PMID:15489164
| Citation |
Dorrestein, PC, Zhai, H, McLafferty, FW and Begley, TP (2004) The biosynthesis of the thiazole phosphate moiety of thiamin: the sulfur transfer mediated by the sulfur carrier protein ThiS. Chem. Biol. 11:1373-81 |
|---|---|
| Abstract |
Thiamin-pyrophosphate is an essential cofactor in all living systems. The biosynthesis of both the thiazole and the pyrimidine moieties of this cofactor involves new biosynthetic chemistry. Thiazole-phosphate synthase (ThiG) catalyses the formation of the thiazole moiety of thiamin-pyrophosphate from 1-deoxy-D-xylulose-5-phosphate (DXP), dehydroglycine and the sulfur carrier protein (ThiS), modified on its carboxy terminus as a thiocarboxylate (ThiS-thiocarboxylate). Thiazole biosynthesis is initiated by the formation of a ThiG/DXP imine, which then tautomerizes to an amino-ketone. In this paper we study the sulfur transfer from ThiS-thiocarboxylate to this amino-ketone and trap a new thioenolate intermediate. Surprisingly, thiazole formation results in the replacement of the ThiS-thiocarboxylate sulfur with an oxygen from DXP and not from the buffer, as shown by electrospray ionization Fourier transform mass spectrometry (ESI-FTMS) using (18)O labeling of the 13C-, 15N-depleted protein. These observations further clarify the mechanism of the complex thiazole biosynthesis in bacteria. |
| Links |
PubMed Online version:10.1016/j.chembiol.2004.08.009 |
| Keywords |
Amino Acid Sequence; Bacillus subtilis/enzymology; Carrier Proteins/biosynthesis; Catalysis; Escherichia coli Proteins/biosynthesis; Molecular Sequence Data; Pentosephosphates/biosynthesis; Spectrometry, Mass, Electrospray Ionization/methods; Sulfur Compounds/analysis; Sulfur Compounds/chemical synthesis; Thiamine/biosynthesis; Thiamine/chemistry; Thiamine Triphosphate/chemical synthesis; Thiamine Triphosphate/metabolism; Thiazoles/chemistry; Thiazoles/metabolism; Transferases/chemistry; Transferases/metabolism |
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