Fauconnot Laëtitia, Robert Fabien, Villard Renaud, Dionisi Fabiola
Nestlé Research Center, Nestec Ltd., Vers-chez-les-Blanc, P.O. Box 44, CH-1000 Lausanne 26, Switzerland.
Chem Phys Lipids. 2006 Feb;139(2):125-36. doi: 10.1016/j.chemphyslip.2005.11.004. Epub 2005 Dec 22.
The chemical synthesis of pure triacylglycerol (TAG) regioisomers, that contain long chain polyunsaturated fatty acids, such as arachidonic acid (AA) or docosahexaenoic acid (DHA), and saturated fatty acids, such as lauric acid (La) or palmitic acid (P), at defined positions, is described. A single step methodology using (benzotriazol-1-yloxy)-tripyrrolidinophosphonium hexafluorophosphate (PyBOP), an activator of carboxyl group commonly used in peptide synthesis and occasionally used in carboxylic acid esterification, has been developed for structured TAG synthesis. Identification of the fatty acyl chains for each TAG species was confirmed by atmospheric pressure chemical ionisation mass spectrometry (APCI-MS) and fatty acid positional distribution was determined by (1)H and (13)C NMR spectra. The generic described procedures can be applied to a large variety of substrates and was used for the production of specific triacylglycerols of defined molecular structures, with high regioisomeric purity. Combination of MS and NMR was shown to be an efficient tool for structural analysis of TAG. In particular, some NMR signals were demonstrated to be regioisomer specific, allowing rapid positional analysis of LC-PUFA containing TAG.
本文描述了纯三酰甘油（TAG）区域异构体的化学合成方法，这些异构体在特定位置含有长链多不饱和脂肪酸，如花生四烯酸（AA）或二十二碳六烯酸（DHA），以及饱和脂肪酸，如月桂酸（La）或棕榈酸（P）。已开发出一种单步方法，使用（苯并三唑-1-基氧基）-三吡咯烷基鏻六氟磷酸盐（PyBOP），这是一种常用于肽合成且偶尔用于羧酸酯化的羧基活化剂，用于合成结构化TAG。通过大气压化学电离质谱（APCI-MS）确认了每种TAG物种的脂肪酰基链，并通过（1）H和（13）C NMR光谱确定了脂肪酸的位置分布。所描述的通用程序可应用于多种底物，并用于生产具有特定分子结构、高区域异构体纯度的特定三酰甘油。结果表明，MS和NMR的结合是TAG结构分析的有效工具。特别是，一些NMR信号被证明具有区域异构体特异性，可实现对含LC-PUFA的TAG的快速位置分析。
