Calcium promoted phenolic coupling by superoxide radical —a possible lignification reaction in wood

Summary The reaction of enzymatically generated superoxide radical with coniferyl alcohol in aqueous solution at pH 8.0 was studied. In the absence of calcium (II) no reaction occurred, but with a calcium (II) concentration of about 50 mM or more, coniferyl alcohol was oxidized by the superoxide radical. Dehydrodiconiferyl alcohol and pinoresinol were identified in the reaction mixture. From this result it is concluded that in the presence of calcium (II) the superoxide radical can achieve a one electron oxidation of coniferyl alcohol.It is suggested that a superoxide-generating enzyme outside the cell wall is responsible for the lignification. This suggestion is based on knowledge of the pore structure of wood cell walls, the high calcium concentration in non-lignified cells, the course of lignification and the existence of superoxide-producing enzyme systems in plant cell walls.The author gratefully acknowledges the skiful technical assistance of Mr. Johan Lindberg