title: Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation.
abstract: Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 μM) were reacted with Fe(III) (100 or 200 μM) alone and in combination with Cu(II) (25 or 50 μM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated.
authors.affiliation: Department of Food Science, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Gal Y
authors.initials: GY
authors.lastname: Kreitman
authors.affiliation: 44 Sandwich Road, Ash, Canterbury, Kent CT3 2AF, United Kingdom.
authors.forename: John C
authors.initials: JC
authors.lastname: Danilewicz
authors.affiliation: School of Agriculture, Food and Wine, Waite Research Institute, The University of Adelaide , PMB 1, Glen Osmond, South Australia 5064, Australia.
authors.forename: David W
authors.initials: DW
authors.lastname: Jeffery
authors.affiliation: Department of Food Science, The Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Ryan J
authors.initials: RJ
authors.lastname: Elias
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006862:Hydrogen Sulfide / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D014920:Wine / Q000032:analysis*
chemical_list: D013438:Sulfhydryl Compounds; D003300:Copper; D007501:Iron; D010100:Oxygen; D006862:Hydrogen Sulfide
keywords: H2S; copper; iron; oxidation; reaction mechanism; thiols; wine aroma