COMPUTATIONAL MODEL OF THE CATALYTIC CYCLE OF ORGANOSELENIUM ANTIOXIDANTS

The chemistry of the enzyme glutathione peroxidase and synthetic organoselenium enzyme mimics has been a significant research interest for more than three decades. In this work, the results of a computational study employing modern electronic structure methods to model the reactions of a synthetic glutathione peroxidase mimic are presented. \n\nThe ability of nine density-functional theory methods and thirteen basis sets to predict both molecular geometries and bond dissociation energies in organoselenium compounds is examined. This is used to determine the best methodology to employ for the study of glutathione peroxidase mimics.\n\nThe key reactions in the catalytic mechanism of the organoselenium antioxidant N,N-dimethyl-benzylamine-2-selenol are the focus of the remainder of the document. This is a three-step mechanism which includes many of the organic forms adopted by selenium compounds, including selenol, oxoacids, and selenylsulfides. In the first step of the cycle, the well-studied reduction of hydrogen peroxide by a selenol and a diselenide is modelled. The second step modelled is a substitution reaction at the selenium centre of a selenenic acid with a thiol. The final step discussed is the reduction of the selenium centre in a selenylsulfide, regenerating the selenol and forming a disulfide species. Each mechanism is evaluated by discussing both molecular geometries and reaction energetics. \n\nTo close the document, the peroxide reduction reaction is revisited to determine the effects of substitution on the phenyl ring of the synthetic antioxidant. This serves as a preliminary attempt to improve the antioxidant efficiency of this compound. In addition to a discussion of the changes in reaction energetics predicted, the topology of the electron density is studied using the quantum theory of atoms in molecules to better understand how the distribution of electron density is affected by substituents.

Récupéré en direct depuis OpenAlex et désinversé. Les résumés ne sont pas conservés dans cette base de données : les index inversés représentent 8,6 Go des 9,3 Go de texte de la base, et le serveur dispose de 13 Go libres.