Universität zu Köln

Nava, Matthew, Martin-Drumel, Marie-Aline ORCID: 0000-0002-5460-4294, Lopez, Christopher A., Crabtree, Kyle N., Womack, Caroline C., Nguyen, Thanh L., Thorwirth, Sven ORCID: 0000-0001-8200-6710, Cummins, Christopher C., Stanton, John F. and McCarthy, Michael C. (2016). Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H2S and Nitroso Chemistries. J. Am. Chem. Soc., 138 (36). S. 11441 - 11445. WASHINGTON: AMER CHEMICAL SOC. ISSN 0002-7863

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Abstract

Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H2S biochemistries, but its existence and stability in vivo remain controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H2S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H2S + N2O3 -> HSNO + HNO2, where N2O3 is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H2S may form HNO and HSSH. The length of the S-N bond has been derived to high precision and is found to be unusually long: 1.84 angstrom, the longest S-N bond reported to date for an R-SNO compound. The present structural and, particularly, reactivity investigations of this elusive molecule provide a firm foundation to better understand its potential physiological chemistry and propensity to undergo S-N bond cleavage in vivo.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Nava, Matthew UNSPECIFIED UNSPECIFIED UNSPECIFIED Martin-Drumel, Marie-Aline UNSPECIFIED orcid.org/0000-0002-5460-4294 UNSPECIFIED Lopez, Christopher A. UNSPECIFIED UNSPECIFIED UNSPECIFIED Crabtree, Kyle N. UNSPECIFIED UNSPECIFIED UNSPECIFIED Womack, Caroline C. UNSPECIFIED UNSPECIFIED UNSPECIFIED Nguyen, Thanh L. UNSPECIFIED UNSPECIFIED UNSPECIFIED Thorwirth, Sven UNSPECIFIED orcid.org/0000-0001-8200-6710 UNSPECIFIED Cummins, Christopher C. UNSPECIFIED UNSPECIFIED UNSPECIFIED Stanton, John F. UNSPECIFIED UNSPECIFIED UNSPECIFIED McCarthy, Michael C. UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-262336
DOI:	10.1021/jacs.6b05886
Journal or Publication Title:	J. Am. Chem. Soc.
Volume:	138
Number:	36
Page Range:	S. 11441 - 11445
Date:	2016
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	0002-7863
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language NITRIC-OXIDE SOLUTIONS; S-NITROSOTHIOLS; HYDROGEN-SULFIDE; DISSOCIATION-ENERGIES; VENTILATORY RESPONSE; HNO; ISOMERIZATION; DECOMPOSITION; SPECTROSCOPY; GENERATION Multiple languages Chemistry, Multidisciplinary Multiple languages
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/26233