Free radical scavenging properties of guaiacol oligomers: a combined experimental and quantum study of the guaiacyl-moiety role.

Natural polyphenols are known to exhibit a lot of different biological properties, including antioxidant activity. For some polyphenols these activities are attributed to the presence of a guaiacol moiety. In the present paper we focus on the role of this moiety. For this purpose nine different compounds were enzymatically synthesized from guaiacol. To elucidate the structure-activity relationship of these polyphenols, DFT-(PCM)B3P86/6-311+G(2d,3pd)//(PCM)B3P86/6-31+G(d,p) calculations supported the experimental DPPH free radical scavenging activities. The antioxidant activities were correlated to (i) O-H BDEs (bond dissociation enthalpies), (ii) BDE(D) (BDE of a second H atom abstraction from the phenoxyradicals), (iii) spin density, (iv) HOMO (highest occupied molecular orbital) distribution, (v) IPs (ionization potentials), (vi) DeltaG and DeltaG(#) free energies of HAT (H atom transfer), and (vii) HAT rate constants. BDE(D) appeared to be the most important descriptor to understand the free radical scavenging ability of these compounds.