Applications of Mass Spectrometry for the Examination of Pectic Polysaccharides

  • R. R. Selvendran
  • B. J. H. Stevens
Part of the Modern Methods of Plant Analysis book series (MOLMETHPLANT, volume 3)

Abstract

Mass spectrometry has proved to be an important technique for the study of carbohydrate derivatives from a range of tissues, and its potential applications for the elucidation of the structural features of polysaccharides have been discussed in a number of reviews (Lindberg 1972; Lönngren and Svensson 1974; McNeil et al. 1982a). As the basic concepts of interpretation of mass spectra from carbohydrate derivatives have been adequately reviewed (Kochetkov and Chizhov 1966; Hanessian 1971; Lönngren and Svensson 1974; Kováčik et al. 1978), no attempt will be made to interpret the spectra in detail. However, attention will be drawn to some of the distinctive and characteristic features associated with the fragmentation pathways used for the identification of derivatives from pectic polysaccharides.

Keywords

Methylation Analysis Pectic Polysaccharide Alditol Acetate Partial Acid Hydrolysis Glycosyl Residue 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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References

  1. Albersheim P, Nevins DJ, English PD, Karr A (1967) A method for the analysis of sugars in plant cell wall polysaccharides by gas-liquid chromatography. Carbohydr Res 5:340–345CrossRefGoogle Scholar
  2. Aman P, McNeil M, Franzén L-E, Darvill AG, Albersheim P (1981) Structural elucidation, using HPLC-MS and GLC-MS, of the acidic polysaccharide secreted by Rhizobium meliloti strain 1021. Carbohydr Res 95:263–282CrossRefGoogle Scholar
  3. Ashford D, Desai NN, Allen AK, Neuberger A, O’Neill MA, Selvendran RR (1982) Structural studies of the carbohydrate moieties of lectins from potato (Solanum tuberosum) tubers and thorn-apple (Datura stramonium) seeds. Biochem J 201:199–208PubMedGoogle Scholar
  4. Aspinall GO (1969) Gums and mucilages. In: Tipson RS, Horton D (eds) Advances in car bohydrate chemistry and biochemistry, vol 24. Academic, New York, pp 333–379Google Scholar
  5. Aspinall GO (1980) Chemistry of cell wall polysaccharides. In: Preiss J (ed) Carbohydrates — structure and function. Academic, New York, pp 473–500 (The Biochemistry of Plants, vol 3)Google Scholar
  6. Aspinall GO (1982) Chemical characterization and structure determination of polysaccharides. In: Aspinall GO (ed) The polysaccharides, vol 1. Academic, New York, pp 35–131Google Scholar
  7. Aspinall GO, Baillie J (1963) Gum tragacanth. Part I. Fractionation of the gum and the structure of tragacanthic acid. J Chem Soc 1702–1714Google Scholar
  8. Aspinall GO, Chaudhari AS (1975) Base-catalysed degradations of carbohydrates. X. Degradation by ß-elimination of methylated degraded leocarpan A. Can J Chem 53:2189–2193Google Scholar
  9. Aspinall GO, Fanous HK (1984) Structural investigations on the non-starchy polysaccharides of apples. Carbohydr Polymers 4:193–214CrossRefGoogle Scholar
  10. Aspinall GO, Jiang K-S (1974) Rapeseed hull pectin. Carbohydr Res 38:247–255CrossRefGoogle Scholar
  11. Aspinall GO, Whitehead CC (1970a) Mesquite gum. I. The 4-O-methylglucuronogalactan core. Can J Chem 48:3840–3849CrossRefGoogle Scholar
  12. Aspinall GO, Whitehead CC (1970b) Mesquite gum. II. The arabinan peripheral chains. Can J Chem 48:3850–3855CrossRefGoogle Scholar
  13. Aspinall GO, Charlson AJ, Hirst EL, Young R (1963). The location of L-Rhamnopyranose residues in gum arabic. J Chem Soc, pp 1696–1702Google Scholar
