Selenol Nitrosation and <i>Se</i>‐Nitrososelenol Homolysis: A Reaction Path with Possible Biochemical Implications

Wismach, Cathleen; Mont, Wolf‐Walther du; Jones, Peter G.; Ernst, Ludger; Papke, Ulrich; Mugesh, Govindasamy; Kaim, Wolfgang; Wanner, Matthias; Becker, K. D.

doi:10.1002/anie.200453872

Cited by 23 publications

(16 citation statements)

References 35 publications

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“…7 Our group has a long-standing interest in exploring the role of intramolecular coordination in the stabilization of relatively unstable organochalcogen species. 8 We, and others, have successfully implemented this strategy for the stabilization of novel species; 12 (E = Se, Te). Extending this concept, we envisaged that the hydrolysis of RTeX 3 (3) (R = 2-phenylazophenyl; X = Cl, Br), having an intramolecularly coordinating group, may lead to the isolation of well-defined hydrolysis and/or condensation products.…”

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confidence: 99%

Hydrolysis of 2-phenylazophenyltellurium trihalides: isolation of an unprecedented homometallic, discrete heptanuclear organotellurium oxidecluster

et al. 2010

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confidence: 99%

Hydrolysis of 2-phenylazophenyltellurium trihalides: isolation of an unprecedented homometallic, discrete heptanuclear organotellurium oxidecluster

et al. 2010

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“…12s in ESI{). 17 However, based on reported studies, 5,9,10,12,13 the following two reactions (reactions (5) and/or (6)) are most likely responsible for the RSNO decomposition.…”

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confidence: 99%

“…Further investigations are needed to determine whether a plausible intermediate, a nitrosotellurol species (ArTeNO), can in fact be formed during this reaction, as suggested for the similar organoseleniummediated RSNO decomposition. 10 Otherwise, the ArTeSR species may be directly produced via reaction (6), and this intermediate could participate in the catalytic cycle. In fact, it is hard to differentiate between ArTeTeAr and ArTeSR species in the presence of RSH and/or RSNO probably due to the fast equilibria reactions involving all of these species (reactions (1)-( 6)).…”

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confidence: 99%

Organoditelluride-mediated catalytic S-nitrosothiol decomposition

Hwang

Meyerhoff

2007

J. Mater. Chem.

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An organoditelluride (5,59-ditelluro-2,29-dithiophenecarboxylic acid) and a polymeric derivative thereof are shown to exhibit catalytic decomposition of S-nitrosothiols such as S-nitrosoglutathione (GSNO) and S-nitrosocysteine (CySNO).Physiological S-nitrosothiols (RSNOs) such as S-nitrosoglutathione (GSNO), S-nitrosocysteine (CySNO), and S-nitrosoalbumin (AlbSNO) are known to serve as storage and transfer agents of physiologically active nitric oxide (NO). 1 Because of the many biological functions of NO, including smooth muscle relaxation, anti-platelet activity, anti-inflammatory activity, and involvement in wound healing, 2 the decomposition of RSNOs to NO is of great interest. 3 Known methods for the decomposition of RSNOs to NO include catalytic reactions by metal ions (Cu + , Fe 2+ , Hg 2+ , and Ag + ) 4 and organodiselenides (RSeSeR) 5 as well as air, photoand thermal-induced decomposition pathways. 6 Some enzymes such as glutathione peroxidase (GPx), 5 thioredoxin (Trxn), 7 and protein disulfide isomerase (PDI), 8 are also known for their ability to generate NO from RSNOs. Although a few groups have proposed a mechanism for selenium-mediated RSNO decomposition, 5,9,10 the exact catalytic mechanism is not yet clear. Considering the similar chemical properties of selenium and tellurium, including the well known GPx activities of organodichalcogenides, [11][12][13] it is plausible that organotellurium compounds could also liberate NO from RSNOs. Indeed, we now report that certain organoditelluride species (RTeTeR), specifically, 5,59-ditelluro-2,29-dithiophenecarboxylic acid 1 and its polymeric derivative 3 (see Scheme 1), can catalyze RSNO decomposition to NO in the presence of endogenous reducing agents such as glutathione (GSH) or cysteine (CySH) at physiological pH.Organoditelluride 1 was synthesized by modifying a previously reported procedure (see Scheme 1). 14 The 5,59-positioned regioisomer was isolated as the major product, as identified by NMR through the substitution of a deuterium on the Te site using NaOD (see Fig. 1s in ESI{). Further, organoditelluride 1 was tethered to an amine modified hydrophilic polyurethane (HPU: Tecophilic, SP-93A-100), resulting in 10.5 mg cm 23 density of organoditelluride 1 in the polymer based on the Te analysis via ICP-MS (see Scheme 1 and synthetic details in ESI{). This polymer is useful for studying both the mechanism and the potential biomedical applications of the new organotellurium chemistry.

