Scientific Reports of the Faculty of Agriculture, Okayama University
Published by the Faculty of Agriculture, Okayama University
ONLINE ISSN : 2186-7755

Chemoenzymatic Synthesis of Phospholipid Hydroperoxides

Baba, Naomichi
Yoneda, Kenji
Sasakura, Keiji
Shigeta, Yasutami
Kishida, Yasuhiro
Aoishi, Akihiro
Daido, Hiroko
Iwasa, Junkichi
Tahara, Shoichi
Kaneko, Takao
Matsuo, Mitsuyoshi
Shimizu, Sakayu
Abstract
Chemoenzymatic synthesis of 1-stearoyl-2-hydropeoxyacyl-sn-glycerophospholipids including phosphatidylcholine (PC-OOH), phosphatidic acid (PA-OOH), phosphatidylethanolamine (PE-OOH), phosphatidylglycerol (PG-OOH) and phosphatidylserine (PS-OOH). The hydroperoxy acyl moieties were prepared via hydroperoxidation of linoleic, dihomo-γ-linolenic and arachidonic acids by soybean, potate lipoxygenase or autoxidation. Their hydroperoxy group was protected as a dimethylperacetal before condensation with lysophosphatidylcholine. Optically active lysophosphatidylcholine was prepared via short pathway involving lipase-catalyzed direct enantioselective stearoylation of 2-O-benzylglycerol and choline phosphate synthesis. Peroxy fatty acids and lysophosphatidylcholine thus obtained were condensed using dicyclohexylcarbodiimide in chloroform. Removing the peracetal group in the product and purification by reverse-phase chromatography afforded the desired PC-OOH’s. PA-OOH, PG-OOH, PE-OOH and PS-OOH were obtained by phospholipase-D catalyzed transphosphatidylation from PC-OOH. As a reference compound for biological studies of hydroperoxy phopholipid, PC-OH's were also prepared in which hydroxy unsaturated fatty acyl group was linked to the sn-2 position of the glycerophospholipids.
Keywords
phospholipid
peroxide
hydroperoxide
phospholipase D
lipoxygenase
ISSN
0474-0254 
NCID
AN00033029