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Identification of Flavone Glucuronide Isomers by Metal Complexation and Tandem Mass Spectrometry: Regioselectivity of Uridine 5 '-Diphosphate-Glucuronosyltransferase Isozymes in the Biotransformation of Flavones

  作者 ROBOTHAM SCOTT A; BRODBELT JENNIFER S  
  选自 期刊  Journal of Agricultural and Food Chemistry;  卷期  2013年61-7;  页码  1457-1463  
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[摘要]Flavone glucuronide isomers of five flavones (chrysin, apigenin, luteolin, baicalein, and scutellarein) were differentiated by collision-induced dissociation of [Co(II) (flavone-H) (4,7-diphenyl-1,10-phenanthroline)2r complexes. The complexes were generated via postcolumn addition of a metal ligand solution after separation of the glucuronide products generated upon incubation of each flavone with an array of uridine 5'-diphosphate (UDP)-glucuronosyltransferase (UGT) isozymes. Elucidation of the glucuronide isomers allowed a systematic investigation of the regioselectivity of 12 human UGT isozymes, including 8 UGT1A and 4 UGT2B isozymes. Glucuronidation of the 7-0H position was the preferred site for all the flavones except for luteolin, which possessed adjacent hydroxyl groups on the B ring. For all flavones and UGT isozymes, glucuronidation of the 5-OH position was never observed. As confirmed by the metal complexation/MS/MS strategy, glucuronidation of the 6-OH position only occurred for baicalein and scutellarein when incubated with three of the UGT isozymes.

 
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