title: Substituent effects on O--H bond dissociation enthalpies and ionization potentials of catechols: a DFT study and its implications in the rational design of phenolic antioxidants and elucidation of structure-activity relationships for flavonoid antioxidants.
abstract: Density functional theory (DFT) on B3LYP/6-31G(d,p) level was employed to investigate the substituent effects on O--H bond dissociation enthalpies (BDEs) and ionization potentials (IPs) of catechols. It was revealed that the ortho hydroxyl of catechol was effective for the reduction of the O--H BDE; however, the group had little influence on the IP. The para substituent effects upon O--H BDEs and IPs for catechols were roughly the same as those for monophenols, and this gave the catechol moiety more potential than monophenol to be used as a lead compound in rational design of phenolic antioxidants. In addition, the 1,4-pyrone effects on O--H BDEs of catecholic rings A or B of flavonoids were also investigated. Although 1,4-pyrone extended the conjugation system of flavonoids, it was not beneficial to reduce the O--H BDE as a result of its electron-withdrawing property. Thus, 1,4-pyrone was unlikely to be favorable to enhance the H-abstraction activity of flavonoids.
authors.affiliation: Laboratory for Computational Biology Shandong University of Technology Zibo 255049, P.R. China. zhanghy@sdut.edu.cn
authors.forename: Hong-Yu
authors.initials: HY
authors.lastname: Zhang
authors.forename: You-Min
authors.initials: YM
authors.lastname: Sun
authors.forename: Xiu-Li
authors.initials: XL
authors.lastname: Wang
mesh_terms: D000975:Antioxidants / Q000737:chemistry*; D002396:Catechols / Q000737:chemistry*; D015195:Drug Design; D005419:Flavonoids / Q000737:chemistry*; D015394:Molecular Structure; D013329:Structure-Activity Relationship; D013816:Thermodynamics
chemical_list: D000975:Antioxidants; D002396:Catechols; D005419:Flavonoids