Regiospecific Enzymatic Oxygenation of cis-Vaccenic Acid in the Marine Phototrophic Bacterium Erythrobacter sp. strain MG3

The fatty acid composition of the marine phototrophic bacterium Erythrobacter sp. strain MG3 was analysed. The involvement of an unusual enzymatic peroxidation of the allylic carbon 10 of cis-vaccenic acid in this strain was confirmed. This process, which seems to be a characteristic of some aerobic and anaerobic phototrophic bacteria, appeared to also act on the allylic carbon 10 of octadeca-5,11-dienoic acid. Enzymatic degradation of 10-hydroperoxyoctadec-11(cis)-enoic acid resulting from the peroxidation of cis-vaccenic acid mainly involves reduction to the corresponding hydroxy acid (probably catalysed by peroxygenases) and cleavage to the corresponding oxoacid, which is then biohydrogenated. Abiotic degradation of this hydroperoxide involves allylic rearrangement to 10-hydroperoxyoctadec-11(trans)-enoic and 12-hydroperoxyoctadec-10(trans)-enoic acids and cyclisation to the very unusual 7,10-epoxyoctadec-11(cis)-enoic acid. Several tests carried out at different periods of growth and under different growth conditions allowed to show that the induction of this enzymatic peroxidation process strongly depends on the physiological state of the cells and is enhanced during C-limitation and at low temperatures.