Lipids mass spectrometric analysis

Basile,F. Beverly,M. B. Abbas-Hawks,C. Mowry,C. D. Voorhees,K. J. FIadfield, T. L. Direct mass spectrometric analysis of in situ thermally hydrolyzed and methylated lipids from whole bacterial cells. Anal. Chem. 1998, 70,1555-1562. 

Harrison KA, Murphy RC. 1996. Direct mass spectrometric analysis of ozonides application to unsaturated glycero-phosphocholine lipids. Anal Chem 68 3224. 

Patterson DG Jr, Hampton L, Lapeza Cr Jr, et al. 1987a. High-resolution gas chromatographic/high-resolution mass spectrometric analysis of human serum on a whole-weight and lipid basis for... 

Today, mass spectrometry has become one of the most widely used analytical techniques in the life sciences [11,12], The mass spectrometric analysis of different classes of biomolecules is reviewed in this chapter peptides, proteins, nucleic acids, oligosaccharides and lipids. Several applications are detailed for each class. Metabolomics, which is the omics science of metabolism, will also be examined at the end of the chapter. 

In many cases, sample preparation is mandatory prior to lipid extraction. This crucial process might include tissue homogenization, determination of dry weights, cell numbers, protein content, or DNA content for normalization purposes. The addition of internal standards is not only used to control extraction efficiency, but also is required for lipid quantification by mass spectrometric analysis, in which an ion current is translated into a lipid concentration. Many standard lipids that can be distinguished from endogenously occurring lipids by using rare... 

The determination of the sites of the C—C double bonds in unsaturated fatty acid derivatives and other lipids plays an outstanding role in the analytical application of mass spectrometry. Much work has been published on the localization of double bonds in monoolefins, and a number of extensive reviews has appeared on the topic . Two major methodologies have been employed. In the first one, unsaturated C—C bonds are converted to appropriate derivatives by synthesis in the liquid phase, which are then subjected to mass spectrometric analysis mostly by using standard El techniques. These methods will be mentioned only briefly in the next section, including some recent work which has not yet been mentioned in the reviews. The second methodology takes advantage of the bimolecular reactivity of neutral olefins with ionic reagents in the gas phase,... 

Fig. 3. Chemical and enzymatic treatment to reduce the size and complexity of the GPI anchor for mass spectrometric analysis. PIPLC removed the acylalkylglycerol lipids, then endoproteinase Lys C cut the amino acid chain after Lys220, giving the C-terminal peptide attached to the phosphorylated glycan. Incubation with 50% aqueous HF was used to hydrolyze the phosphodiester bonds and to release the glycan and the peptide, which were separated by RP-HPLC and analyzed independently.

For example, the yeast Pityrosporum ovale, the major scalp resident, is able to metabolize lipid substrates to 4-hydroxy-aclds which readily undergo ring closure to the volatile and odorous Y lactones. The technique of headspace concentration on Tenax followed by gas chromatographic/mass spectrometric analysis has been used to profile all the volatiles produced by Pityrosporum (Figure 1). These compounds Include isopentanol, benzyl... 

The preparation of samples for mass spectrometric analysis almost always requires recovery of the analyte from a matrix, often followed by further preparative steps prior to introduction of the sample into the ion source. Such destructive processes are unacceptable when the objective is to determine the specific location of a particular compound within a biological sample, e.g., the location of a certain lipid in a tissue, and led to the development of imaging mass spectrometry with MALDI as the ionization method, although DESI is also applicable. 

Pike, L. J., X. Han, K. N. Chung, and R. W. Gross. 2002. Lipid rafts are enriched in ara-chidonic acid and plasmenylethanolamine and their composition is independent of caveohn-l expression A quantitative electrospray ionization/mass spectrometric analysis, 41 2075-88. 

Laakso, P. and Kallio, H. (1996) Optimization of the mass spectrometric analysis of triacylglycerols using negative ion chemical ionisation with ammonia. Lipids, 31, 33-42. 

The use of SPH strategy to enrich carbonylated species prior to mass spectrometric analysis is advantageous compared with direct immunoaffinity approaches. While the SPH method has the potential to enrich carbonylated peptides modified by a wide array of lipid peroxidation end products such as MDA, HNE, HHE, and acrolein, for example, an immunoaffinity approach requires separate antibodies against each kind of carbonyl adducts. Derivatization of peptide carbonyls with, for example, 2,4-dinitrophenylhydrazine (DNPH), and then, performing immunoaffinity-based enrichment with immobilized antidinitrophenyl antibodies, may preclude the need for separate antibodies [27]. However, these derivatives may form at low yields and, in addition, according to our experience, they tend to detach the DNPH tags with each processing step because of their instability. 

ARCHAEOMETRIC DATA FROM MASS SPECTROMETRIC ANALYSIS OF ORGANIC MATERIALS PROTEINS, LIPIDS, TERPENOID RESINS, LIGNOCELLULOSIC POLYMERS, AND DYESTUFF... 

