title: Analysis of the diastereoisomers of the cysteinylated aroma precursor of 3-sulfanylhexanol in Vitis vinifera grape must by gas chromatography coupled with ion trap tandem mass spectrometry.
abstract: The diastereoisomeric distribution of S-3-(hexan-1-ol)cysteine (P-3SH), the cysteinylated precursor of 3-sulfanylhexan-1-ol (3SH) in Vitis vinifera grape juice, was determined by a new method. This procedure is based on the purification of P-3SH in a small volume of must (500 microL) by affinity chromatography, followed by the separation of chiral molecules in derivative forms by gas chromatography coupled with ion trap tandem mass spectrometry (GC-MS/MS). The diastereoisomers were easily separated using heptafluorobutyric anhydride and heptafluorobutanol (HFBA and HFOH) as derivatization reagents. Method validation was conducted using samples of grape juice, synthetic must, fermenting must, and wine that were fortified with P-3SH at concentrations of 0.6 and 2.5 microM. The relative standard deviation (RSD) and limit of detection (LOD) of the GC-MS/MS method were 4.6% and 1.5 nM, respectively. P-3SH assays in Bordeaux white grape juice affected by Botrytis cinerea showed an unusually increased proportion of the RS form of the precursor (approximately RR:RS=30:70) as compared to a diastereoisomer ratio (in the vicinity of 50:50) in healthy grape juice.
authors.affiliation: Université Victor Segalen Bordeaux 2, Faculté d'Oenologie, UMR Oenologie, INRA, Institut des Sciences de la Vigne et du Vin, 351 cours de la Libération, Talence Cedex, France.
authors.forename: Cécile
authors.initials: C
authors.lastname: Thibon
authors.forename: Svitlana
authors.initials: S
authors.lastname: Shinkaruk
authors.forename: Takatoshi
authors.initials: T
authors.lastname: Tominaga
authors.forename: Bernard
authors.initials: B
authors.lastname: Bennetau
authors.forename: Denis
authors.initials: D
authors.lastname: Dubourdieu
mesh_terms: D003545:Cysteine / Q000031:analogs & derivatives* / Q000032:analysis; D005285:Fermentation; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods; D015203:Reproducibility of Results; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013237:Stereoisomerism; D053719:Tandem Mass Spectrometry / Q000379:methods; D027843:Vitis / Q000737:chemistry*
chemical_list: C528100:S-3-(hexan-1-ol)cysteine; D003545:Cysteine