  14. Aspinall GO, Cottrell IW, Egan SV, Morrison IM, Whyte JNC (1967) Polysaccharides of soy-beans. Part IV. Partial hydrolysis of the acidic polysaccharide complex from cotyledon meal. J Chem Soc (C), pp 1071–1080Google Scholar
  15. Aspinall GO, Craig JWT, Whyte JL (1968a) Lemon-peel pectin. Part 1. Fractionation and partial hydrolysis of water-soluble pectin. Carbohydr Res 7:442–452CrossRefGoogle Scholar
  16. Aspinall GO, Gestetner B, Molloy JA, Uddin M (1968b) Pectic substances from Lucerne (Medicago Sativa). Part II. Acidic oligosaccharides from partial hydrolysis of leaf and stem pectic acids. J Chem Soc (C), pp 2554–2559Google Scholar
  17. Aspinall GO, Cottrell JW, Molloy JA, Uddin M (1970) Lemon-peel pectin. III. Fractionation of pectic acids from lemon-peel and lucerne. Can J Chem 48:1290–1295CrossRefGoogle Scholar
  18. Björndal H, Hellerqvist CG, Lindberg B, Svensson S (1970) Gas liquid chromatography and mass spectrometry in methylation analysis of polysaccharides. Angew Chem Int Ed 9:610–619CrossRefGoogle Scholar
  19. Chizhov OS, Kadentsev VI, Solov’yov AA, Levonowitch PF, Dougherty RC (1976) Polysaccharide sequencing by mass spectrometry: Chemical ionisation spectra of permethyl glycosylalditols. J Org Chem 41:3425–3428CrossRefGoogle Scholar
  20. Conchie J, Hay AJ, Lomax JA (1982) A comparison of some hydrolytic and gas chromatographic procedures used in methylation analysis of the carbohydrate units of glycopeptides. Carbohydr Res 103:129–132PubMedCrossRefGoogle Scholar
  21. Darvill AG, McNeil M, Albersheim P (1978) Structure of plant cell walls VIII. A new pectic polysaccharide. Plant Physiol 62:418–422PubMedCrossRefGoogle Scholar
  22. Darvill AG, McNeil M, Albersheim P (1980) General and facile method for distinguishing 4-linked aldopyranosyl residues from 5-linked aldofuranosyl residues. Carbohydr Res 86:309–315CrossRefGoogle Scholar
  23. Dell A, Morris HR, Egge HE, von Nicolai H, Strecker G (1983a) Fast-atom-bombardment mass-spectrometry for carbohydrate-structure determination. Carbohydr Res 115:41-52CrossRefGoogle Scholar
  24. Dell A, Oates JE, Morris HR, Egge H (1983b) Structure determination of carbohydrates and glycosphino-lipids by fast-atom-bombardment mass spectrometry. Int J Mass Spectrom Ion Phys 46:415–418CrossRefGoogle Scholar
  25. Fales HM, Milne GWA (1969). Chemical ionization mass spectrometry of complex molecules. J Am Chem Soc 91:3682–3685PubMedCrossRefGoogle Scholar
  26. Fichtinger-Schepman AMJ (1980) Structural studies on the polysaccharide associated with the coccoliths of the alga Emiliania huxleyi (Lohmann) Kamptner. PhD Thesis, University of UtrechtGoogle Scholar
  27. Fichtinger-Schepman AMJ, Kamerling JP, Versluis C, Vliegenthart JFG (1980) Structural analysis of acidic polysaccharides derived from the methylated, acidic polysaccharide associated with coccoliths of Emiliania huxleyi (Lohmann) Kamptner. Carbohydr Res 86:215–225CrossRefGoogle Scholar
  28. Gerwig GJ, Kamerling JP, Vliegenthart JFG (1978) Determination of the D and L configuration of neutral monosaccharides by high-resolution capillary G.L.C. Carbohydr Res 62:349–357CrossRefGoogle Scholar
  29. Geyer R, Geyer H, Kunnhardt S, Mink W, Stirm S (1983) Methylation analysis of complex carbohydrates in small amounts: Capillary gas chromatography-mass fragmentography of methylalditol acetates obtained from N-glycosidically linked glycoprotein oligosaccharides. Anal Biochem 133:197–207PubMedCrossRefGoogle Scholar
  30. Grob K, Grob K Jr (1978) On-column injection on to glass capillary columns. J Chromatogr 151:311–320CrossRefGoogle Scholar
