxyanions. In: Kroneck, P., Sosa Torres, M. (eds) Sustaining Life on Planet Earth: Metalloenzymes Mastering Dioxygen and Other Chewy Gases. Metal Ions in Life Sciences, vol 15. Springer, Cham. https://doi.org/10.1007/978-3-319-12415-5_3

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