Mass Spectra of Cysteine Derivatives

  • Mendel Friedman
Part of the Advances in Experimental Medicine and Biology book series (AEMB, volume 86A)


The mass spectra of a series of cysteine derivatives of structure X-CH2CH2SCH2CH(NH2)COOH were examined to assess the influence of the electron-witndrawing functional group X on the mass spectral fragmentation patterns. Measurable molecular ions were present in most of the spectra although in some cases such peaks had relative abundances below a few per cent. More useful information on the nature of the substituent could be obtained from the M — 74 peak corresponding to cleavage C2H4O2N at the sulfur atom. the results show that mass spectroscopy is valuable for identifying the S-alkyl side chain in S-alkyl cysteine derivatives, a process frequently required in studies on chemical modification of sulfhydryl groups and in determining disulfide bonds in proteins. the observed fragmentation patterns are discussed in terms of localization of positive charges of ionic species on either sul-ful, nitrogen, or heterocyclic rings and in terms of substituent effects on available decomposition pathways.


Sulfur Atom Butyl Ester Decomposition Pathway Homolytic Cleavage Cysteine Derivative 


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  1. Brown, E. V. and Moser, R. J. (1971). Mass spectra of some 2-,3-, and 4-pyridine carboxylic acids. Further evidence of a N-H interaction from loss of carbon dioxide. J. Heterocyclic Chem., 8, 189–192.CrossRefGoogle Scholar
  2. Cavins, J. F. and Friedman, M. (1970). Preparation and evaluation of S-β-(4-pyridylethyl)-L-cysteine as an internal standard for amino acid analyses. Anal. Biochem., 35, 489–493.PubMedCrossRefGoogle Scholar
  3. Elliott, W. H. and Waller, G. R. (1972). Vitamins and cofactors. In “Biochemical Applications of Mass Spectrometry,” G. R Waller, Ed., Wiley-Interscience, New York, New York, Chapter 18.Google Scholar
  4. Friedman, M. (1973). “The Chemistry and Biochemistry of the Sulfhydryl Group in Amino Acids, Peptides, and Proteins,” Pergamon Press, Oxford, England and Elmsford, New York, 485 + viii p.Google Scholar
  5. Friedman, M. and Noma, A. T. (1970). Cystine content of wool. Textile Res. J., 40, 1073–1078.CrossRefGoogle Scholar
  6. Friedman, M. and Romersberger, J. A. (1968). Relative influences of electron-withdrawing functional groups on basicities of amino acid derivatives. J. Org. Chem., 33, 154–157.PubMedCrossRefGoogle Scholar
  7. Friedman, M. and Tillin, S. J. (1970). Flame-resistant wool. Textile Res. J., 40, 1045–1047.CrossRefGoogle Scholar
  8. Friedman, M., Cavins, J. E., and Wall, J. S. (1965). Relative nucleophilic reactivities of amino groups and mercaptide ions in addition reactions with α,β-unsaturated compounds. J. Amer. Chem. Soc., 87, 3672–3682.CrossRefGoogle Scholar
  9. Friedman, M., Noma, A. T., and Masri, M. S. (1973). New internal standards for basic amino acid analyses. Anal. Biochem., 51, 280–287.PubMedCrossRefGoogle Scholar
  10. Harpp, D. N. and Gleason, J. G. (1971). Preparation and mass spectral properties of cystine and lanthionine derivatives. A novel synthesis of L-lanthionine by selective desulfuriza-tion. J. Org. Chem., 36, 73–80.PubMedCrossRefGoogle Scholar
  11. Kiryushkin, A. A., Gorlenko, V. A., Agadzhanyan, Ts.E., Rosinov, B. V., Ovchinnikov, Yu. A., and Shemyakin, M. M. (1968). Mass spectrometric determination of the amino acid sequence in cystine and cysteine-containing peptides. Experientia, 24, 883–885.Google Scholar
  12. Krull, L. H., Gibbs, D. E., and Friedman, M. (1971). 2-Vinyl-quinoline, a reagent to determine protein sulfhydryl groups spectrophotometrically. Anal. Biochem., 49, 80–85.CrossRefGoogle Scholar
  13. Nishimura, H. and Mizutani, J. (1975). Photochemistry and radiation chemistry of sulfur-containing amino acids. A novel reaction of 1-propenylthiyl radicals. J. Org. Chem., 40, 1567–1575.PubMedCrossRefGoogle Scholar
  14. Nishimura, H., Tahara, S., Okuyama, H., and Mizutani, J. (1972). Mass spectra of sulphur-containing amino acids and peptides. Tetrahedron, 28, 4503–4513.CrossRefGoogle Scholar
  15. Polan, N. L., McMurray, W. J., Lipsky, S. R., and Lande, S. (1970). Mass spectroscopy of cysteine-containing peptides. Biochem. Biophys. Res. Commun., 38, 1127–1133.PubMedCrossRefGoogle Scholar
  16. Shemyakin, M. M., Ovchinnikov, Yu. A., and Kiryushkin, A. A. (1971). Mass spectrometry of amino acids and peptides. In “Mass Spectrometry: Techniques and Applications,” G. W. A. Milne, Ed., Wiley-Interscience, New York, New York, pp. 289–325.Google Scholar
  17. Toubiana, R., Barnett, J. E. G., Sach, E., Das, B. C., and Lederer, E. (1970). Determination of amino acid sequences in peptides by mass spectrometry. Desulfurization of sulfur-containing peptides. FEBS Letters, 8, 207–209.PubMedCrossRefGoogle Scholar
  18. Tsang, C. W. and Harrison, A. G. (1976). Chemical ionization of amino acids. J. Amer. Chem. Soc., 98, 1301–1308.CrossRefGoogle Scholar
  19. Tschesche, H., Schneider, M., and Wachter, E. (1972). Mass spectral identification and quantification of phenylthiohydantoin derivatives from Edman degradation of proteins: cysteine derivatives. FEBS Letters, 23, 367–372.PubMedCrossRefGoogle Scholar
  20. Presented at the 159th National Meeting of the American Chemical Society, Houston, Texas, Feb. 22-27, 1970, Abstracts p. ANAL 91.Google Scholar

Copyright information

© Plenum Press, New York 1977

Authors and Affiliations

  • Mendel Friedman
    • 1
  1. 1.Agricultural Research Service, U.S. Department of AgricultureWestern Regional Research LaboratoryBerkeleyUSA

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