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“…For example, an essential selenium-containing antioxidant enzyme called glutathione peroxidase (GPx) can be inactivated by treating it with RSNO or endogenous NO [20][21][22][23][24][25], presumably through the Se-nitrosation of selenocysteine [25,27]. In contrast to the extensive studies undertaken on S-nitrosothiols, however, chemical information about their selenium analogues is lacking to date despite their potential physiological importance [31]. To elucidate the mechanism of NOmediated modification of selenoproteins, reference data on Se-nitrosated species are thus indispensable.…”

Section: Introductionmentioning

confidence: 99%

“…To elucidate the mechanism of NOmediated modification of selenoproteins, reference data on Se-nitrosated species are thus indispensable. In this area, Nagase and coworkers synthesized a Se-nitroselenol and calculated its spectral properties [32], and Becker and coworkers discussed the homolysis of Se-nitrososelenol [31]. Owing to the weak 4p-2p orbital overlap, the selenium-nitrogen bond of the SeNO group is expected to be weaker than the sulfur-nitrogen bond of the SNO group, such that Se-nitrososelenols are likely to be more labile than S-nitrosothiols.…”

Section: Introductionmentioning

confidence: 99%

The theoretical comparison between two model NO carriers, MeSNO and MeSeNO

Lai

Chou

2007

J Mol Model

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In this study, we apply a hybrid DFT functional, MPW1LYP, to make a comparison between MeSNO and MeSeNO. Due to the mesomeric effect and negative hyperconjugation, Se-nitrososelenols seem to be more unstable than S-nitrosothiols regarding unimolecular decomposition. Interestingly, however, the barrier of the transnitrosation reaction of MeSeNO is larger than that of MeSNO, disregarding nucleophiles in the gas phase. Using the polarizable continuum model to consider the water solvent effect, the transnitrosation reactions of MeXNO and YMe- (X = S, Se; Y = S, Se) are found to undergo concerted reactions, in sharp contrast to the two-step reaction pathways concluded in the gas phase. Moreover, the barriers of the transnitrosation reactions of MeSNO for nucleophiles SMe- and SeMe- from the gas phase to the aqueous solution are found to be decreased, while the transnitrosation reactions of MeSeNO are essentially barrierless in aqueous solution.

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Selenol Nitrosation and Se‐Nitrososelenol Homolysis: A Reaction Path with Possible Biochemical Implications

Abstract: Dedicated to Professor Reinhard Schmutzler on the occasion of his 70th birthdayThe biological role of nitric oxide (NO) as a secondary messenger, for instance in the cardiovascular system, has been known for more than a decade. Nitrosation of the cysteine

Cited by 23 publications

References 35 publications

Hydrolysis of 2-phenylazophenyltellurium trihalides: isolation of an unprecedented homometallic, discrete heptanuclear organotellurium oxidecluster

Hydrolysis of 2-phenylazophenyltellurium trihalides: isolation of an unprecedented homometallic, discrete heptanuclear organotellurium oxidecluster

Organoditelluride-mediated catalytic S-nitrosothiol decomposition

The theoretical comparison between two model NO carriers, MeSNO and MeSeNO

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