Hypotaurine Oxidation: An HPLC-Mass Approach
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.
KeywordsAmino Acid Analysis Sulfinic Acid Kochi Medical School APCI Interface Involve Hydroxyl Radical
Unable to display preview. Download preview PDF.
- 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.Duprè, S., Spirito, A., Pinnen, F. Sugahara, K., and Kodama, H., manuscript in preparation.Google Scholar
- 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.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.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
- 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.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.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.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.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.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