Electronic and Spatial Structures of Water-Soluble Dinitrosyl Iron Complexes with Thiol-Containing Ligands Underlying Their Ability to Act as Nitric Oxide and Nitrosonium Ion DonorsReportar como inadecuado




Electronic and Spatial Structures of Water-Soluble Dinitrosyl Iron Complexes with Thiol-Containing Ligands Underlying Their Ability to Act as Nitric Oxide and Nitrosonium Ion Donors - Descarga este documento en PDF. Documentación en PDF para descargar gratis. Disponible también para leer online.

Journal of BiophysicsVolume 2011 2011, Article ID 878236, 14 pages

Review ArticleN. N. Semyonov Institute of Chemical Physics, Russian Academy of Sciences, Kosygin Street 4, Moscow 119991, Russia

Received 5 November 2011; Accepted 22 December 2011

Academic Editor: Eaton Edward Lattman

Copyright © 2011 Anatoly F. Vanin and Dosymzhan Sh. Burbaev. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The ability of mononuclear dinitrosyl iron commplexes M-DNICs with thiolate ligands to act as NO donors and to trigger S-nitrosation of thiols can be explain only in the paradigm of the model of the Fe

NO

2 core {FeNO2}

according to the Enemark-Feltham classification. Similarly, the {RS

2Fe

NO

2}

structure describing the distribution of unpaired electron density in M-DNIC corresponds to the low-spin state with a d

electron configuration of the iron atom and predominant localization of the unpaired electron on MO and the square planar structure of M-DNIC. On the other side, the formation of molecular orbitals of M-DNIC including orbitals of the iron atom, thiolate and nitrosyl ligands results in a transfer of electron density from sulfur atoms to the iron atom and nitrosyl ligands. Under these conditions, the positive charge on the nitrosyl ligands diminishes appreciably, the interaction of the ligands with hydroxyl ions or with thiols slows down and the hydrolysis of nitrosyl ligands and the S-nitrosating effect of the latter are not manifested. Most probably, the S-nitrosating effect of nitrosyl ligands is a result of weak binding of thiolate ligands to the iron atom under conditions favoring destabilization of M-DNIC.





Autor: Anatoly F. Vanin and Dosymzhan Sh. Burbaev

Fuente: https://www.hindawi.com/



DESCARGAR PDF




Documentos relacionados