A new cytotoxic fatty acid (5Z,9Z)-22-methyl-5,9-tetracosadienoic acid and the sterols from the far eastern sponge Geodinella robusta.
A new fatty acid, (5Z,9Z)-22-methyl-5,9-tetracosadienoic acid (1a), and a rare fatty acid, (5Z,9Z)-23-methyl-5,9-tetracosadienoic acid (2a), the predominant constituents of the free fatty acid fraction from the lipids of the sponge Geodinella robusta, were isolated and partly separated by reversed phase high-performance liquid chromatography, followed by multifold crystallization from MeOH to give 1a and 2a in 70% and 60% purity, respectively. These fatty acids were identified as (5Z,9Z)-22- and (5Z,9Z)-23-methyl-5,9-tetracosadienoic acids by nuclear magnetic resonance techniques, including distortionless enhancement by polarization transfer, heteronuclear multiple quantum connectivity, and correlation spectroscopy experiments, as well as from mass-spectrometric data for their methyl esters, the methyl esters of their perhydro derivatives, and their pyrrolidides. Mixtures of 1a and 2a showed cytotoxic activity against mouse Ehrlich carcinoma cells and a hemolytic effect on mouse erythrocytes. The sterol fraction from the same sponge was analyzed by gas-liquid chromatography-mass spectrometry, and 24-methylenecholesterol was identified as a main constituent of this fraction. The implications of the co-occurrence of membranolytic long-chain fatty acids and 24-methylenecholesterol as a main membrane sterol are discussed in terms of the phenomenon of biochemical coordination.
Makarieva
Tatyana N
TN
Laboratory of the Marine Natural Products, Pacific Institute of Bioorganic Chemistry of the Russian Academy of Sciences, Vladivostok.
Santalova
Elena A
EA
Gorshkova
Irina A
IA
Dmitrenok
Andrei S
AS
Guzii
Alla G
AG
Gorbach
Vladimir I
VI
Svetashev
Vassilii I
VI
Stonik
Valentin A
VA
D000818:Animals; D002286:Carcinoma, Ehrlich Tumor / Q000188:drug therapy; D002851:Chromatography, High Pressure Liquid; D003603:Cytotoxins / Q000302:isolation & purification* / Q000494:pharmacology*; D004912:Erythrocytes / Q000187:drug effects; D005231:Fatty Acids, Unsaturated / Q000302:isolation & purification* / Q000494:pharmacology*; D008401:Gas Chromatography-Mass Spectrometry; D006461:Hemolysis / Q000187:drug effects; D066298:In Vitro Techniques; D009682:Magnetic Resonance Spectroscopy; D051379:Mice; D011161:Porifera / Q000737:chemistry*; D013261:Sterols / Q000737:chemistry*
C464979:22-methyl-5,9-tetracosadienoic acid; D003603:Cytotoxins; D005231:Fatty Acids, Unsaturated; D013261:Sterols; C074583:23-methyl-5,9-tetracosadienoic acid