Abstract
The application of mass spectrometry towards the structural analysis of the most interesting sulfated biopolymers of the brown algae—fucoidans only developed relatively recently. During method development, many problems, both chemical and instrumental, have to be solved. For example, mass spectrometry has a limitation in the analysis of anionic high molecular weight (HMW) polysaccharides because of the labile nature of sulfate groups which cause the polysaccharide to desulfate rather than ionize. Thus, decomposition methods should be developed taking into account the structural features of such a complex and fragile compound. The selection of optimal instrument settings for the electrospray ionization mass spectrometry (ESIMS) and of matrix media for matrix-assisted laser desorption/ionization mass spectrometry (MALDIMS) is also required. When optimal parameters for mass spectrometric analyses are found, the application of these methods to the elucidation of structural features of fucoidans (by studying their fragments) allows researchers to rapidly obtain new and unique data, often impossible to achieve by other techniques. Herein, we describe tandem mass spectrometry of sulfated fucooligosaccharides, obtained by an autohydrolysis technique from structurally different fucoidans.
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Aleksandrov ML, Gall LN, Krasnov NV et al (1984) Mechanism of ion formation during the electrohydrodynamic sputtering of a liquid into a vacuum. J Anal Chem USSR 39:1268–1274
Yamashita M, Fenn JB (1984) Electrospray ion source. Another variation of the free-jet theme. J Phys Chem 88:4451–4459
Hillenkamp F, Karas M (1990) Mass-spectrometry of peptides and proteins by matrix-assisted ultraviolet-laser desorption ionization. Meth Enzymol 193:280–295
Karas M, Hillenkamp F (1988) Laser desorption ionization of proteins with molecular masses exceeding 10000 daltons. Anal Chem 60:2299–2301
Harvey DJ (1999) Matrix-assisted laser desorption/ionization mass spectrometry of carbohydrates. Mass Spectrom Rev 18:349–450
Zaia J (2004) Mass spectrometry of oligosaccharides. Mass Spectrom Rev 23:161–227
Kusaykin M, Bakunina I, Sova V et al (2008) Structure, biological activity, and enzymatic transformation of fucoidans from the brown seaweeds. Biotechnol J 3:904–915
Cumashi A, Ushakova NA, Preobrazhenskaya ME et al (2007) A comparative study of the anti-inflammatory, anti-coagulant, anti-angiogenic, and anti-adhesive activities of nine different fucoidans from brown seaweeds. Glycobiol 17:541–552
Bilan MI, Usov AI (2008) Structural analysis of fucoidans. Nat Prod Comms 3:1639–1648
Shevchenko NM, Anastyuk SD, Gerasimenko NI et al (2007) Polysaccharide and lipid composition of the brown seaweed Laminaria gurjanovae. Bioorg Khim 33:96–107
Shevchenko N, Anastyuk S, Menshova R et al (2015) Further studies on structure of fucoidan from brown alga Saccharina gurjanovae. Carbohydr Polym 121:207–216
Daniel R, Chevolot L, Carrascal M et al (2007) Electrospray ionization mass spectrometry of oligosaccharides derived from fucoidan of Ascophyllum nodosum. Carbohydr Res 342:826–834
Marais M-F, Joseleau J-P (2001) A fucoidan fraction from Ascophyllum nodosum. Carbohydr Res 336:155–159
Tissot B, Salpin JY, Martinez M et al (2006) Differentiation of the fucoidan sulfated L-fucose isomers constituents by CE-ESIMS and molecular modeling. Carbohydr Res 341:598–609
Karlsson NG, Karlsson H, Hansson GC (1996) Sulphated mucin oligosaccharides from porcine small intestine analysed by four-sector tandem mass spectrometry. J Mass Spectrom 31:560–572
Minamisawa T, Hirabayashi J (2005) Fragmentations of isomeric sulfated monosaccharides using electrospray ion trap mass spectrometry. Rapid Commun Mass Spectrom 19:1788–1796
Saad OM, Leary JA (2004) Delineating mechanisms of dissociation for isomeric heparin disaccharides using isotope labeling and ion trap tandem mass spectrometry. J Am Soc Mass Spectrom 15:1274–1286
