Sphingolipids mass spectrometry

Bartke, N., Fischbeck, A., Humpf, H. U. (2006). Analysis of sphingolipids in potatoes Solanum tuberosum L.) and sweet potatoes Ipomoea batatas (L.) Lam.) by reversed phase high-performance liquid chromatography electrospray ionization tandem mass spectrometry (HPLC-ESl-MS/MS). Mol. Nutr. Food Res., 50,1201-1211. 

H. Egge Structural analysis of blood group ABH, I, i, Lewis and related glyco-sphingolipids. Application of high resolution NMR and FAB mass spectrometry... 

T. Fujiwaki, M. Tasaka, N. Takahashi, H. Kobayashi, Y. Murakami, T. Shimada, and S. Yamaguchi, Quantitative evaluation of sphingolipids using delayed extraction matrix-assisted laser desorption ionization time-of-flight mass spectrometry with sphingosylphosphorylcholine as an internal standard. Practical application to cardiac valves from a patient with Fabry disease, J. Chromatogr. B. 832 (2006) 97-102. 

Lipids are made up of many classes of very different molecules that all show solubility properties in organic solvents. Mass spectrometry plays a key role in the biochemistry of lipids. Indeed, mass spectrometry allows not only the detection and determination of the structure of these molecules but also their quantification. For practical reasons, only the fatty acids, acylglycerols and bile acids are discussed here, although other types of lipids such as phospholipids, [253-256] steroids, [257-259] prostaglandins, [260] ceramides, [261,262] sphingolipids [263,264] and leukotrienes [265,266] have been analysed successfully by mass spectrometry. Moreover, the described methods will be limited to those that are based only on mass spectrometry, even if the majority of these methods generally are coupled directly or indirectly with separation techniques such as GC or HPLC. A book on the mass spectrometry of lipids was published in 1993. [267]... 

Mano, N., Oda, Y. and Yamada, K. (1997) Simultaneous quantitative determination method for sphingolipid metabolites by liquid chromatography/ionspray ionization tandem mass spectrometry. Anal. Biochem., 244 (2), 291-300. 

Bielawski, J., Szulc, Z. M., Hannun, Y. A., Bielawska, A. Simultaneous quantitative analysis of bioactive sphingolipids by high-performance liquid chromatography-tandem mass spectrometry. Methods 39 (2006) 82-91. 

Merrill AH, Jr., Sullards MC, Allegood JC, Kelly S, Wang E. Sphingolipidomics high-throughput, structure-specific, and quantitative analysis of sphingolipids by liquid chromatography tandem mass spectrometry. Methods 36(2005) 207-224. 

Colsch et al., 2007). Because the diagnosis may be complicated in cases of arylsulfatase A pseudodeficiency and sphingolipid activator protein deficiency, this measurement of sulfatide in the urinary sediment of affected individuals by a rapid, sensitive, and specific mass spectrometric method has been long wanted (Whitfield et al., 2001). Urinary sulfatides are now commonly detected using electrospray ionization-tandem mass spectrometry by means of the precursor ion scan 97. Levels are considerably increased to X20-30 folds as compared to controls which allows the rapid screening of a large number of samples. 

On a practical level, the sphingolipid field is caught somewhat awkwardly between old and new nomenclatures due to differences in the information that one gets from traditional analytical methods such as radiolabeling followed by thin-layer chromatography versus more structure-specific methods such as mass spectrometry (MS). 

Fig. 13. Major fragmentation sites of sphingolipids that are useful for analysis by electrospray tandem mass spectrometry [6].

The analysis and identification of sphingolipids have recently been substantially improved by the use of gas-liquid chromatography, fast-atom bombardment mass spectrometry, nuclear magnetic resonance spectroscopy and selective enzymatic cleavage. Despite these efforts, however, many important members of this class of biomolecules remain relatively inaccessible. Isolation of pure compounds is still difficult because of the diversity and heterogeneity of lipids. Effective synthetic routes to these compounds are, therefore, extremely important to investigate their chemical and biological properties. 

Fang, R, Ho, C.-T., Sang, S., and Rosen, R.T., Determination of sphingolipids in nuts and seeds by a single quadrupole liquid chromatography-mass spectrometry method, J. Food Lipids, 12, 327-343, 2005. 

One of the most powerful techniques used in Upid analysis today is HPLC coupled with mass spectrometry (HPLC/MS). Several mass spectrometric ionization techniques, such as fast atom bombardment (FAB) [23], electrospray ionization (ESI) [29,30], ionspray ionization (ISI) [31], and atmospheric pressure chemical ionization (APCI) [22,30,32] have been used. By using HPLC/MS, one can get information on the molecular structure of the intact lipids, which helps differentiate molecular species within different lipid classes. By using tandem mass spectrometry (MS/MS), identification of molecular species of different sphingolipids can be achieved in an easier and more sensitive way. There are many other advantages of using MS, such as small sample size, minimal sample preparation, and lack of need for derivatization, speeds, and sensitivity. In the literature, sphingolipids of both animal and plant origin were analyzed by MS. 

Thus, the ions of m/z 421 and 720 in the negative ion mode are found to be very useful for the structural determination of glycosyl phosphosphingolipids (phosphodihexose-sphingolipids) in the analyses by FAB mass spectrometry, because these ion peaks are characteristic of a phosphodihexose and a phytosphingosine (4-hydroxy-Ci -sphinganine) containing phosphodihexose, respectively. 

In recent years, HPLC coupled with ESI-MS has become a well-established method for the identification and detection of chemical stmctures of lipids, including sphingolipids. Recently, Sugawara and coworkers [44] identified the chemical structures of glucosylceramides from maize, rice, mushroom, and sea cucumber by liquid chromatography-ion trap mass spectrometry with an ESI interface. In the positive full-scan mode, [M-t-HJ" ", [M-l-H—H2O ] , or [M-l-H—162]" (loss of glucose) was used for MS/MS analysis to obtain the product ions, which were used for the identification of the glucocerebrosides. 

Adams, J. and Ann, Q. (1993) Structure determination of sphingolipids by mass spectrometry. 

Seng, J.A., Ellis, S.R., Hughes, J.R., Maccarone, A.T., Truscott, R.J., Blanksby, S.J., and Mitchell, T.W. 2014. Characterisation of sphingolipids in the human lens by thin layer chromatography-desorption electrospray ionisation mass spectrometry, Biochim. Biophys. Acta, 1841 1285-1291. 

The Estimation of Sphingolipids by Gas Chromatography-Chemical Ionization Mass Spectrometry of Their Derived Aldehydes with Particular Reference to the Ceramides of Children s Plasma... 

Key words Imaging MALDI mass spectrometry, sphingolipids, oscillating capillary nebulizer,... 

Imaging MALDI Mass Spectrometry of Sphingolipids Using an... 

Manicke, N.E., Wiseman, J.M., Ifa, D.R. and Cooks, R.G. (2008) Desorption electrospray ionization (DESI) mass spectrometry and tandem mass spectrometry (MS/MS) of phosphohpids and sphingolipids Ionization, addnct formation, and fragmentation. J. Am. Soc. Mass Spectrom. 19, 531-543. 

Ejsing, C.S., Moehring, T., Bahr, U., Duchoslav, E., Karas, M., Simons, K. and Shevchenko, A. (2006) Collision-induced dissociation pathways of yeast sphingolipids and their molecular profiling in total lipid extracts A study by quadrupole TOP and linear ion trap-orbitrap mass spectrometry. J. Mass Spectrom. 41, 372-389. 

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