  31. Hakomori S (1964) A rapid permethylation of glycolipid, and polysaccharide catalyzed by methylsulfinyl carbanion in dimethylsulfoxide. J Biochem (Tokyo) 55:205–207Google Scholar
  32. Hanessian S (1971) Mass spectrometry in the determination of structure of certain natural products containing sugars. In: Glick D (ed) Methods of biochemical analysis, vol 19, Interscience Publishers, John Wiley, New York, pp 105–228CrossRefGoogle Scholar
  33. Harada K, Ito S, Takeda N, Suzuki M, Tatematsu A (1983) Sequence determination of per-methylated oligosaccharides by chemical ionization mass spectrometry. Biomed Mass Spectrom 10:5–12CrossRefGoogle Scholar
  34. Harris PJ, Henry RJ, Blakeney AB, Stone BA (1984). An improved procedure for the meth ylation analysis of oligosaccharides and polysaccharides. Carbohydr Res 127:59–73PubMedCrossRefGoogle Scholar
  35. Jansson PE, Kenne L, Liedgren H, Lindberg B, Lönngren J (1976) A practical guide to the methylation analysis of carbohydrates. Chem Commun Univ Stockholm, No 8Google Scholar
  36. Kärkkäinen J (1970) Analysis of disaccharides as permethylated disaccharide alditols by gas-liquid chromatography-mass spectrometry. Carbohydr Res 14:27–33CrossRefGoogle Scholar
  37. Kärkkäinen J (1971) Structural analysis of trisaccharides as permethylated methyl glycosides by gas-liquid chromatography-mass spectrometry. Carbohydr Res 17:1–10CrossRefGoogle Scholar
  38. Klok J, Cox HC, De Leeuw JW, Schenck PA (1982) Analysis of synthetic mixtures of partially methylated alditol acetates by capillary gas chromatography, gas chromatography-electron impact mass spectrometry and gas chromatography-chemical ionization mass spectrometry. J Chromatogr 253:55–64CrossRefGoogle Scholar
  39. Kochetkov NK, Chizhov OS (1966) Mass spectrometry of carbohydrate derivatives. In: Adv Carbohydr Chem Biochem 21:29–93Google Scholar
  40. Kovâcik V, Bauer S, Rosik J, Kovâç P (1968a) Mass spectrometry of uronic acid derivatives. III. The fragmentation of methyl ester methyl glycosides of methylated uronic and aldobiouronic acids. Carbohydr Res 8:282–290CrossRefGoogle Scholar
  41. Kovâcik V, Bauer S, Rosik J (1968b) Mass spectrometry of uronic acid derivatives. IV. The fragmentation of methyl ester methyl glycosides of methylated aldotriouronic acids. Carbohydr Res 8:291–294CrossRefGoogle Scholar
  42. Kovâcik V, Mihâlov V, Hirsch J, Kovâc P (1978). Mass spectrometry of uronic acid derivatives. Biomed Mass Spectrom 5:136–145PubMedCrossRefGoogle Scholar
  43. Lau JM, McNeil M, Darvill AG, Albersheim P (1985) Structure of the backbone of rhamnogalacturonan-1, a pectic polysaccharide in the primary cell walls of plants. Carbohydr Res 137:111–125CrossRefGoogle Scholar
  44. Lee Y-C, Ballou CE (1965) Preparation of mamanobiose, mannotriose, and a new mannotetraose from Saccharomyces cerevisiae mannan. Biochemistry 4:257–264CrossRefGoogle Scholar
  45. Leontein KB, Lindberg B, Lönngren J (1978). Assignment of absolute configuration of sugars by GLC of their acetylated glycosides formed from chiral alcohols. Carbohydr Res 62:359–362CrossRefGoogle Scholar
  46. Lindberg B (1972) Methylation analysis of polysaccharides. In: Ginsburg V (ed) Methods in enzymology, vol XXVIII. Academic, New York, pp 178–195Google Scholar
  47. Lindberg B, Lönngren J (1976) Specific degradation of polysaccharides containing uronic acid residues. Methods Carbohydr Chem 7:142–148Google Scholar
  48. Lindberg B, Lönngren J (1978) Methylation analysis of complex carbohydrates: General procedure and application for sequence analysis. In: Ginsburg V (ed) Methods in enzymology, vol L, complex carbohydrates, part C. Academic, New York, pp 3–33Google Scholar
