Relative Quantification of Phospholipids Based on Isotope-Labeled Methylation by Nanoflow Ultrahigh Performance Liquid Chromatography-Tandem Mass Spectrometry: Enhancement in Cardiolipin Profiling. 2017

Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
Department of Chemistry, Yonsei University , 50 Yonsei-ro, Seodaemun-gu, Seoul 03722, Korea.

In this study, lipid analysis based on isotope-labeled methlylation (ILM) was performed by nanoflow ultrahigh performance liquid chromatography-eletrospray ionization-tandem mass spectrometry (nUPLC-ESI-MS/MS) for enhanced detection and quantification of targeted phospholipids. ILM depends on methylation of phosphate groups by (trimethylsilyl)diazomethane, and the ILM based quantitation with reversed phase nUPLC-ESI-MS/MS provides advantages in PL profiling such as enhanced detectability of methylated PLs owing to increased hydrophobicity and substantial increase in resolution due to the increase of retention. Efficacy of ILM in nUPLC-ESI-MS/MS analysis was evaluated in the selected reaction monitoring (SRM) method by varying the mixing ratio of H-/D-methylated PL standards, which resulted in the successful quantification of 24 species, including phosphatidic acid (PA), phosphatidylserine (PS), phosphatidylglycerol (PG), ceramide-1-phosphate (Cer1P), phosphoinositides, and cardiolipin (CL), with ∼6.6% variation in the calculated ratio of H-/D-methylated PLs. The method was applied to the lipid extracts from a DU145 cell line after D-allose treatment, resulting in the quantification of 83 PLs of which results were not statistically different from those obtained by conventional quantification methods. Morever, detection and quantification of CLs and PAs were evidenced to be highly effective when used with the ILM method as 43 CLs and 20 PAs from cellular lipid extracts were analyzed while only 18 CLs and 12 PAs were identified when conventional methods were carried out. This proves the ILM combined with LC-MS to be a promising method for analysis of the aforementioned classes of lipids. Overall, the study highlighted the applicability of targeted quantification by the ILM method in lipidomic analysis and demonstrated an improvement in the detection of less abundant anionic PLs.

UI MeSH Term Description Entries
D008745 Methylation Addition of methyl groups. In histo-chemistry methylation is used to esterify carboxyl groups and remove sulfate groups by treating tissue sections with hot methanol in the presence of hydrochloric acid. (From Stedman, 25th ed) Methylations
D010743 Phospholipids Lipids containing one or more phosphate groups, particularly those derived from either glycerol (phosphoglycerides see GLYCEROPHOSPHOLIPIDS) or sphingosine (SPHINGOLIPIDS). They are polar lipids that are of great importance for the structure and function of cell membranes and are the most abundant of membrane lipids, although not stored in large amounts in the system. Phosphatides,Phospholipid
D002851 Chromatography, High Pressure Liquid Liquid chromatographic techniques which feature high inlet pressures, high sensitivity, and high speed. Chromatography, High Performance Liquid,Chromatography, High Speed Liquid,Chromatography, Liquid, High Pressure,HPLC,High Performance Liquid Chromatography,High-Performance Liquid Chromatography,UPLC,Ultra Performance Liquid Chromatography,Chromatography, High-Performance Liquid,High-Performance Liquid Chromatographies,Liquid Chromatography, High-Performance
D003903 Deuterium The stable isotope of hydrogen. It has one neutron and one proton in the nucleus. Deuterons,Hydrogen-2,Hydrogen 2
D003978 Diazomethane A diazonium compound with the formula CH2N2. Diazirine
D006801 Humans Members of the species Homo sapiens. Homo sapiens,Man (Taxonomy),Human,Man, Modern,Modern Man
D014297 Trimethylsilyl Compounds Organic silicon derivatives used to characterize hydroxysteroids, nucleosides, and related compounds. Trimethylsilyl esters of amino acids are used in peptide synthesis. Compounds, Trimethylsilyl
D045744 Cell Line, Tumor A cell line derived from cultured tumor cells. Tumor Cell Line,Cell Lines, Tumor,Line, Tumor Cell,Lines, Tumor Cell,Tumor Cell Lines
D053719 Tandem Mass Spectrometry A mass spectrometry technique using two (MS/MS) or more mass analyzers. With two in tandem, the precursor ions are mass-selected by a first mass analyzer, and focused into a collision region where they are then fragmented into product ions which are then characterized by a second mass analyzer. A variety of techniques are used to separate the compounds, ionize them, and introduce them to the first mass analyzer. For example, for in GC-MS/MS, GAS CHROMATOGRAPHY-MASS SPECTROMETRY is involved in separating relatively small compounds by GAS CHROMATOGRAPHY prior to injecting them into an ionization chamber for the mass selection. Mass Spectrometry-Mass Spectrometry,Mass Spectrometry Mass Spectrometry,Mass Spectrometry, Tandem
D056148 Chromatography, Reverse-Phase A chromatography technique in which the stationary phase is composed of a non-polar substance with a polar mobile phase, in contrast to normal-phase chromatography in which the stationary phase is a polar substance with a non-polar mobile phase. Chromatography, Reversed-Phase Liquid,Reversed-Phase Chromatography,Reversed-Phase Liquid Chromatography,Reverse-Phase Chromatography,Reverse-Phase Liquid Chromatography,Chromatography, Reverse Phase,Chromatography, Reversed-Phase,Reverse Phase Chromatography,Reversed Phase Chromatography

Related Publications

Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
December 2008, The Analyst,
Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
June 2021, Analytica chimica acta,
Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
July 2011, Analytical and bioanalytical chemistry,
Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
August 2011, Analytical and bioanalytical chemistry,
Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
February 2022, Analytica chimica acta,
Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
May 2024, Rapid communications in mass spectrometry : RCM,
Jong Cheol Lee, and Seul Kee Byeon, and Myeong Hee Moon
April 2014, Journal of agricultural and food chemistry,
Copied contents to your clipboard!