Selective oxidation and reduction of methionine residues in peptides and proteins by oxygen exchange between sulfoxide and sulfide.
Treatment of amino acids, peptides, and proteins with aqueous solution of dimethyl sulfoxide (Me2SO) and hydrochloric acid (HCl) resulted in the oxidation of methionine to methionine sulfoxide. In addition to methionine, SH groups are also oxidized, but this reaction proceeds after a lag period of 2 h. Other amino acids are not modified by aqueous Me2SO/HCl. The reaction is strongly pH-dependent. Optimal conditions are 1.0 M HCl, 0.1 M Me2SO, at 22 degrees C. The reaction exhibits pseudo-first order kinetics with Kobs = 0.23 +/- 0.015 M-1 min-1 at 22 degrees C. Incubation of methionine sulfoxide with dimethyl sulfide and HCl resulted in the conversion of methionine sulfoxide to methionine. This reaction is fast (t1/2 = 4 min at room temperature) and quantitative at relatively anhydrous condition (i.e. at H2O:concentrated HCl:dimethyl sulfide ratio of 2:20:1). Quantitative conversions of methionine sulfoxide back to methionine are obtained in peptides and proteins as well, with no observable other side reactions in amino acids and proteins. The wide applications of this selective oxidation and reduction of methionine residues are demonstrated and discussed.
D000324:Adrenocorticotropic Hormone / Q000378:metabolism; D055598:Chemical Phenomena; D002621:Chemistry; D002700:Chloramines / Q000494:pharmacology; D004121:Dimethyl Sulfoxide / Q000494:pharmacology; D006851:Hydrochloric Acid / Q000494:pharmacology; D008715:Methionine / Q000031:analogs & derivatives / Q000378:metabolism*; D010084:Oxidation-Reduction; D011506:Proteins / Q000378:metabolism*; D013053:Spectrophotometry; D013440:Sulfides / Q000378:metabolism*; D013454:Sulfoxides / Q000378:metabolism*; D014105:Tosyl Compounds; D014364:Tryptophan / Q000031:analogs & derivatives / Q000378:metabolism
D002700:Chloramines; D011506:Proteins; D013440:Sulfides; D013454:Sulfoxides; D014105:Tosyl Compounds; C016300:chloramine-T; C006392:N-acetyltryptophan; D014364:Tryptophan; D000324:Adrenocorticotropic Hormone; D008715:Methionine; D006851:Hydrochloric Acid; C013111:methionine sulfoxide; D004121:Dimethyl Sulfoxide