Computational Studies on the A Cluster of Acetyl-Coenzyme A Synthase: Geometric and Electronic Properties of the NiFeC Species and Mechanistic Implications

Journal of the American Chemical Society

Volumn 125, Issue 46, 2003, Pages 13962-13963

  Schenker, Ralph P ^a   Brunold, Thomas C ^a  

^a UNIVERSITY OF WISCONSIN MADISON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETYL COENZYME A SYNTHASE; ENZYME; UNCLASSIFIED DRUG;

ARTICLE; CALCULATION; DENSITY FUNCTIONAL THEORY CALCULATION; ENZYME ACTIVE SITE; ENZYME ANALYSIS; ENZYME MECHANISM; ENZYME STRUCTURE; HYDROGEN BOND; MAGNETISM; METHYLATION; MOSSBAUER SPECTROSCOPY; OXIDATION REDUCTION REACTION; STRUCTURE ANALYSIS; X RAY CRYSTALLOGRAPHY;

ALDEHYDE OXIDOREDUCTASES; IRON; IRON-SULFUR PROTEINS; KINETICS; MODELS, MOLECULAR; MULTIENZYME COMPLEXES; NICKEL;

EID: 0242415146     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja037893q     Document Type: Article

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21. For computational details, see Supporting Information.
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23. In the as-isolated ACS samples used for the EXAFS studies in ref 10, no CO is bound to the Cu ion. It can be expected that the Cu-S bonds would lengthen upon CO binding, which could at least partly explain the difference between the average experimental Cu-S distance and the one obtained for model 2.
24. 2+ unit prevented us from computing meaningful g values.
25. The fact that only one of the two Ni ions in model 1 exhibits sizable hyperfine coupling is in line with the finding in ref 7 that a single Ni atom was sufficient to simulate the ENDOR spectra.
26. p center and is thus difficult to predict quantitatively (see Craft, J. L.; Mandimutsira, B. S.; Fujita, K.; Riordan, C. G.; Brunold, T. C. Inorg. Chem. 2003, 42, 859-867).
27. 61Ni) = -0.50.
28. Q = 1.21 mm/s.6b
29. Fe34 = 9/2. See Supporting Information for details.
30. Model 3 was generated from optimized model 1 by removal of the CO ligand and subsequent geometry optimization using the same constraints as for 1 and 2. Key computational results are shown in Tables S5 and S6.
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