Author ORCID Identifier
https://orcid.org/0000-0002-2956-9781
Document Type
Article
Publication Date
2-2008
Publication Title
Journal of the American Chemical Society
Volume
130
Issue
11
First Page
3328
Last Page
3334
Abstract
Density functional theory methods have been employed to systematically investigate the overall mechanism of the second half-reaction of nitric oxide synthases. The initial heme-bound hydrogen peroxide intermediate previously identified is found to first undergo a simple rotation about its O−O peroxide bond. Then, via a “ping-pong” peroxidase-like mechanism the −OinH− proton is transferred back onto the substrate's −NO oxygen then subsequently onto the outer oxygen of the resulting Feheme−OOH species. As a result, Oout is released as H2O with concomitant formation of a compound I-type (Feheme−O) species. Formation of the final citrulline and NO products can then be achieved in one step via a tetrahedral transition structure resulting from direct attack of the Feheme−O moiety at the substrate's guanidinium carbon center. The possible role of alternative mechanisms involving a protonated compound II-type species or an initial transfer of only the −NH− hydrogen of the NHOH+ group of Nω-hydroxy-l-arginine is also discussed.
DOI
10.1021/ja072650+
Recommended Citation
Robinet, Jesse J.; Cho, Kyung-Bin; and Gauld, James. (2008). A Density Functional Theory Investigation on the Mechanism of the Second Half-Reaction of Nitric Oxide Synthase. Journal of the American Chemical Society, 130 (11), 3328-3334.
https://scholar.uwindsor.ca/chemistrybiochemistrypub/128