Photolytic preparation and isomerization of thionyl imide, thiocyanic acid, thionitrous acid, and nitrogen hydroxide sulfide in an argon matrix:  an experimental and theoretical study

Nonella, Marco; Huber, J. Robert; Ha, T.‐K.

doi:10.1021/j100304a014

Cited by 54 publications

(39 citation statements)

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“…However, a key aspect of HSNO's properties that seems to have been overlooked in these discussions is its mobile hydrogen, allowing facile 1,3 hydrogen shift and formation of four isomers with the same chemical equation (13)-a feature described in the seminal studies by Goehring in the 1950s (23) and by Müller and Nonella later on (24,25) that distinguishes HSNO from all other RSNOs (26). The same feature also contributes to the short half-life of the molecule at ambient temperatures, making it more probable that other yet unknown entities are involved as biological mediators of the NO/H 2 S cross-talk.…”

Section: Significancementioning

confidence: 99%

Key bioactive reaction products of the NO/H₂S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Cortese‐Krott

Kuhnle

Dyson

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

254

280

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Experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide (H 2 S) signaling pathways are intimately intertwined, with mutual attenuation or potentiation of biological responses in the cardiovascular system and elsewhere. The chemical basis of this interaction is elusive. Moreover, polysulfides recently emerged as potential mediators of H 2 S/sulfide signaling, but their biosynthesis and relationship to NO remain enigmatic. We sought to characterize the nature, chemical biology, and bioactivity of key reaction products formed in the NO/sulfide system. At physiological pH, we find that NO and sulfide form a network of cascading chemical reactions that generate radical intermediates as well as anionic and uncharged solutes, with accumulation of three major products: nitrosopersulfide (SSNO − ), polysulfides, and dinitrososulfite [N-nitrosohydroxylamine-N-sulfonate (SULFI/NO)], each with a distinct chemical biology and in vitro and in vivo bioactivity. SSNO − is resistant to thiols and cyanolysis, efficiently donates both sulfane sulfur and NO, and potently lowers blood pressure. Polysulfides are both intermediates and products of SSNO − synthesis/decomposition, and they also decrease blood pressure and enhance arterial compliance. SULFI/NO is a weak combined NO/nitroxyl donor that releases mainly N 2 O on decomposition; although it affects blood pressure only mildly, it markedly increases cardiac contractility, and formation of its precursor sulfite likely contributes to NO scavenging. Our results unveil an unexpectedly rich network of coupled chemical reactions between NO and H 2 S/sulfide, suggesting that the bioactivity of either transmitter is governed by concomitant formation of polysulfides and anionic S/N-hybrid species. This conceptual framework would seem to offer ample opportunities for the modulation of fundamental biological processes governed by redox switching and sulfur trafficking.sulfide | nitric oxide | nitroxyl | redox | gasotransmitter N itrogen and sulfur are essential for all known forms of life on Earth. Our planet's earliest atmosphere is likely to have contained only traces of O 2 but rather large amounts of hydrogen sulfide (H 2 S) (1). Indeed, sulfide may have supported life long before the emergence of O 2 and NO (2, 3).* This notion is consistent with a number of observations: H 2 S is essential for efficient abiotic amino acid generation as evidenced by the recent reanalysis of samples of Stanley Miller's original spark discharge experiments (4), sulfide is an efficient reductant in protometabolic reactions forming RNA, protein, and lipid precursors (5), and sulfide is both a bacterial and mitochondrial substrate (6), enabling even multicellular lifeforms to exist and reproduce under conditions of permanent anoxia (7). Thus, although eukaryotic cells may have originated from the symbiosis of sulfurreducing and -oxidizing lifeforms within a self-contained sulfur redox metabolome (8), sulfide may have been essential even earlier by providing the basic building blocks of ...

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Section: Significancementioning

confidence: 99%

Key bioactive reaction products of the NO/H₂S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Cortese‐Krott

Kuhnle

Dyson

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

254

280

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“…14,15 The molecule was produced from photolysis of HNSO, a low-lying stable structural isomer of HSNO (∆H ≥ 10 kcal/mol, 16 see Supplementary Information). Recently, HSNO has been detected under physiologically relevant conditions through protonation of [SNO] − or treatment of S-nitrosoglutathione with sodium sulde by infrared, 15 N NMR and mass spectroscopy. 2 Additionally, coordinated HSNO has been transiently observed by mass spectroscopy 17 and very recently a crystal structure was obtained of an RSNO coordinated to a copper complex.…”

mentioning

confidence: 99%

“…20,24 To explain these paradoxical bonding properties, theoretical models of the electronic structure of RSNOs include contributions from conventional (R−S−N− −O), zwit- In a serendipitous discovery, we found that when a mixture of H 2 S and NO heavily diluted in an inert buer gas (Ne) is expanded into a vacuum chamber, intense rotational lines of a previously unknown molecule, now unambiguously identied as HSNO, are observed by Fourier-transform microwave (FTMW) spectroscopy, a highly sensitive and selective technique which has been used to detect many molecules, both familiar and exotic. 26,27 Rotational transitions ( Figure 1) have been measured for both the cis and trans conformers of the main isotopologue of HSNO and four singly-substituted isotopic species (DSNO, H 34 SNO, HS 15 NO, HSN 18 O). From these data, highly accurate molecular parameters (rotational, centrifugal distortion, and hyperne constants) have been derived (Table S1).…”

