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Novel thioether bond revealed by a 1.7 Å crystal structure of galactose oxidase

Nature volume 350, pages 87–90 (1991)Cite this article

Abstract

GALACTOSE oxidase is an extracellular enzyme secreted by the fungus Dactylium dendroides. It is monomeric, with a relative molecular mass of 68,000, catalyses the stereospecific oxidation of a broad range of primary alcohol substrates and possesses a unique mononuclear copper site essential for catalysing a two-electron transfer reaction during the oxidation of primary alcohols to corresponding aldehydes1. Recent evidence2 arguing against a Cu(III)-Cu(I) couple3 implies the existence of a second redox-active site proposed to involve pyrroloquinoline quinone4 or a tyrosine radical5,6. We now report the crystal structure of galactose oxidase at 1.7 Å resolution. This reveals a unique structural feature at the copper site with a novel thioether bond linking Cys 228 and Tyr 272 in a stacking interaction with Trp 290. We propose that these molecular components stabilize the protein free-radical species essential for catalysis and thus provide a 'built-in' secondary cofactor. This feature may represent a new mechanism for mediating electron transfer in metalloenzymes in the absence of exogenous cofactors.

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Authors and Affiliations

  1. Department of Biochemistry and Molecular Biology, University of Leeds, Leeds, LS2 9JT, UK

    Nobutoshi Ito, Simon E. V. Phillips, Conrad Stevens, Zumrut B. Ogel, Michael J. McPherson, Jeffery N. Keen, Kapil D. S. Yadav & Peter F. Knowles

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  1. Nobutoshi Ito
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  2. Simon E. V. Phillips
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  3. Conrad Stevens
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  4. Zumrut B. Ogel
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Ito, N., Phillips, S., Stevens, C. et al. Novel thioether bond revealed by a 1.7 Å crystal structure of galactose oxidase. Nature 350, 87–90 (1991). https://doi.org/10.1038/350087a0

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