title: A method to quantify quinone reaction rates with wine relevant nucleophiles: a key to the understanding of oxidative loss of varietal thiols.
abstract: Quinones are key reactive electrophilic oxidation intermediates in wine. To address this question, the model 4-methyl-1,2-benzoquinone was prepared to study how it reacts with wine nucleophiles. Those investigated included the varietal volatile thiols 4-methyl-4-sulfanylpentan-2-one (4MSP), 3-sulfanylhexan-1-ol (3SH), and 2-furanmethanethiol (2FMT); hydrogen sulfide (H2S); glutathione (GSH); sulfur dioxide; ascorbic acid (AA); and the amino acids methionine (Met) and phenylalanine (Phe) in the first kinetic study of these reactions. Products were observed in fair to quantitative yields, but yields were negligible for the amino acids. The reaction rates of 4-methyl-1,2-benzoquinone toward the nucleophiles were quantified by UV-vis spectrometry monitoring the loss of the quinone chromophore. The observed reaction rates spanned three orders of magnitude, from the unreactive amino acids (Met and Phe) (KNu = 0.0002 s(-1)) to the most reactive nucleophile, hydrogen sulfide (KH2S = 0.4188 s(-1)). Analysis of the kinetic data showed three categories. The first group consisted of the amino acids (Met and Phe) having rates of essentially zero. Next, phloroglucinol has a low rate (KPhl = 0.0064 s(-1)). The next group of compounds includes the volatile thiols having increasing reactions rates K as steric inhibition declined (K4MSP = 0.0060 s(-1), K3SH = 0.0578 s(-1), and K2FMT = 0.0837 s(-1)). These volatile thiols (4MSP, 3SH, 2FMT), important for varietal aromas, showed lower K values than those of the third group, the wine antioxidant compounds (SO2, GSH, AA) and H2S (KNu = 0.3343-0.4188 s(-1)). The characterization of the reaction products between the nucleophiles and 4-methyl-1,2-benzoquinone was performed by using HPLC with high-resolution MS analysis. This study presents the first evidence that the antioxidant compounds, H2S, and wine flavanols could react preferentially with oxidation-induced quinones under specific conditions, providing insight into a mechanism for their protective effect.
authors.affiliation: Department of Viticulture and Enology, University of California , Davis, California 95616, United States.
authors.forename: Maria
authors.initials: M
authors.lastname: Nikolantonaki
authors.forename: Andrew L
authors.initials: AL
authors.lastname: Waterhouse
mesh_terms: D016227:Benzoquinones / Q000032:analysis / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D005663:Furans / Q000737:chemistry; D005978:Glutathione / Q000737:chemistry; D000441:Hexanols / Q000737:chemistry; D006862:Hydrogen Sulfide / Q000737:chemistry; D007700:Kinetics; D013058:Mass Spectrometry / Q000379:methods; D008715:Methionine / Q000737:chemistry; D010084:Oxidation-Reduction; D010422:Pentanones / Q000737:chemistry; D010649:Phenylalanine / Q000737:chemistry; D011809:Quinones / Q000032:analysis* / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000032:analysis / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000737:chemistry; D014920:Wine / Q000032:analysis
chemical_list: D016227:Benzoquinones; D005663:Furans; D000441:Hexanols; D010422:Pentanones; D011809:Quinones; D013438:Sulfhydryl Compounds; D013458:Sulfur Dioxide; C088487:4-methyl-1,2-benzoquinone; D010649:Phenylalanine; C530764:4-methyl-4-sulfanylpentan-2-one; D008715:Methionine; D005978:Glutathione; C443400:2-methyl-3-furanthiol; C477019:3-mercaptohexanol; D006862:Hydrogen Sulfide