  49. Lindberg B, Lönngren J, Thompson JL (1973) Degradation of polysaccharides containing uronic acid residues. Carbohydr Res 28:351–357CrossRefGoogle Scholar
  50. Lomax JA, Conchie J (1982) Separation of methylated alditol acetates by glass capillary gas chromatography and their identification by computer. J Chromatogr 236:385–394CrossRefGoogle Scholar
  51. Lönngren J, Svensson S (1974) Mass spectrometry in structural analysis of natural carbohydrates. In: Tipson RS, Horton D (eds) Advances in carbohydrate chemistry and biochemistry, vol 29. Academic, New York, pp 41–106Google Scholar
  52. McNeil M (1983) Elimination of internal glycosyl residues during chemical ionization — mass spectrometry of per-O-alkylated oligosaccharide alditols. Carbohydr Res 123:31-40CrossRefGoogle Scholar
  53. McNeil M, Albersheim P (1977) Chemical-ionization mass spectrometry of methylated hexitol acetates. Carbohydr Res 56:239–248CrossRefGoogle Scholar
  54. McNeil M, Darvill AG, Albersheim P (1980) Structure of plant cell walls. X. Rhamnogalacturonan-1, a structurally complex pectic polysaccharide in the walls of suspension-cultured sycamore cells. Plant Physiol 66:1128–1134PubMedCrossRefGoogle Scholar
  55. McNeil M, Darvill AG, Aman A, Franzén L-E, Albersheim P (1982a) Structural analysis of complex carbohydrates using high-performance liquid chromatography, and mass spectrometry. In: Gingsburg V (ed) Methods in enzymology, Complex carbohydrates, vol 83. Academic, New York, pp 3–45CrossRefGoogle Scholar
  56. McNeil M, Darvill AG, Albersheim P (1982b) Structure of plant cell walls. XII. Identification of seven differently linked glycosyl residues attached to 0–4 of the 2,4-linked L-rhamnosyl residues of rhamnogalacturonan 1. Plant Physiol 70:1586–1591CrossRefGoogle Scholar
  57. McNeil M, Darvill AG, Fry SC, Albersheim P (1984). Structure and function of the primary cell wall of plants. Annu Rev Biochem 53:623–663CrossRefGoogle Scholar
  58. Moor J, Waight ES (1975) The mass spectra of permethylated oligosaccharides. Biomed Mass Spectrom 2:36–45PubMedCrossRefGoogle Scholar
  59. O’Neill MA, Roberts K (1981) Methylation analysis of cell wall glycoproteins and glycopeptides from Chlamydomonas reinhardii. Phytochemistry 20:25–28CrossRefGoogle Scholar
  60. O’Neill MA, Selvendran RR (1980) Methylation analysis of cell wall material from Phaseolus vulgaris and Phaseolus coccineus. Carbohydr Res 79:115–124CrossRefGoogle Scholar
  61. O’Neill MA, Selvendran RR (1983) Isolation and partial characterisation of a xyloglucan from the cell walls of Phaseolus coccineus. Carbohydr Res 111:239–255CrossRefGoogle Scholar
  62. O’Neill MA, Selvendran RR (1985) Structural analysis of the xyloglucan from Phaseolus coccineus cell walls using cellulase derived oligosaccharides. Carbohydr Res 145:45-58CrossRefGoogle Scholar
  63. Peat S, Whelan WJ, Edwards TE (1961) Polysaccharides of baker’s yeast. Part IV. Mannan. J Chem Soc, pp 29–34Google Scholar
  64. Ring SG, Selvendran RR (1978) Purification and methylation analysis of cell wall material from Solanum tuberosum. Phytochemistry 17:745–752CrossRefGoogle Scholar
  65. Ring SG, Selvendran RR (1980) Isolation and analysis of cell wall material from beeswing wheat bran. Phytochemistry 19:1723–1730CrossRefGoogle Scholar
  66. Ring SG, Selvendran RR (1981) An arabinogalactoxyloglucan from the cell wall of Solanum Tuberosum. Phytochemistry 20:2511–2519CrossRefGoogle Scholar