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confidence: 99%

Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries

et al. 2016

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Thionitrous acid (HSNO), a potential key intermediate in biological signaling pathways, has been proposed to link NO and H 2 S biochemistries, but its existence and stability in vivo remains controversial. We establish that HSNO is spontaneously formed in high concentration when NO and H 2 S gases are mixed at room temperature in the presence of metallic surfaces. Our measurements reveal that HSNO is formed by the reaction H 2 S + N 2 O 3 → HSNO + HNO 2 , where N 2 O 3 is a product of NO disproportionation. These studies also suggest that further reaction of HSNO with H 2 S may form HNO and HSSH. The length of the SN bond has been derived to high precision, and is found to be unusually long: 1.84 Å the longest SN bond reported to date for an R-SNO compound. The present structural and, particularly, reactivity investigations of this elusive molecule provide a rm foundation to better understand its potential physiological chemistry and propensity to undergo SN bond clevage in vivo.The intriguing similarities between the biological proles of NO and H 2 S, two important gasotransmitters acting notably as blood pressure mediators, have raised questions about the possibility of`cross-talk' between the two species. 1Such an interaction could explain the surprisingly benecial eects of these signaling molecules as it may allow H 2 S to modulate the availability of NO within the body.2 The vast majority of NO in vivo is bound as S-nitrosothiols (RSNO), a family of molecules well known for their crucial role in response to oxygen deprivation 35 as well as for being important biological reservoir for NO. 6,7 RSNOs are typically formed through the reaction of nitrosylating agents with thiols (RSH), 8 Once formed, RSNOs can also act as nitrosylating agents thus highlighting their role as NO shuttles at the cellular level.The simplest RSNO, thionitrous acid (HSNO), has been proposed to be the product of the reaction between NO and H 2 S; 9 other possible species have been implicated in this cross-talk', including nitrosopersulde (SSNO − ) and Nnitrosohydroxylamine-N -sulfonate.10 Unlike larger RSNOs, HSNO is thought to be able to freely diuse through cell membranes 2 suggesting that it has the ability to transnitrosate proteins removed from the sites where NO is synthesized, and therefore could play a key role in cellular redox regulation.11 Understanding the role of small molecules such as NO and HNO in biological signal transduction has resulted in important advances in medicine. 12,13 To shed light on the role of HSNO in vivo, sensors are currently being developed to image this elusive molecule. However, the biochemistry (formation, transport, decomposition) of HSNO remains poorly understood and the structure of the molecule has not been determined to date. HSNO has been spectroscopically characterized by infrared measurements in low temperature argon matrices.14,15 The molecule was produced from photolysis of HNSO, a low-lying stable structural isomer of HSNO (∆H ≥ 10 kcal/mol, 16 see Supplementary Information). ...

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“…The simplest sulfinylimine HNSO, also known as thionylimide, was first prepared by the spontaneous gas phase reaction of ammonia and thionyl chloride at room temperature [2]. Theoretical studies using ab initio molecular orbital and density functional calculations have identified cis-HNSO as the most stable structure on the potential energy surface (PES) and predicted an additional seven structural isomers [3], four of which had already been prepared photolytically from HNSO in a low-temperature matrix and probed by spectroscopic methods [4][5][6][7]. Ultraviolet absorption spectroscopy of HNSO indicated electronic excitation centered at the S atom [8].…”

Section: Introductionmentioning

confidence: 99%

High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands

Puškar

Robertson

2006

Journal of Molecular Spectroscopy

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Photolytic preparation and isomerization of thionyl imide, thiocyanic acid, thionitrous acid, and nitrogen hydroxide sulfide in an argon matrix: an experimental and theoretical study

Cited by 54 publications

References 0 publications

Key bioactive reaction products of the NO/H₂S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Key bioactive reaction products of the NO/H₂S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries

High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands

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Photolytic preparation and isomerization of thionyl imide, thiocyanic acid, thionitrous acid, and nitrogen hydroxide sulfide in an argon matrix: an experimental and theoretical study

Cited by 54 publications

References 0 publications

Key bioactive reaction products of the NO/H2S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Key bioactive reaction products of the NO/H2S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H2S and Nitroso Chemistries

High-resolution FTIR spectroscopy of HNSO—Analysis of the highly perturbed ν4, ν6 and 2ν5 bands

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About

Key bioactive reaction products of the NO/H₂S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Key bioactive reaction products of the NO/H₂S interaction are S/N-hybrid species, polysulfides, and nitroxyl

Spontaneous and Selective Formation of HSNO, a Crucial Intermediate Linking H₂S and Nitroso Chemistries