Intramolecular hydrogen transfer reactions of thiyl radicals from glutathione: formation of carbon-centered radical at Glu, Cys, and Gly.
Glutathione thiyl radicals (GS(•)) were generated in H(2)O and D(2)O by either exposure of GSH to AAPH, photoirradiation of GSH in the presence of acetone, or photoirradiation of GSSG. Detailed interpretation of the fragmentation pathways of deuterated GSH and GSH derivatives during mass spectrometry analysis allowed us to demonstrate that reversible intramolecular H-atom transfer reactions between GS(•) and C-H bonds at Cys[(α)C], Cys[(β)C], and Gly[(α)C] are possible.
Department of Pharmaceutical Chemistry, University of Kansas, 2095 Constant Avenue, Lawrence, KA 66047, USA.
Olivier
O
Mozziconacci
Todd D
TD
Williams
Christian
C
Schöneich
D000096:Acetone / Q000737:chemistry; D000578:Amidines / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D003545:Cysteine / Q000737:chemistry*; D041961:Deuterium Exchange Measurement; D017666:Deuterium Oxide / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry*; D018698:Glutamic Acid / Q000737:chemistry*; D005978:Glutathione / Q000737:chemistry*; D019803:Glutathione Disulfide / Q000737:chemistry; D005998:Glycine / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D010782:Photolysis; D021241:Spectrometry, Mass, Electrospray Ionization; D014466:Ultraviolet Rays; D014867:Water / Q000737:chemistry
D000578:Amidines; D005609:Free Radicals; D014867:Water; D000096:Acetone; D018698:Glutamic Acid; C046728:2,2'-azobis(2-amidinopropane); D002244:Carbon; D006859:Hydrogen; D005978:Glutathione; D017666:Deuterium Oxide; D003545:Cysteine; D005998:Glycine; D019803:Glutathione Disulfide