Effect of Methoxy Substituents on the Activation Barriers of the Glutathione Peroxidase-Like Mechanism of an Aromatic Cyclic Seleninate

Molecules

Craig A. Bayse¹  Ashley L. Shoaf² 

[1] Department of Chemistry and Biochemistry, Old Dominion University, Hampton Boulevard, Norfolk, VA 23529, USA; E-Mail

关键词: organoselenium compounds;    antioxidants;    glutathione peroxidase;    density functional theory;   

DOI  :  10.3390/molecules200610244

来源: mdpi

【 摘 要 】

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.

【 授权许可】

CC BY   
© 2015 by the authors; licensee MDPI, Basel, Switzerland.