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Publication Type
Journal Article
Author, Analytic
Aquart, Danielle V.; Dasgupta, Tara P.
Author Affiliation, Ana.
Department of Chemistry
Article Title
Dynamics of interaction of vitamin C with some potent nitrovasodilators, S-nitroso-N-acetyl-D,L-penicillamine (SNAP) and S-nitrosocaptopril (SNOCap), in aqueous solution
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Journal Title
Biophysical Chemistry
Translated Title
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Reprint Status
Refereed
Date of Publication
2004
Volume ID
107
Issue ID
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Page(s)
117-131
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ISSN
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Notes
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Abstract
The reductive decomposition of both SNAP and SNOCap by ascorbate in aqueous solution (in the presence of EDTA) was throughly investigated. Nitric oxide (NO) release from the reaction occurs in an ascorbate concentration and pH dependent manner. Rates and hence NO release increased drastically with increasing pH, signifying that the most highly ionized form of ascorbate is the more reactive species. The experiments were monitored spectrophotometrically, and second-order rate constants calculated at 37 C for the reduction of SNAP are kb=9.811.39x10-3 M-1 s-1 and kc=66238 M-1 s-1 and for SNOCap are kb=2.571.29x10-2 M-1 s-1 and kc=49.71.3 M-1 s-1. kb and kc are the second-order rate constants via the ascorbate monoanion (HA-) and dianion (A2-) pathways, respectively. Activation parameters were also calculated and are DHb=937 kJ mol-1, DSb=152 J K-1 mol-1 and DHc=515 kJ mol-1, DSc= -283 J K-1 mol-1 with respect to the reactions involving SNAP. Those for the reaction between SNOCap and ascorbate were calculated to be DHb=6311 kJ mol-1, DSb= -7120 J K-1 mol-1 and DHc=1037 kJ mol-1, DSc=1188 J K-1 mol-1. The effect of Cu2+/Cu+ ions on the reductive decompositions of these S-nitrosothiols was also investigated in absence of EDTA. SNOCap exhibits relatively high stability at near physiological conditions (37 C and pH 7.55) even in the presence of micromolar concentrations of Cu+, with decomposition rate constant being 0.011 M-1 s-1 in comparison to SNAP which is known to be more susceptible to catalytic decomposition by Cu+ (second-order rate constant of 20 M-1 s-1 at pH 7.4 and 25 C). It was also observed that the reductive decomposition of SNAP is not catalyzed by alkali metal ions, however, there was an increase in rate as the ionic strength increases from 0.2 to 0.5 mol dm-3 NaCl.....
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