Phospholipid composition of human blood plasma as detected by matrix-assisted laser desorption/ionization mass spectrometry: new observations

T14N2

B.L. Milman, N.V. Lugovkina, I.K. Zhurkovich

The dependence of matrix-assisted laser desorption/ionization (MALDI) mass spectra of lipids extracted from human blood plasma and corresponding lipid compositions on different experimental conditions was studied. Not only numerous compounds from groups of lysophosphatidylcholines (LPC) and phosphatidylcholines (PC) but also lipid oxidation products including six oxidized LPC, were detected. They were available in the original samples and also produced by the reaction with air oxygen molecules resulted in their accumulation in samples under analysis. A higher sensitivity of MALDI detection was observed for less hydrophobic LPC as compared to more hydrophobic PC and was explained. The hydrophobicity/lipophilicity factor was possibly revealed when the matrix of 2,5-dihydroxybenzoic acid has been replaced by α-cyano-4-hydroxycinnamic acid. The latter was rarely used in MALDI of lipids and may be suitable for the selective determination of LPC and oxidized LPC.

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Determination of methylphosphonic acid in human blood plasma by high-performance liquid chromatography tandem mass spectrometry

T13N4

T.M. Baygildiev, I.A. Rodin, A.N. Stavrianidi, A.V. Braun, O.A. Shpigun, I.V. Rybalchenko

 Using high performance liquid chromatography combined with tandem mass spectrometric detection, an approach for the determination of the most stable nerve agent biomarker, methylphosphonic acid, in human blood plasma has been developed. The proposed method is based on the derivatization reaction of methylphosphonic acid with p-bromophenacyl bromide. Optimization of conditions for human plasma sample preparation, mass spectrometric detection conditiones and gradient elution program has been performed. The proposed approach has demonstrated satisfactory reproducibility and selectivity of the determination, limit of detection for methylphosphonic acid in human plasma was 3 ng ml−1.

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Comparative determination of fatty acid composition of low-molecular components of blood plasma by three mass spectrometry techniques: the ‘old-new’ exercise in lipidomics

T12N2

B.L. Milman, V.A. Utsal′, N.V. Lugovkina, I.A. Kotryakhov,  I.K. Zhurkovich

Fatty acid composition of lipid low-molecular components of human blood plasma was determined by the combination of analytical techniques, such as gas chromatography/mass spectrometry and high-resolution electrospray MS1 and MS2 with direct flow injection. More than two tens of fatty acid methyl esters were identified in lipid extracts subjected to methanolysis. Direct injection electrospray MS led to recognition of 21 lysophosphatidylcholines and 25 phosphatidylcholine sum compositions. Fatty acid distributions over analytical signal intensities in groups of methyl esters and lysophosphatidylcholines were demonstrated to be similar to each other and highly correlated. The fatty acid distribution for phosphatidylcholine was correlated to those to a lesser extent. At the same time, the analytical signal intensities of lysophosphatidylcholines and phosphatidylcholine was observed to be highly correlated to concentrations of these lipid compounds in blood plasma determined by the similar technique of direct injection MS and available in the literature.

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Выявление дифференциальных признаков плоскоклеточного рака легкого

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