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

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

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

Hemant K Joshi,John H Enemark,

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".

Geometrical control of the active site electronic structure of pyranopterin enzymes by metal-dithiolate folding: aldehyde oxidase. Publishing Authors By Initials

HK Joshi,JH Enemark,

For similar inorganic chemicals: sulfur compounds research abstracts see: inorganic chemicals: sulfur compounds research

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

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: Journal of the American Chemical Society

VOLUME: 126

Page Numbers: 11784-5

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 29

MONTH: Sep

YEAR: 2004

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

Number of References:

LANGUAGE: eng

NlmUniqueID: 7503056

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

KEYWORDS: Sulfur Compounds

MESH TERMS: metabolism

Chemical & Substance for Abstract: Geometrical control of the active site electronic structure of pyranopterin enzymes by metal-dithiolate folding: aldehyde oxidase. Information

Substance Name: Aldehyde Oxidase

Registry Number: EC 1.2.3.1

Grant and Affiliation Information for Geometrical control of the active site electronic structure of pyranopterin enzymes by metal-dithiolate folding: aldehyde oxidase.

AFFILIATION: Department of Chemistry, The University of Arizona, Tucson, Arizona 85721, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM-37773

ACRONYM: GM

MEDLINETA: J Am Chem Soc

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