title: Mechanistic investigations on the efficient catalytic decomposition of peroxynitrite by ebselen analogues.
abstract: In this study, ebselen and its analogues are shown to be catalysts for the decomposition of peroxynitrite (PN). This study suggests that the PN-scavenging ability of selenenyl amides can be enhanced by a suitable substitution at the phenyl ring in ebselen. Detailed mechanistic studies on the reactivity of ebselen and its analogues towards PN reveal that these compounds react directly with PN to generate highly unstable selenoxides that undergo a rapid hydrolysis to produce the corresponding seleninic acids. The selenoxides interact with nitrite more effectively than the corresponding seleninic acids to produce nitrate with the regeneration of the selenenyl amides. Therefore, the amount of nitrate formed in the reactions mainly depends on the stability of the selenoxides. Interestingly, substitution of an oxazoline moiety on the phenyl ring stabilizes the selenoxide, and therefore, enhances the isomerization of PN to nitrate.
authors.affiliation: Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India.
authors.forename: Krishna P
authors.initials: KP
authors.lastname: Bhabak
authors.forename: Amit A
authors.initials: AA
authors.lastname: Vernekar
authors.forename: Surendar R
authors.initials: SR
authors.lastname: Jakka
authors.forename: Gouriprasanna
authors.initials: G
authors.lastname: Roy
authors.forename: Govindasamy
authors.initials: G
authors.lastname: Mugesh
mesh_terms: D001393:Azoles / Q000138:chemical synthesis / Q000737:chemistry*; D002264:Carboxylic Acids / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D006868:Hydrolysis; D054833:Isoindoles; D008958:Models, Molecular; D015394:Molecular Structure; D016566:Organoselenium Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D030421:Peroxynitrous Acid / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D001393:Azoles; D002264:Carboxylic Acids; D054833:Isoindoles; D016566:Organoselenium Compounds; C473453:seleninic acid; D030421:Peroxynitrous Acid; C042986:ebselen