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* Departamento de Análises Clínicas e Toxicológicas, Instituto de Química, Universidade de São Paulo, São Paulo, SP, Brazil
Faculdade de Ciências Farmacêuticas, and Departamento de Bioquímica, Instituto de Química, Universidade de São Paulo, São Paulo, SP, Brazil
1 To whom correspondence should be addressed. e-mail: dspa{at}usp.br
Nitric oxide (NO) and NO-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 (Ch18:2NO2) ammonium adduct. The presence of the nitro group was confirmed by using [15N]nitrite, which gave a product with m/z 712, with the same chromatographic and spectrometric characteristics of those of m/z 711. Furthermore, a C-NO2 structure was also demonstrated in Ch18:2NO2 by infrared analysis (Vmax 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 or its metabolites play during in vivo lipid oxidation, generating a compensatory mechanism of protection in vascular disease.
Abbreviations: Ch18:2, cholesteryl linoleate (cholesteryl 9,12-octadecadienoate); Ch18:2NO2, cholesteryl nitrolinoleate; [3H]-Ch18:2, [1
,2
(n)-3H]cholesteryl linoleate; IR, infrared; LC-ESI/MS/MS, liquid chromatography/electrospray ionization tandem mass spectrometry; LONO, nitritelinoleate; LONO2, nitratelinoleate; NO2, nitrogen dioxide radical
Supplementary key words nitration cholesteryl linoleate lipoproteins mass spectrometry
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