Mass Spectrometric Analysis of Deuterium Dual Labeled Blood Lipids Biomed. Mass Spectrom. 6(2) 67-71 (1979) CA 91 104679y... 

Fredrickson HL, De Leeuw JW, Tas AC, Van der Greef J, La Vos GF, Boon JJ. Fast atom bombardment (tandem) mass spectrometric analysis of intact polar ether lipids extractable from the extremely halophilic archaebacterium/fafoiactenww cutivubrum. Biomed Environ Mass Speetrom. 1989 18 96-105. 

Kahlke and Richterich 1965) and plasma lipids of Refsum s (1946) case T. E. (Kahlke 1964 a). Methods and results were identical in both instances although a nuclear resonance spectrum was obtained only in the first case and a complete mass spectrometric analysis only in the second case. Phytanic acid was isolated by preparative gas-liquid chromatography from a mixture of fatty acid methyl esters. Traces of stearic acid were removed as the urea inclusion compound by treatment with a saturated methanolic solution of urea (Cason et al. 1953). After repeated crystallization from acetone at minus 70—80 C and drying under vacuum at minus 10 C, phytanic acid was obtained as a white crystalline powder with a melting point of minus 7—6 C. At room temperature phytanic acid is a colorless, odorless oil. The lack of hydrogen uptake with exhaustive... 

Figure 4.2 Representative positive- and negative-ion ESI mass spectra acquired under weak acidic, neutral, and weak basic conditions. A lipid extract of mouse spinal cord at 48 days was prepared and mass spectrometric analysis was performed [26]. Positive- and negative-ion ESI mass spectra as indicated were acquired after direct infusion in the presence of 0.5% acetic acid (a and b), 5 mM ammonium acetate (c and d), and 10 pM lithium hydroxide (e and f) in the infused solution. IS, pPE, and ST stand for internal standard, plasmenylethanolamine, and sulfatide, respectively.

Murphy, R.C. and Axelsen, P.H. (2011) Mass spectrometric analysis of long-chain lipids. Mass Spectrom. Rev. 30, 579-599. 

As the development of lipidomics field, mass spectrometric analysis of plant lipids has been advanced accordingly. The branch of lipidomics in analysis of plant cellular lipids utilizing mass spectrometry was specifically called plant lipidomics [1], As described early in the book (Chapter 3), all kinds of MS-based lipidomics approaches, particularly those based on ESl-MS or ESI-MS/MS, could be used in plant lipidomics. The advantages of ESl-MS-based methods over traditional lipid analytical approaches for analysis of plant lipids were extensively discussed [1-3]. 

Specific polyketide hpids present in M. tuberculosis interact with the host and are required for virulence. Mass spectrometric analysis was conducted to monitor this type of lipids [53]. It was discovered that the size and abundance of two lipid virulence factors, phthiocerol dimycocerosate and sulfolipid-1, were controlled by the availability of a common precursor, methyl malonyl CoA. These results suggested that growth of M. tuberculosis on fatty acids during infection led to increased flux of methyl malonyl CoA through lipid biosynthetic pathways, resulting in increased virulence lipid synthesis. 

Although several technologies have been used in lipidomics to identify, quantify, and understand the structure and function of lipids in biological systems, it is clear that the progress of lipidomics has been accelerated by the development of modern mass spectrometry (e.g., electrospray ionization (ESI) and matrix-assisted laser desorption/ionization). Mass spectrometric analysis of lipids plays a key role in the discipline. Therefore, this book is focused on the mass spectrometry of lipids that has occurred in these years. Other technologies for analysis of lipids, particularly those with chromatography, can be found in the book entitled Lipid Analysis Isolation, Separation, Identification and Lipidomic Analysis written by Drs William W. Christie and Xianlin Han. Readers who are interested in classical techniques and applications of mass spectrometry for analysis of lipids should refer to Dr Robert C. Murphy s book entitled Mass Spectrometry of Lipids. 

Figure 20.9. Two-dimensional mass spectrometric analysis of GPIns molecular species in a lipid extract of mouse myocardium. The lipid extract of mouse myocardium was prepared by a modified Bligh and Dyer procedure as previously described. Each MS or MS/MS trace of the 2D ESI mass spectrum was acquired by sequentially programmed, customized scans operating under Xcalibur software. For negative-ion tandem mass spectrometry in the precursor-ion (PI) mode, the first quadrupole was scanned in the selected mass range and the second quadrupole was used as a coUision cell while the third quadrupole was fixed to monitor the ion of interest (i.e., either inositol phosphate, glycerophosphate, or a fatty acyl carboxylate fragmented from GPIns molecular species). All mass spectral traces were displayed after being normalized to the base peak in each individual trace.

R. Marsili, Comparison of solid-phase microextraction and dynamic headspace methods for the gas chromatographic-mass spectrometric analysis of light-induced lipid oxidation products in milk, J. Chrom. Sci. 37 17-23 (1999). 

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