Cholesteryl nitrolinoleate, a nitrated lipid present in human blood plasma and lipoproteins

被引:59
作者
Lima, ES
Di Mascio, P
Abdalla, DSP [1 ]
机构
[1] Univ Sao Paulo, Fac Ciencias Farmaceut, Dept Anal Clin & Toxicol, Sao Paulo, Brazil
[2] Univ Sao Paulo, Inst Quim, Dept Bioquim, BR-01498 Sao Paulo, Brazil
关键词
nitration; cholesteryl linoleate; lipoproteins; mass spectrometry;
D O I
10.1194/jlr.M200467-JLR200
中图分类号
Q5 [生物化学]; Q7 [分子生物学];
学科分类号
071010 ; 081704 ;
摘要
Nitric oxide ((NO)-N-.) and (NO)-N-.-derived reactive species (e.g., peroxynitrite anion, nitrogen dioxide radical) react with lipids containing unsaturated fatty acids to generate nitrated species. In the present work, we synthesized, characterized, and detected a nitrated derivative of cholesteryl linoleate (Ch18:2) in human blood plasma and lipoproteins using a high-pressure liquid chromatography coupled to electrospray ionization tandem mass spectrometry method. It was synthesized by a reaction of Ch18:2 with nitronium. tetrafluoroborate, yielding a species with m/z 711, which is characteristic of the cholesteryl nitrolinoleate (Ch18:2NO(2)) ammonium adduct. The presence of the nitro group was confirmed by using [N-15]nitrite, which gave a product with MA 712, with the same chromatographic and spectrometric characteristics of those of m/z 711. Furthermore, a C-NO2 structure was also demonstrated in Ch18:2NO(2) by infrared analysis (V-max 1549, 1374 cm(-1)). A stable product with m/z of 711, showing the same chromatographic characteristics and fragmentation pattern as those of synthesized standard, was found in human blood plasma and lipoproteins of normolipidemic subjects. The presence of this novel nitrogen-containing lipid product in human plasma and lipoproteins could represent a potential indicator of the oxidative/nitrative roles that (NO)-N-. or its metabolites play during in vivo lipid oxidation, generating a compensatory mechanism of protection in vascular disease.
引用
收藏
页码:1660 / 1666
页数:7
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