Summary
Identification of 3-dimethylsulfoniopropionate (DMSP) most often relies upon indirect methods, such as gas chromatographic analysis of dimethyl sulfide (DMS) released after treatment with base. Conventional electron ionization mass spectrometry (EI-MS) has traditionally not played a major role in the direct characterization of tertiary sulfonium compounds, such as DMSP, because of the low inherent volatility of these molecules. The development of desorption/ionization MS techniques, which do not require the sample to be introduced in the gas phase, has permitted DMSP and its analogs to be analyzed directly by mass spectrometry. Fast atom bombardment mass spectrometry, introduced in the early 1980’s, is a simple technique that provides ions representative of the intact molecule with little fragmentation. With stable isotope labeled analogs as internal standards, we have used FAB-MS to routinely identify and quantify DMSP levels in a variety of plant tissues. FAB-MS has also been employed recently to characterize synthetic potential precursors of DMSP and to follow isotope incorporation patterns in biosynthetic studies. Other alternative ionization techniques, including plasma desorption and electrospray ionization mass spectrometry have also shown some promise for the characterization of DMSP. Recently, a new approach based on gas chromatography/mass spectrometry (GC-MS) has been developed to analyze DMSP and its analogs. The carboxyl group is first protected by t-butyldi-methysilylation, and after co-injection of the derivatized sample with a catalyst, a nucleophile-assisted on-column demethylation step converts nonvolatile tertiary sulfonium compounds to their volatile S-methyl analogs. The GC-MS method has an advantage over direct MS analysis, since retention times and mass spectral data provide two dimensional characterization. Further, this method is particularly suitable for mixture analysis and the required instrumentation is widely available.
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References
Blunden, G., M.M. ElBarouni, S.M. Gordon, W.F.H. McLean and D.J. Rogers. 1981. Extraction, purification and characterization of Dragendorf-positive compounds from some British marine algae. Botanica Mar. 24: 451–456.
Blunden, G. and S.M. Gordon. 1986. Betaines and their sulfonio analogues in marine algae. Prog. Phycol. Res. 4: 39–80.
Bonham, CC, K.V. Wood, W.-J. Yang, A. Nadolska-Orczyck, Y. Samaras, D.A. Gage, J. Poupart, M. Burnet, A.D. Hanson and D. Rhodes. 1995. Identification of quaternary ammonium and tertiary sulfonium compounds by plasma desorption mass spectrometry. J. Mass Spectrom. (in press).
Gorham, J. S.J. Coughlan, R. Storey and R.G. Wyn-Jones. 1981. Estimation of quaternary ammonium and tertiary sulfonium compounds by thin layer electrophoresis and scanning reflectance densitometry. J. Chromatogr. 210: 550–554.
Grone, T. and G.O. Kirst. 1992. The effect of nitrogen deficiency, methionine and inhibitors of methionine metabolism on the DMSP contents of Tetraselmis subcordiformis (Stein) Mar. Biol. 112, 497–503.
Hanson, A. D. and D. A. Gage. 1991. Identification and determination by fast atom bombardment mass spectrometry of the compatible solute choline-O-sulphate in Limonium species and other halophytes. Aust. J. Plant Physiol. 18: 317–327.
Hanson, A. D., and D. A. Gage. 1996. 3-Dimethylsulfoniopropionate biosynthesis and use by flowering plants. In R. P. Kiene, P. T. Visscher, M. D. Keller, and G. O. Kirst (ed.), Biological and environmental chemistry of DMSP and related sulfonium compounds. Plenum, New York.
Hanson, A. D., Z. H. Huang and D. A. Gage. 1993. Evidence that the putative compatible solute 5-dimethylsulfoniopentanoate is an extraction artifact. Plant Physiol. 101: 1391–1393.
Hanson, A. D., J. Rivoal and D. A. Gage. 1993b. Synthesis and accumulation of 3-dimethylsulfonio-propionate in the halophyte Wedelia biflora. Plant Physiol. 102:(S) 905.
Hanson, A. D., J. Rivoal, L. Paquet and D. A. Gage. 1994. Biosynthesis of 3-dimethylsulfoniopropionate in Wollastonia biflora (L.) DC: Evidence that S-methylmethionine is an intermediate. Plant Physiol. 105: 103–110.
