Hypotaurine Oxidation: An HPLC-Mass Approach

  • Silvestro Dupré
  • Alessandra Spirito
  • Kazunori Sugahara
  • Hiroyuki Kodama
Part of the Advances in Experimental Medicine and Biology book series (AEMB, volume 442)


Hypotaurine reacts with various reactive oxygen species, although mainly with hydroxyl radicals. The compound bis-aminoethyl-α-disulfone (H2N-CH2-CH2-SO2-SO2-CH2-CH2-NH2) has been proposed as one of the intermediate products during the ultraviolet light-catalyzed oxidation of hypotaurine13. The disulfone has been proposed as a product of the hydroxyl radical quenching activity of hypotaurine6 and has been demonstrated to be present in vitro after hypotaurine oxidation by Fenton’s reagent or in the presence of enzymatically-generated hydroxyl radicals7. The sulfonyl radical RSO2· has been hypothesized as a reaction intermediate6,7. In an attempt to understand in more detail the reaction of hypotaurine with Fenton’s reagent, we studied this reaction by LC/APCI-MS which evaluates the time course of product formation and the production of intermediates. The presence of bis-aminoethyl-α-disulfone among the reaction products could not be demonstrated by this technique. Attempts to synthesize this compound by reported methods for the synthesis of other α-disulfones or by reaction involving chemically- or enzymatically-generated hydroxyl radicals were also unsuccessful.


Amino Acid Analysis Sulfinic Acid Kochi Medical School APCI Interface Involve Hydroxyl Radical 
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  1. 1.
    Allen, P., Karger, L., Haygood, J.D., and Shrensel, J., 1951, Aliphatic sulfinic acids. III. Preparation of aliphatic alpha-disulfones, J. Org. Chem., 16:767–770.CrossRefGoogle Scholar
  2. 2.
    Allen, P. and Brook, J.W., 1962, Preparation of alkyl thiolsulfinates, thiolsulfonates and α-disulfones, J. Org. Chem., 27:1019–1020.CrossRefGoogle Scholar
  3. 3.
    Aruoma O.L., Halliwell B., Hoey B.M., and Butler J., 1988, The antioxidant action of taurine, hypotaurine and their metabolic precursors, Biochem. J., 256:251–255.PubMedGoogle Scholar
  4. 4.
    Duprè, S., Fontana, M., Pitari, G., and Cavallini, D., 1996, In vitro reactions of hypotaurine, in Adv. Exp. Med. Biol. “Taurine 2: Basic and Clinical Aspects”, Huxtable, R.J., Azuma, J., Kuriyama, K., Nakagawa, M., and Baba, A., eds., Plenum Press, New York, Vol. 403, pp 3–8.Google Scholar
  5. 5.
    Duprè, S., Spirito, A., Pinnen, F. Sugahara, K., and Kodama, H., manuscript in preparation.Google Scholar
  6. 6.
    Fellman, J.H. and Roth, E.S., 1985, The biological oxidation of hypotaurine to taurine: hypotaurine as an antioxidant, in Progr. Clin. Biol. Res. “Taurine: Biological Actions and Clinical Perspectives”, Oja, S.S., Ahtee, L., Kontro, P. and Paasonen, M.K., eds., Alan R. Liss, Inc., New York, Vol. 179, pp 71–82.Google Scholar
  7. 7.
    Fellman, J.H., Green, T.R., and Eicher, A.L., 1987, The oxidation of hypotaurine to taurine: bis-aminoethyl-α-disulfone, a metabolic intermediate in mammalian tissue, in Adv. Exp. Med. Biol. “The Biology of Taurine: Methods and Mechanism”, Huxtable, R.J., Franconi, F., and Giotti, A., eds., Plenum Press, New York, Vol. 217, pp. 39–48.Google Scholar
  8. 8.
    Hoyle, J., 1990, The oxidation and reduction of sulphinic acids and their derivatives, in “The Chemistry of sulphinic acids, esters and their derivatives”, Patai, S., ed., John Wiley & Sons, New York, pp. 463.Google Scholar
  9. 9.
    Kice, J.L. and Bowers, K.W., 1962, The mechanism of the disproportionation of sulfinic acids, J. Amer. Chem. Soc., 84:605–610.CrossRefGoogle Scholar
  10. 10.
    Kice, J.L. and Kasparek G.J., 1969, Quantitative comparison of nucleophilic substitution at sulfonyl vs. sulfinyl sulfur. The hydrolysis of aryl α-disulfones in aqueous dioxane, J. Amer. Chem. Soc., 91:5510–5516.CrossRefGoogle Scholar
  11. 11.
    Pihlaja, K., 1988, Mass spectra of sulfoxides and sulfones, in “The Chemistry of Sulphones and Sulphoxides”, S. Patai, ed., Wiley and Sons, pp. 149.Google Scholar
  12. 12.
    Pihlaja, K., 1990, Mass spectra of sulfinic acids, in “The Chemistry of Sulphinic Acids, Esters and Their Derivatives”, S. Patai, ed., Wiley and Sons, pp. 107-128.Google Scholar
  13. 13.
    Ricci, G., Duprè, S., Federici, G., Spoto, G., Matarese, R.M., and Cavallini, D., 1978, Oxidation of hypotaurine to taurine by ultraviolet irradiation, Physiol. Chem. & Phys., 10:435–441.Google Scholar
  14. 14.
    Schöberl, A. and Wagner, A. 1955a, Methoden zur Herstellung und Umwandlung von Thiosulfon-und Thiosulfinsäureestern, in “Methoden der Organischen Chemie (Houben-Weyl)”, E. Müller, ed., G. Thieme Verlag, Stuttgart, 4th ed., Vol. 9, pp. 689–691.Google Scholar
  15. 15.
    Schöberl, A. and Wagner, A., 1955b, Methoden zur Herstellung und Umwandlung von Sulfonen und Sulfoximinen, in “Methoden der Organischen Chemie (Houben-Weyl)”, E. Müller, ed., Vol. 9, 4th ed., G. Thieme Verlag, Stuttgart, pp. 254–255.Google Scholar
  16. 16.
    Toennies, G. and Lavine, T.F., 1934, The oxidation of cystine in non-aqueous media. III. Products of exhaustive oxygenation of cystine perchlorate in acetonitrile, J. Biol. Chem., 105:107–115.Google Scholar
  17. 17.
    Wellish, E., Gibstein, E., and Sweeting, O.J., 1961, Thermal decomposition of sulfinic acids, J. Org. Chem., 27:1810–1812.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 1998

Authors and Affiliations

  • Silvestro Dupré
    • 1
  • Alessandra Spirito
    • 1
  • Kazunori Sugahara
    • 2
  • Hiroyuki Kodama
    • 2
  1. 1.Dipartimento di Scienze Biochimiche and Centro di Biologia Molecolare del C.N.R.Università di Roma “La Sapienza”RomaItaly
  2. 2.Department of ChemistryKochi Medical SchoolOkocho, Nankoku KochiJapan

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