Language:

Reaction of Hydrogen Sulfide with Disulfide and Sulfenic Acid to Form the Strongly Nucleophilic Persulfide

The Journal of biological chemistry, 2015-11, Vol.290 (45), p.26866-26880 [Peer Reviewed Journal]

2015 © 2015 ASBMB. Currently published by Elsevier Inc; originally published by American Society for Biochemistry and Molecular Biology. ;2015 by The American Society for Biochemistry and Molecular Biology, Inc. ;2015 by The American Society for Biochemistry and Molecular Biology, Inc. 2015 The American Society for Biochemistry and Molecular Biology, Inc. ;ISSN: 0021-9258 ;EISSN: 1083-351X ;DOI: 10.1074/jbc.M115.672816 ;PMID: 26269587

Full text available

Citations Cited by

Actions
1. Add to My Research
2. Remove from My Research
3. E-mail
4. Print
5. Permalink
6. Citation
7. EasyBib
8. EndNote
9. RefWorks
10. Delicious
11. Export RIS
12. Export BibTeX

Title:
Reaction of Hydrogen Sulfide with Disulfide and Sulfenic Acid to Form the Strongly Nucleophilic Persulfide
Author: Cuevasanta, Ernesto ; Lange, Mike ; Bonanata, Jenner ; Coitiño, E. Laura ; Ferrer-Sueta, Gerardo ; Filipovic, Milos R. ; Alvarez, Beatriz
Subjects: Cell Line ; disulfide ; Disulfides - chemistry ; Disulfides - metabolism ; Enzymology ; Human Umbilical Vein Endothelial Cells ; Humans ; hydrodisulfide ; hydrogen sulfide ; Hydrogen Sulfide - chemistry ; Hydrogen Sulfide - metabolism ; In Vitro Techniques ; Kinetics ; Models, Biological ; Models, Chemical ; Molecular Weight ; Oxidation-Reduction ; persulfide ; Serum Albumin - chemistry ; Serum Albumin - metabolism ; sulfenic acid ; Sulfenic Acids - chemistry ; Sulfenic Acids - metabolism ; sulfhydryl ; Sulfhydryl Compounds - chemistry ; Sulfhydryl Compounds - metabolism ; Sulfides - chemistry ; Sulfides - metabolism ; thiol
Is Part Of: The Journal of biological chemistry, 2015-11, Vol.290 (45), p.26866-26880
Description: Hydrogen sulfide (H2S) is increasingly recognized to modulate physiological processes in mammals through mechanisms that are currently under scrutiny. H2S is not able to react with reduced thiols (RSH). However, H2S, more precisely HS−, is able to react with oxidized thiol derivatives. We performed a systematic study of the reactivity of HS− toward symmetric low molecular weight disulfides (RSSR) and mixed albumin (HSA) disulfides. Correlations with thiol acidity and computational modeling showed that the reaction occurs through a concerted mechanism. Comparison with analogous reactions of thiolates indicated that the intrinsic reactivity of HS− is 1 order of magnitude lower than that of thiolates. In addition, H2S is able to react with sulfenic acids (RSOH). The rate constant of the reaction of H2S with the sulfenic acid formed in HSA was determined. Both reactions of H2S with disulfides and sulfenic acids yield persulfides (RSSH), recently identified post-translational modifications. The formation of this derivative in HSA was determined, and the rate constants of its reactions with a reporter disulfide and with peroxynitrite revealed that persulfides are better nucleophiles than thiols, which is consistent with the α effect. Experiments with cells in culture showed that treatment with hydrogen peroxide enhanced the formation of persulfides. Biological implications are discussed. Our results give light on the mechanisms of persulfide formation and provide quantitative evidence for the high nucleophilicity of these novel derivatives, setting the stage for understanding the contribution of the reactions of H2S with oxidized thiol derivatives to H2S effector processes. Background: Hydrogen sulfide (H2S) modulates physiological processes in mammals. Results: The reactivity of H2S toward disulfides (RSSR) and albumin sulfenic acid (RSOH) to form persulfides (RSSH) was assessed. Conclusion: H2S is less reactive than thiols. Persulfides have enhanced nucleophilicity. Significance: This kinetic study helps rationalize the contribution of the reactions with oxidized thiol derivatives to H2S biology.
Publisher: United States: Elsevier Inc
Language: English
Identifier: ISSN: 0021-9258
EISSN: 1083-351X
DOI: 10.1074/jbc.M115.672816
PMID: 26269587
Source: MEDLINE
PubMed Central
Alma/SFX Local Collection

Back to results list


INSPIRE LIBRARY - TON DUC THANG UNIVERSITY	(84-028) 37 755 057	Feedback
19 Nguyen Huu Tho St. Dist.7, HCM	thuvien@tdtu.edu.vn	Feedback

Reaction of Hydrogen Sulfide with Disulfide and Sulfenic Acid to Form the Strongly Nucleophilic Persulfide

Searching Remote Databases, Please Wait