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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
14
pubmed:dateCreated
2008-7-7
pubmed:abstractText
Hitherto, the decay mechanisms of nitrosated dithiols as well as formation of related products have not been conclusively elucidated. In this paper, we demonstrate that nitrosated dl-dithiothreitol (DTT) decays via two independent pathways, that is, one producing exclusively nitric oxide and one producing (initially) nitroxyl (HNO/3NO-). The importance of the two decomposition pathways depends on the degree of nitrosation of DTT. Dinitroso-dithiothreitol (NODTTNO) generates quantitatively nitric oxide, whereas mononitroso-dithiothreitol (NODTT) yields initially nitroxyl. Since NODTT and DTT are both targets for nitroxyl, their availability governs the HNO-derived formation of nitric oxide (with NODTT as reactant) or hydroxyl amine and ammonium ion (with DTT as reactant). The formation of NH4+ from the HNO-DTT reaction probably proceeds by a stepwise, NH2OH-independent mechanism, because DTT-derived sulfinamide was identified by N-15 NMR spectrometry as an intermediate. Our data are in line with the assumption that triplet nitroxyl (3NO-) is formed by a unimolecular decay of the deprotonated (thiolate) form of NODTT, because CBS-QB3 calculations predict the existence of a low-lying triplet state of the latter species. The identified pathways are proposed to be of general importance for physiological systems because control experiments showed that the physiological dithiol thioredoxin reacts in a similar manner.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Jul
pubmed:issn
1477-0520
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:volume
6
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
2560-73
pubmed:meshHeading
pubmed:year
2008
pubmed:articleTitle
Dependence of product formation from decomposition of nitroso-dithiols on the degree of nitrosation. Evidence that dinitroso-dithiothreitol acts solely as an nitric oxide releasing compound.
pubmed:affiliation
Institut für Physiologische Chemie, Universitätsklinikum Essen, Hufelandstrasse 55, 45122, Essen, Germany.
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't