A new family of very long chain alpha,omega-dicarboxylic acids is a major structural fatty acyl component of the membrane lipids of Thermoanaerobacter ethanolicus 39E.

Abstract

A new family of alpha,omega-dicarboxylic, very long chain fatty acids was isolated and characterized from the lipids of thermophilic anaerobic eubacterium, Thermoanaerobacter ethanolicus 39E. After the isolation of the membrane, the fatty acyl components were converted to methyl esters by acid-catalyzed methanolysis. The esterified fatty acyl components were purified by a variety of chromatographic techniques and analyzed by gas chromatography (GC) and GC-mass spectrometry (MS). One of the isolated, esterified alpha,omega-dicarboxylic, very long chain fatty acids was characterized by mass spectrometry, 1H and 13C NMR spectroscopy and Fourier transform infrared spectroscopy. NMR experiments used included double quantum filtered correlated spectroscopy (DQF-COSY) to establish spin connectivities and polarization transfer (DEPT) to measure the multiplicity of carbon signals split by protons. Based on these results, the structures of the other components could be deduced from their mass spectra. The new family of very long chain fatty acid methyl esters are alpha,omega-13,16-dimethylheptacosanedioate dimethyl ester (C29), alpha,omega-13,16-dimethyloctacosanedioate dimethyl ester (C30), alpha,omega-13,16-dimethylnonacosanedioate dimethyl ester (C31), and alpha,omega-13,16-dimethyltriacotanedioate dimethyl ester (C32). This family of fatty acids make up about 40% of fatty acyl components of the membrane of Thermoanaerobacter ethanolicus 39E. Almost all (> 90%) of the very long chain, alpha,omega-dicarboxylic fatty acid was alpha,omega-13,16-dimethyloctacosanedioic acid. A careful analysis of the structures of the alpha,omega-dicarboxylic acid strongly implies that the synthetic mechanism for formation is by tail-to-tail (omega)coupling of regular iso-branched fatty acids across opposite sides of the membrane.