Desaire H, Leary JA (2000) Utilization of MS3 spectra for the multicomponent quantification of diastereomeric N-acetylhexosamines. J Am Soc Mass Spectrom 11:1086–1094
Domon B, Costello CE (1988) A systematic nomenclature for carbohydrate fragmentations in Fab-MsMs spectra of glycoconjugates. Glycoconjugate J 5:397–409
Zaia J, Miller MJ, Seymour JL et al (2007) The role of mobile protons in negative ion CID of oligosaccharides. J Am Soc Mass Spectrom 18:952–960
Anastyuk SD, Shevchenko NM, Nazarenko EL et al (2009) Structural analysis of a fucoidan from the brown alga Fucus evanescens by MALDI-TOF and tandem ESI mass spectrometry. Carbohydr Res 344:779–787
Bilan MI, Grachev AA, Ustuzhanina NE et al (2002) Structure of a fucoidan from the brown seaweed Fucus evanescens C. Ag. Carbohydr Res 337:719–730
Ciancia M, Matulewicz MC, Stortz CA et al (1991) Room-temperature, low-field Cla spectra of degraded carrageenans. 2. On the specificity of the autohydrolysis reaction in Kappa/Iota and Mu/Nu structures. Int J Biol Macromol 13:337–340
Zvyagintseva TN, Shevchenko NM, Chizhov AO et al (2003) Water-soluble polysaccharides of some far-eastern brown seaweeds: distribution, structure, and their dependence on the developmental conditions. J Exp Mar Biol Ecol 294:1–13
Anastyuk SD, Shevchenko NM, Dmitrenok PS et al (2011) Investigation of a sulfate transfer during autohydrolysis of a fucoidan from the brown alga Fucus evanescens by tandem ESIMS. Carbohydr Res 346:2975–2977
Anastyuk SD, Shevchenko NM, Ermakova SP et al (2012) Anticancer activity in vitro of a fucoidan from the brown alga Fucus evanescens and its low-molecular fragments, structurally characterized by tandem mass-spectrometry. Carbohydr Polym 87:186–194
Anastyuk SD, Shevchenko NM, Nazarenko EL et al (2010) Structural analysis of a highly sulfated fucan from the brown alga Laminaria cichorioides by tandem MALDI and ESI mass spectrometry. Carbohydr Res 345:2206–2212
Anastyuk SD, Imbs TI, Shevchenko NM et al (2012) ESIMS analysis of fucoidan preparations from Costaria costata, extracted from alga at different life-stages. Carbohydr Polym 90:993–1002
Anastyuk SD, Barabanova AO, Correc G et al (2011) Analysis of structural heterogeneity of κ/β-carrageenan oligosaccharides from Tichocarpus crinitus by negative-ion ESI and tandem MALDI mass spectrometry. Carbohydr Polym 86:546–554
Chen P, Baker AG, Novotny MV (1997) The use of osazones as matrices for the matrix-assisted laser desorption/ionization mass spectrometry of carbohydrates. Anal Biochem 244:144–151
Anastyuk SD, Shevchenko NM, Dmitrenok PS et al (2012) Structural similarities of fucoidans from brown algae Silvetia babingtonii and Fucus evanescens, determined by tandem MALDI-TOF mass spectrometry. Carbohydr Res 358:78–81
Bilan MI, Grachev AA, Shashkov AS et al (2006) Structure of a fucoidan from the brown seaweed Fucus serratus L. Carbohydr Res 341:238–245
Bilan MI, Grachev AA, Ustuzhanina NE et al (2004) A highly regular fraction of a fucoidan from the brown seaweed Fucus distichus L. Carbohydr Res 339:511–517
Yu G, Zhao X, Yang B et al (2006) Sequence determination of sulfated carrageenan-derived oligosaccharides by high-sensitivity negative-ion electrospray tandem mass spectrometry. Anal Chem 78:8499–8505
Pomin VH, Valente AP, Pereira MS et al (2005) Mild acid hydrolysis of sulfated fucans: a selective 2-desulfation reaction and an alternative approach for preparing tailored sulfated oligosaccharides. Glycobiology 15:1376–1385
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The work was supported by FEB RAS grant 15-II-5-016.
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Anastyuk, S.D., Shevchenko, N.M., Gorbach, V.I. (2015). Fucoidan Analysis by Tandem MALDI-TOF and ESI Mass Spectrometry. In: Stengel, D., Connan, S. (eds) Natural Products From Marine Algae. Methods in Molecular Biology, vol 1308. Humana Press, New York, NY. https://doi.org/10.1007/978-1-4939-2684-8_19
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DOI: https://doi.org/10.1007/978-1-4939-2684-8_19
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