Synthesis of novel phospholipids that bind phenylalkanols and hydroquinone via phospholipase D-catalyzed transphosphatidylation.
Phenylalkanols such as tyrosol and hydroxytyrosol (h-tyrosol), which possess antioxidant and anticancer properties, were phosphatidylated by phospholipase D (PLD)-catalyzed transphosphatidylation. After a 24-hour reaction of phosphatidylcholine (PC) and tyrosol with PLD, a new product was detected by TLC and identified to phosphatidyl-tyrosol by high-resolution MS and NMR analyses. The optimum reaction conditions were as follows: soyPC 50μmol, tyrosol 500μmol, ethyl acetate 1.6ml, PLD 1.6U, 0.2m sodium acetate buffer (pH 5.6) 0.8ml, 37°C for 24 hours. Under the optimum reaction conditions, the yields of phosphatidyl-tyrosol, hydroquinone (HQ), 2-(4-aminophenyl)ethanol (4APE), h-tyrosol and 2-phenylethanol (PEA) were 87±3.7, 13±1.3, 90±2.3, 64±5.5 and 85±1.0mol%, respectively. Furthermore, from the results of transphosphatidylation of soyPC with several phenylethanols and phenylpropanols, we established the following details about the reaction specificity of transphosphatidylation by PLD from Streptomyces sp.: (1) para-amino and para-hydroxyl groups in the benzene ring of PEA derivatives do not affect the transphosphatidylation by PLD, whereas meta-hydroxyl group slightly inhibits the transphosphatidylation. (2) Meta- and ortho-methyl groups in the benzene ring of PEA derivatives also slightly inhibit the transphosphatidylation. (3) Secondary and tertiary alcohols and hydroquinone are difficult to transphosphatidylate by PLD.
Yamamoto
Yukihiro
Y
Faculty of Fisheries Sciences, Hokkaido University, 3-1-1 Minato, Hakodate, Hokkaido 041-0821, Japan.
Kurihara
Hideyuki
H
Miyashita
Kazuo
K
Hosokawa
Masashi
M
D055162:Biocatalysis; D002855:Chromatography, Thin Layer; D006873:Hydroquinones / Q000737:chemistry / Q000378:metabolism*; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D010626:Phenylethyl Alcohol / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism; D010713:Phosphatidylcholines / Q000737:chemistry / Q000378:metabolism; D010739:Phospholipase D / Q000378:metabolism*; D010743:Phospholipids / Q000138:chemical synthesis* / Q000378:metabolism*; D013302:Streptomyces / Q000201:enzymology*; D013997:Time Factors
D006873:Hydroquinones; D010713:Phosphatidylcholines; D010743:Phospholipids; C011867:4-hydroxyphenylethanol; D010739:Phospholipase D; C017251:1,2-oleoylphosphatidylcholine; D010626:Phenylethyl Alcohol; C031927:hydroquinone