Free Radical Scavenging Properties of Guaiacol Oligomers: A Combined Experimental and Quantum Study of the Guaiacyl-Moiety Role

Abstract

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) ΔG and ΔG^# 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.