title: Chemical interactions between odor-active thiols and melanoidins involved in the aroma staling of coffee beverages.
abstract: Comparative aroma dilution analyses of the headspaces of aqueous solutions containing either the total volatiles isolated from a fresh coffee brew, or these volatiles remixed with the melanoidins isolated from coffee brew, revealed a drastic decrease in the concentrations of the odorous thiols 2-furfurylthiol, 3-methyl-2-butenthiol, 3-mercapto-3-methylbutyl formate, 2-methyl-3-furanthiol, and methanethiol when melanoidins were present. Among these thiols, 2-furfurylthiol was affected the most: e.g., its concentration decreased by a factor of 16 upon addition of melanoidins. This was accompanied by a decrease in the overall roasty-sulfury aroma. Quantitations performed by means of stable isotope dilution assays confirmed the rapid loss of all thiols with increasing time while keeping the coffee brew warm in a thermos flask. Using [2H2]-2-furfurylthiol as an example, [2H]-NMR and LC/MS spectroscopy gave strong evidence that thiols are covalently bound to the coffee melanoidins via Maillard-derived pyrazinium compounds formed as oxidation products of 1,4-bis-(5-amino-5-carboxy-1-pentyl)pyrazinium radical cations (CROSSPY). Using synthetic 1,4-diethyl diquaternary pyrazinium ions and 2-furfurylthiol, it was shown that 2-(2-furyl)methylthio-1,4-dihydro-pyrazines, bis[2-(2-furyl)methylthio]-1,4-dihydro-pyrazines, and 2-(2-furyl)methylthio-hydroxy-1,4-dihydro-pyrazines were formed as the primary reaction products. Similar results were obtained for models in which either 1,4-diethyl diquaternary pyrazinium ions were substituted by Nalpha-acetyl-L-lysine/glycolaldehyde, or the 2-furfurylthiol by 2-methyl-3-furanthiol and 3-mercapto-3-methylbutyl formate. On the basis of these results it can be concluded that the CROSSPY-derived pyrazinium intermediates are involved in the rapid covalent binding of odorous thiols to melanoidins, and, consequently, are responsible for the decrease in the sulfury-roasty odor quality observed shortly after preparation of the coffee brew.
authors.affiliation: Deutsche Forschungsanstalt für Lebensmittelchemie, Lichtenbergstrasse 4, D-85748 Garching, Germany. thomas.hofmann@lrz.tum.de
authors.forename: Thomas
authors.initials: T
authors.lastname: Hofmann
authors.forename: Peter
authors.initials: P
authors.lastname: Schieberle
mesh_terms: D001665:Binding Sites; D003069:Coffee / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D009682:Magnetic Resonance Spectroscopy; D015416:Maillard Reaction; D008956:Models, Chemical; D009812:Odorants / Q000032:analysis*; D011108:Polymers / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014835:Volatilization
chemical_list: D003069:Coffee; D011108:Polymers; D013438:Sulfhydryl Compounds; C011908:melanoidin polymers