  67. Sandford PA, Conrad HE (1966) The structure of the Aerobacter aerogenes A3 (51) polysaccharide. I. A reexamination using improved procedures for methylation analysis. Biochemistry 5:1508–1517PubMedCrossRefGoogle Scholar
  68. Selvendran RR (1983) Applications of gas chromatography-mass spectrometry for cell wall analysis. In: Frigerio A (ed) Recent developments in mass spectrometry in biochemistry, medicine and environmental research 8. Elsevier Scientific Publishing, Amsterdam, pp 159–176Google Scholar
  69. Selvendran RR (1985) Developments in the chemistry and biochemistry of pectic and hemicellulosic polymers. J Cell Sci Suppl 2:51–88PubMedGoogle Scholar
  70. Selvendran RR, DuPont MS (1984) Problems associated with the analysis of dietary fibre and some recent developments. In: King RD (ed) Developments in food analysis techniques 3. Elsevier Applied Science Publishers, London, pp 1–68Google Scholar
  71. Selvendran RR, March JF, Ring SG (1979) Determination of aldoses and uronic acid content of vegetable fibre. Anal Biochem 96:282–92PubMedCrossRefGoogle Scholar
  72. Selvendran RR, Stevens BJH, O’Neill MA (1985) In: Brett CT, Hillman JR (eds) Biochemistry of plant cell walls, Society for experimental biology seminar series, vol 28. Cambridge University Press, pp 37–78Google Scholar
  73. Stephen AM (1983) Other plant polysaccharides. In: Aspinall GO (ed) The polysaccharides, vol 2. Academic, pp 98–193Google Scholar
  74. Stevens BJH, Selvendran RR (1984) Pectic polysaccharides of cabbage (Brassica oleracea var. Decema) Phytochemistry 23:109–115CrossRefGoogle Scholar
  75. Sweet DP, Shapiro RH, Albersheim P (1974) The mass spectral fragmentation of partially ethylated alditol acetates, a derivative used in determining the glycosyl linkage composition of polysaccharides. Biomed Mass Spectrom 1:263–268PubMedCrossRefGoogle Scholar
  76. Sweet DP, Albersheim P, Shapiro RH (1975) Partially ethylated alditol acetates as derivatives for elucidation of the glycosyl linkage-composition of polysaccharides. Carbohydr Res 40:199–216CrossRefGoogle Scholar
  77. Talmadge K, Keegstra K, Bauer WD, Albersheim P (1973). The structure of plant cell walls. 1. The macromolecular components of the walls of suspension-cultured sycamore cells with a detailed analysis of the pectic polysaccharides. Plant Physiol 51:158–173PubMedCrossRefGoogle Scholar
  78. Taylor RL, Conrad HE (1972) Stoichiometric depolymerization of polyuronides and glycosaminoglycuronans to monosaccharides following reduction of their carbodiimideactivated carboxyl groups. Biochemistry 11:1383–1388PubMedCrossRefGoogle Scholar
  79. Toman R, Karâcsonyi Š, Kubacková M (1975) Studies on the pectin present in the bark of white willow (Salix alba L.): Fractionation and acidic depolymerisation of the water-soluble pectin. Carbohydr Res 43:111–116CrossRefGoogle Scholar
  80. Toman R, Karâcsonyi Š, Kubacková M (1976) Studies on pectin present in the bark of white willow (Salix alba L.) Structure of the acidic and neutral oligosaccharides obtained by partial acid hydrolysis. Cellul Chem Technol 10:561–565Google Scholar
  81. Valent BS, Darvill AG, McNeil M, Robertson BK, Albersheim P (1980) A general and sensitive chemical method for sequencing the glycosyl residues of complex carbohydrates. Carbohydr Res 79:165–192PubMedCrossRefGoogle Scholar

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© Springer-Verlag Berlin Heidelberg 1986

Authors and Affiliations

  • R. R. Selvendran
  • B. J. H. Stevens

There are no affiliations available

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