The acid-promoted reaction of the green tea polyphenol epigallocatechin gallate with nitrite ions.
Exposure of 400 microM (-)-epigallocatechin-3-O-gallate (EGCG), the main polyphenolic constituent of green tea, to equimolar concentrations of nitrite ions in 0.5 M HCl at 37 degrees C resulted in the formation of a distinct pattern of products that were trapped as phenazine derivatives by treatment with o-phenylenediamine. Repeated chromatographic fractionation eventually allowed isolation of four main species, which were identified by 2D NMR and MS analysis as 1b, derived from EGCG quinone 1a, the isomeric oximes 2b,c, arising from nitrosation of EGCG on the pyrogallol B-ring, and the dioxime 4b in which the A-ring was doubly substituted. At lower EGCG concentrations (e.g., 25 microM) and at pH 3, reaction with equimolar amounts of nitrite gave 1b as the first formed species, whereas nitrosation products 2b,c and 4b became detectable only with excess nitrite. Similar reaction of chemically prepared 1a with acidic nitrite led to the formation of 2b,c and 4b, suggesting that this quinone may be an intermediate in the nitrosation of EGCG. Exposure of green tea extracts to acidic nitrite ions resulted in the conversion of EGCG to 1a, detected as 1b. Overall these results substantiate literature reports suggesting that the protective effects of EGCG against nitrosation involve mainly an initial redox exchange process and hint at a hitherto unrecognized property of quinone 1a as a potential scavenger of nitrosating species.
Panzella
Lucia
L
Department of Organic Chemistry and Biochemistry, University of Naples Federico II, Complesso Universitario Monte S. Angelo, Via Cinthia 4, I-80126 Naples, Italy.
Manini
Paola
P
Napolitano
Alessandra
A
d'Ischia
Marco
M
D002392:Catechin / Q000031:analogs & derivatives* / Q000737:chemistry / Q000378:metabolism* / Q000494:pharmacology; D005753:Gastric Mucosa / Q000378:metabolism; D006801:Humans; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D009573:Nitrites / Q000378:metabolism* / Q000633:toxicity; D013662:Tea
D009573:Nitrites; D013662:Tea; D002392:Catechin; C045651:epigallocatechin gallate