title: Application of a molecular sensory science approach to alkalized cocoa (Theobroma cacao): structure determination and sensory activity of nonenzymatically C-glycosylated flavan-3-ols.
abstract: Application of comparative taste dilution analyses on nonalkalized and alkalized cocoa powder revealed the detection of a velvety, smoothly astringent tasting fraction, which was predominantly present in the alkalized sample. LC-MS/MS analysis, 1D- and 2D-NMR, and CD spectroscopy as well as model alkalization reactions led to the unequivocal identification of the velvety, smoothly astringent molecules as a series of catechin- and epicatechin-C-glycopyranosides. Besides the previously reported (-)-epicatechin-8-C-beta-D-galactopyranoside, additional flavan-3-ol-C-glycosides, namely, (-)-epicatechin-8-C-beta-D-glucopyranoside, (-)-catechin-8-C-beta-D-glucopyranoside, (-)-catechin-6-C-beta-D-glucopyranoside, (-)-epicatechin-6-C-beta-D-glucopyranoside, (-)-catechin-8-C-beta-D-galactopyranoside, (-)-catechin-6-C-beta-D-galactopyranoside, (-)-catechin-6-C,8-C-beta-D-diglucopyranoside, (-)-epicatechin-6-C,8-C-beta-D-digalactopyranoside, (-)-catechin-6-C,8-C-beta-D-digalactopyranoside, and epicatechin-6-C,8-C-beta-D-diglucopyranoside, were identified for the first time in cocoa. Most surprisingly, these phenol glycoconjugates were demonstrated by model experiments to be formed via a novel nonenzymatic C-glycosylation of flavan-3-ols. Using the recently developed half-tongue test, human recognition thresholds for the astringent and mouth-drying oral sensation were determined to be between 1.1 and 99.5 micro mol/L (water) depending on the sugar and the intramolecular binding position as well as the aglycone.
authors.affiliation: Institut für Lebensmittelchemie, Universität Münster, Corrensstrasse 45, D-48149 Münster, Germany.
authors.forename: Timo
authors.initials: T
authors.lastname: Stark
authors.forename: Thomas
authors.initials: T
authors.lastname: Hofmann
mesh_terms: D000328:Adult; D002099:Cacao / Q000737:chemistry*; D002392:Catechin / Q000737:chemistry; D005260:Female; D005419:Flavonoids / Q000737:chemistry*; D006027:Glycosides / Q000737:chemistry*; D006031:Glycosylation; D006801:Humans; D006863:Hydrogen-Ion Concentration; D008297:Male; D013329:Structure-Activity Relationship; D013649:Taste
chemical_list: D005419:Flavonoids; D006027:Glycosides; C404987:flavan-3-ol; D002392:Catechin