Arnhold J, Osipov Anatoly N, Spalteholz H, Panasenko Oleg M, Schiller J
Institute of Medical Physics and Biophysics, Medical Department, University of Leipzig, Liebigstr. 27, D-04103 Leipzig, Germany.
Biochim Biophys Acta. 2002 Aug 15;1572(1):91-100. doi: 10.1016/s0304-4165(02)00271-4.
The formation of lysophosphatidylcholines from unsaturated phosphatidylcholines upon treatment with hypochlorous acid was evaluated by means of MALDI-TOF mass spectrometry and 31P NMR spectroscopy. With an increasing number of double bonds in a fatty acid residue, the yield of lysophosphatidylcholines with a saturated fatty acid residue increased considerably in comparison to the total amount of higher molecular weight products like chlorohydrins and glycols. High amounts of lysophosphatidylcholines were formed from phospholipids containing arachidonic or docosahexaenoic acid residues. In phospholipids with monounsaturated fatty acid residues, the position of the double bond did not influence the yield of lyso-products. Besides the exclusive formation of chlorohydrin and glycol, hypochlorous acid caused the cleavage of the unsaturated fatty acid residue independent of its location at the first or second position of the glycerol backbone. In contrast, strong alkaline conditions, i.e. saponification led also to a hydrolysis of the saturated fatty acid residue from phosphatidylcholines. It is concluded that both MALDI-TOF mass spectrometry and 31P NMR spectroscopy are able to detect the formation of lysophosphatidylcholines. We conclude also that the formation of lysophospholipids from unsaturated phosphatidylcholines by hypochlorous acid can be relevant in vivo under acute inflammatory conditions.
通过基质辅助激光解吸电离飞行时间质谱（MALDI - TOF质谱）和³¹P核磁共振光谱（³¹P NMR光谱）评估了用次氯酸处理不饱和磷脂酰胆碱时溶血磷脂酰胆碱的形成情况。随着脂肪酸残基中双键数量的增加，与氯醇和二醇等高分子量产物的总量相比，具有饱和脂肪酸残基的溶血磷脂酰胆碱的产量显著增加。由含有花生四烯酸或二十二碳六烯酸残基的磷脂形成了大量的溶血磷脂酰胆碱。在具有单不饱和脂肪酸残基的磷脂中，双键的位置不影响溶血产物的产量。除了仅形成氯醇和二醇外，次氯酸还会导致不饱和脂肪酸残基的裂解，而与其在甘油主链的第一位或第二位的位置无关。相比之下，强碱性条件，即皂化也会导致磷脂酰胆碱中饱和脂肪酸残基的水解。得出的结论是，MALDI - TOF质谱和³¹P NMR光谱都能够检测溶血磷脂酰胆碱的形成。我们还得出结论，在急性炎症条件下，次氯酸从不饱和磷脂酰胆碱形成溶血磷脂在体内可能具有相关性。
