title: Effect of Methoxy Substituents on the Activation Barriers of the Glutathione Peroxidase-Like Mechanism of an Aromatic Cyclic Seleninate.
abstract: Density functional theory (DFT) models including explicit water molecules have been used to model the redox scavenging mechanism of aromatic cyclic seleninates. Experimental studies have shown that methoxy substitutions affect the rate of scavenging of reactive oxygen species differently depending upon the position. Activities are enhanced in the para position, unaffected in the meta, and decreased in the ortho. DFT calculations show that the activation barrier for the oxidation of the selenenyl sulfide, a proposed key intermediate, is higher for the ortho methoxy derivative than for other positions, consistent with the low experimental conversion rate.
authors.affiliation: Department of Chemistry and Biochemistry, Old Dominion University, Hampton Boulevard, Norfolk, VA 23529, USA. cbayse@odu.edu.
authors.forename: Craig A
authors.initials: CA
authors.lastname: Bayse
authors.affiliation: Department of Chemistry and Biochemistry, Old Dominion University, Hampton Boulevard, Norfolk, VA 23529, USA. ashoa001@odu.edu.
authors.forename: Ashley L
authors.initials: AL
authors.lastname: Shoaf
mesh_terms: D016166:Free Radical Scavengers / Q000737:chemistry*; D005979:Glutathione Peroxidase / Q000737:chemistry; D008738:Methyl Ethers / Q000737:chemistry*; D018716:Molecular Mimicry; D016566:Organoselenium Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D017382:Reactive Oxygen Species / Q000037:antagonists & inhibitors / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry*; D013816:Thermodynamics
chemical_list: D016166:Free Radical Scavengers; D008738:Methyl Ethers; D016566:Organoselenium Compounds; D017382:Reactive Oxygen Species; D013440:Sulfides; D005979:Glutathione Peroxidase
keywords: antioxidants; density functional theory; glutathione peroxidase; organoselenium compounds