ESR studies of radicals generated by ultrasonic irradiation of lignin solution. An application of the spin trapping method

Abstract

An electron spin resonance (ESR) method combined with a spin trapping reagent was successfully applied to trap and characterize unstable radicals which were generated by ultrasonic irradiation of dimethylsulfoxide (DMSO) solution of hardwood, Fagus crenata lignin. It was found, consequently, that a secondary carbon radical, ∼CH· was trapped as the nitroxide spin adduct when the DMSO solution was subjected to ultrasonic irradiation in the presence of a spin trapping reagent: 2, 4, 6-tri-tert-butylnitrosobenzene (BNB) at 50 °C for 60 minutes under vacuum. This means that the alkyl phenyl ether bonds known as lignin linkage bonds were homolytically scissoned by the ultrasonic irradiation, although the phenoxy radical, Ph-O· as the counter radical of the secondary carbon radical was not trapped by the BNB spin trap. Further, the data showed that the primary carbon radical, ∼OCH2 · is trapped by the BNB to form the corresponding spin adduct, indicating that the hydrogen abstraction from the ortho methoxy group in the syringyl and/or guaiacyl moiety is induced by the secondary carbon radical when irradiated. Based on these findings it was concluded that the Ph-O· radicals produced by the homolytic rupture of the alkyl phenyl ether bonds were not trapped by the BNB spin trap. This suggests that large steric hindrances operate between the syringyl with two methoxy moieties and/or guaiacyl with a methoxy moiety at the ortho position, and the BNB molecule bearing two bulky ortho tert-butyl groups.