title: Simple synthesis of diastereomerically pure phosphatidylglycerols by phospholipase D-catalyzed transphosphatidylation.
abstract: A simple method for synthesizing diastereomerically pure phosphatidylglycerols (PtdGro), namely, 1,2-diacyl-sn-glycero-3-phospho-3'-sn-glycerol (R,R configuration) and 1,2-diacyl-sn-glycero-3-phospho-1'-sn-glycerol (R,S configuration), was established. For this purpose, diastereomeric 1,2-O-isopropylidene PtdGro were prepared from 1,2-diacyl-sn-glycero-3-phosphocholine (PtdCho) and enantiomeric 1,2-O-isopropylideneglycerols by transphosphatidylation with phospholipase D (PLD) from Actinomadura sp. This species was selected because of its higher transphosphatidylation activity and lower phosphatidic acid (PtdOH) formation than PLD from some Streptomyces species tested. The reaction proceeded well, giving almost no hydrolysis of PtdCho to PtdOH in a biphasic system consisting of diethyl ether and acetate buffer at 30 degrees C. The isopropylidene protective group was removed by heating the diastereomeric isopropylidene PtdGro at 100 degrees C in trimethyl borate in the presence of boric acid to obtain the desired PtdGro diastereomers. The purities of the products, which were determined by chiral-phase HPLC, were exclusively dependent on the optical purities of the original isopropylidene-glycerols used. The present method is simple and can be utilized for the synthesis of pure PtdGro diastereomers having saturated and unsaturated acyl chains.
authors.affiliation: Graduate School of Fisheries Sciences, Hokkaido University, Hakodate 041-8611, Japan.
authors.forename: Rina
authors.initials: R
authors.lastname: Sato
authors.forename: Yutaka
authors.initials: Y
authors.lastname: Itabashi
authors.forename: Hironori
authors.initials: H
authors.lastname: Fujishima
authors.forename: Hidetoshi
authors.initials: H
authors.lastname: Okuyama
authors.forename: Arnis
authors.initials: A
authors.lastname: Kuksis
mesh_terms: D001426:Bacterial Proteins; D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D007202:Indicators and Reagents; D010713:Phosphatidylcholines / Q000378:metabolism; D010715:Phosphatidylglycerols / Q000138:chemical synthesis* / Q000737:chemistry; D010739:Phospholipase D / Q000378:metabolism*; D010766:Phosphorylation; D013237:Stereoisomerism
chemical_list: D001426:Bacterial Proteins; D007202:Indicators and Reagents; D010713:Phosphatidylcholines; D010715:Phosphatidylglycerols; D010739:Phospholipase D