1-2-oleoylphosphatidylcholine and 4-hydroxyphenylethanol

The phenols hydroxytyrosol and tyrosol made abundantly available through olive oil processing were enzymatically transesterified into effective lipophilic antioxidants with cuphea oil. The hydroxytyrosyl and tyrosyl esters made from cuphea oil were assessed for their ability to partition into, locate within and effect the bilayer behavior of 1,2-dioloeoylphosphatidylcholine liposomes and compared to their counterparts made from decanoic acid. Partitioning into liposomes was on the same scale for both hydroxytyrosyl derivatives and both tyrosyl derivatives. All were found to locate nearly at the same depth within the bilayer. Each was found to affect bilayer behavior in a distinct manner.

Topics: Antioxidants; Cuphea; Decanoic Acids; Esterification; Esters; Lipid Bilayers; Liposomes; Models, Chemical; Molecular Structure; Phenylethyl Alcohol; Phosphatidylcholines; Plant Oils; Time Factors

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.

Topics: Biocatalysis; Chromatography, Thin Layer; Hydroquinones; Isomerism; Magnetic Resonance Spectroscopy; Phenylethyl Alcohol; Phosphatidylcholines; Phospholipase D; Phospholipids; Streptomyces; Time Factors