Geometrical control of the active site electronic structure of pyranopterin enzymes by metal-dithiolate folding: aldehyde oxidase

Journal of the American Chemical Society
Hemant K Joshi, J H Enemark

Abstract

Density functional calculations on geometry-optimized oxidized (Mo(VI)) and reduced (Mo(IV)) analogues of the isolated active site of aldehyde oxidase (MOP), a member of the xanthine oxidase family of pyranopterindithiolate enzymes, show that fold angle changes of the dithiolate ligand modulate the relative metal and dithiolate contributions to the frontier redox orbitals. Proton abstraction from the equatorial aqua ligand of the oxidized Mo(VI) site also flattens the metal dithiolate fold angle. It is proposed that static and/or dynamic changes in the structure of the protein surrounding the active site can induce changes in the dithiolate fold angle and thereby provide a mechanism for electronic buffering of the redox orbital, for fine-tuning the nucleophilicity of the equatorial aqua/hydroxide ligand, and for modulating the electron-transfer regeneration of the active sites of molybdenum and tungsten enzymes via a "dithiolate folding effect".

References

Mar 8, 1994·Biochimica Et Biophysica Acta·R Hille
Aug 20, 1996·Proceedings of the National Academy of Sciences of the United States of America·R HuberM J Romão
Nov 20, 2001·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·J M RebeloM J Romão
Aug 1, 2002·Journal of the American Chemical Society·Katrina PearisoMartin L Kirk
Mar 26, 2003·Proceedings of the National Academy of Sciences of the United States of America·Hemant K JoshiJohn H Enemark

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Citations

May 30, 2009·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Ulf RydeKerstin Starke
Mar 18, 2009·Journal of the American Chemical Society·Sebastian MetzWalter Thiel
Nov 13, 2008·The Journal of Organic Chemistry·Joshua F Alfaro, Jeffrey P Jones
Dec 23, 2015·Inorganic Chemistry·Jing YangMartin L Kirk
Jul 20, 2007·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Matthias Hofmann
Feb 6, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Nicolas ChrysochosCarola Schulzke
Jun 2, 2009·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Matthias Hofmann
Jul 6, 2014·The Journal of Physical Chemistry. a·Michael J van StipdonkJos Oomens

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