title: Model system-based mechanistic studies of black tea thearubigin formation.
abstract: Thearubigins are the most abundant pigments found in black tea, comprising polyphenolic oxidation products, whose composition and chemical nature have remained unresolved until recently. In the course of studying the mechanism of thearubigin formation from green tea flavan-3-ols, a model system, based on electrochemical oxidation of one of the main tea flavan-3-ol substrates, epigallocatechin gallate (EGCG), was employed. Reaction intermediates and products were subsequently analysed using mass spectrometry techniques, allowing for the identification of key intermediates and products. The results provided, for the first time, spectroscopic evidence for the structures of primary oxidation products, and led to the conclusion that oxidation is mainly taking place on the B-ring and the galloyl group, where the oxidized components undergo oxidative coupling for the formation of theaflavins, theasinensins and polyhydroxylated flavan-3-ols, all precursors for thearubigin formation. Furthermore, density functional theory (DFT) calculations were carried out to support key findings.
authors.affiliation: School of Engineering and Science, Chemistry, Jacobs University Bremen, 28759 Bremen, Germany.
authors.forename: Ghada H
authors.initials: GH
authors.lastname: Yassin
authors.affiliation: Olivier van Noortlaan 120, PO Box 114, 3130 AC Vlaardingen, Netherlands.
authors.forename: Jan H
authors.initials: JH
authors.lastname: Koek
authors.affiliation: School of Engineering and Science, Chemistry, Jacobs University Bremen, 28759 Bremen, Germany. Electronic address: n.kuhnert@jacobs-university.de.
authors.forename: Nikolai
authors.initials: N
authors.lastname: Kuhnert
mesh_terms: D002392:Catechin / Q000031:analogs & derivatives* / Q000737:chemistry; D005419:Flavonoids / Q000737:chemistry*; D013058:Mass Spectrometry / Q000379:methods*; D010084:Oxidation-Reduction; D059808:Polyphenols / Q000737:chemistry*; D013662:Tea / Q000737:chemistry*
chemical_list: D005419:Flavonoids; D059808:Polyphenols; D013662:Tea; C086701:thearubigin; C404987:flavan-3-ol; D002392:Catechin
keywords: Density functional theory; ESI tandem LC–MS; Theaflavins; Thearubigins; Theasinensins