Huang, Z. H., D. A. Gage, L. L. Bieber and C. C. Sweeley. 1991. Analysis of acylcarnitines as their N-demethylated ester derivatives by gas chromatography-chemical ionization mass spectrometry. Anal. Biochem. 199: 98–105.
Huang, Z. H., C. C. Sweeley, L. L. Bieber, D. A. Gage, C. Tallarico, G. Bruno and A. Marzo. 1992. A general method for the simultaneous analysis of free carnitine and acylcaraitines by GC-MS of their N-demethylated silylated derivatives. In Proceedings of the 40th ASMS Conference on Mass Spectrometry and Allied Topics, Washington, DC, p. 1091–1092.
James, F., L. Paquet, S. A. Sparace, D. A. Gage and A. D. Hanson. 1995. Evidence implicating dimethylsulfonio-propionaldehyde as an intermediate in dimethylsulfoniopropionate biosynthesis. Plant Physiol., in press.
Larher, F. and J. Hamelin. 1979. L’acide diméthylsulfonium-5 pentanoïque de Diplotaxis tenuifolia. Phytochemistry 18: 1396–1397.
Mudd, S.H. and A.H. Datko. 1990. The S-methylmethionine cycle in Lemna paucicostata. Plant Physiol. 93: 623–630.
Paquet, L., B. Rathinasabapathi, H. Saini, D. A. Gage and A. D. Hanson. 1993. Accumulation of the compatible solute 3-dimethylsulfoniopropionate in sugarcane. Plant Physiol. 102:(S) 936.
Paquet, L., B. Rathinasabapathi, H. Saini, L. Zamir, D. A. Gage, Z.-H. Huang and A. D. Hanson. 1994. Accumulation of the compatible solute 3-dimethylsulfonio-propionate in sugarcane and its relatives, but not other gramineous crops. Aust. J. Plant Physiol. 21: 37–48.
Reed, R. H. 1983. Measurement and osmotic significance of ß-dimethyl-sulphionio-propionate in marine macroalgae. Marine Biology Letters 4: 173–181.
Rhodes, D. 1990. Fast atom bombardment mass spectrometry, p. 95–123. In H. F. Linskens and J. F. Jackson, (eds.), Modern Methods of Plant Analysis, New Ser. Vol. 11: Physical Methods in Plant Science. Berlin/Heidelberg: Springer-Verlag.
Rhodes, D. and A. D. Hanson. 1993. Quaternary ammonium and tertiary sulfonium compounds in higher plants. Ann. Rev. Plant Physiol. Plant Mol. Biol. 44: 357–384.
Rhodes, D., P. Rich, A. C. Myers, C. C. Reuter and G. C. Jamieson. 1987. Determination of betaines by fast atom bombardment mass spectrometry: identification of glycine betaine deficient genotypes of Zea mays. Plant Physiol. 84: 781–788.
Sheets, E. B., and D. Rhodes. 1996. Determination of DMSP and other onium compounds in Tetraselmis subcordiformis by plasma desorption mass spectrometry. In R. P. Kiene, P. T. Visscher, M. D. Keller, and G. O. Kirst (ed.), Biological and environmental chemistry of DMSP and related sulfonium compounds. Plenum, New York.
Smith, R. D., J. A. Loo, Ch. G. Edmonds, Ch. J. Barinaga and H. R. Udseth. 1990. New developments in biochemical mass spectrometry: electrospray ionization. Anal. Chem. 62: 882–899.
Storey, R., J. Gorham, M.G. Pitman, A.D. Hanson and D.A. Gage. 1993. Response of Melanthera biflora to salinity and waters stress. J. Exp. Botany 44: 1551-1560.
White, R.H. 1982. Analysis of dimethyl compounds in marine algae. J. Mar. Res. 40: 529-536.
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Gage, D.A., Hanson, A.D. (1996). Characterization of 3-Dimenthysulfoniopropionate (DMSP) and its Analogs with Mass Spectrometry. In: Kiene, R.P., Visscher, P.T., Keller, M.D., Kirst, G.O. (eds) Biological and Environmental Chemistry of DMSP and Related Sulfonium Compounds. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-0377-0_3
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