Wine Chemistry and Biochemistry

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8D Yeasts and Wine Flavour 347


et al. 1973). Deficiencies in pyridoxine, a cofactor in the methionine biosynthetic


pathway, can also result in large production of H 2 S, particularly in the case of yeast


strains that are unable to synthesize this vitamin (Monk 1986). Lack of biotin can


also cause an increase in the formation of H 2 S (Thomas and Surdin-Kerjan 1997),


possibly due to the role of this vitamin as cofactor in the biosynthesis ofO-acetyl-


L-homoserine (Bohlscheid et al. 2007). Addition of commercially available fermen-


tation nutrients containing the above-mentioned vitamins is a common measure to


reduce the risk of H 2 S production in the wine industry.


Nevertheless, under winemaking conditions, nutrient supplementation has not


eliminated the risk of H 2 S production (Henschke and Jiranek 1991; Jiranek et al.


1995a; Park et al. 2000; Spiropoulos et al.2000). Recent genetic studies highlight


the complexity of regulation of the sulfate reductive assimilation pathway (Lin-


derholm et al. 2006, 2008; Spiropoulos et al. 2000). Controlling sulfite reductase


activity is an obvious target for lowering excessive H 2 S production to acceptable


levels but so far no commercial strains have been developed (Sutherland et al. 2003;


Zambonelli et al. 1975). An inability to control H 2 S liberation by over-expression


of genes associate with H 2 S sequestration (MET17)andS-amino acid biosynthesis


(CYS4andMET6) suggests that metabolite flux might be a limiting factor rather


than inadequate enzyme activities. Analysis of the S-amino acids biosynthetic path-


way, by studying various mutants carrying gene defects, suggests that some of


these genes, or substrates or products of their corresponding protein products, might


play key roles in regulating sulfate reduction (Linderholm et al. 2008). Interactions


between the sulfate assimilation pathway and amino acid pathways and various
metabolites (acetaldehyde) provide an insight into the complexity of pathway regu-


lation (Aranda and del Olmo 2004; Backhus et al. 2001; Marks et al. 2003).


Organic Volatile Sulfur Compounds


Conditions that favour H 2 S production also favour production of other volatile sulfur


compounds, methanethiol and methanethioacetate (Rauhut et al. 1996), suggesting


a metabolic link to methionine catabolism. Catabolism of this amino acid essen-


tially follows the Ehrlich pathway, as shown in Fig 8D.5. The first step involves


transamination to yield the keto acid -keto-gamma-(methylthio)butyric acid, which


is decarboxylated to 3-(methylthio)-1-proprionaldehyde specifically by Ydr380wp,


and reduced to 3-(methylthio)-1-propanol (methionol) by alcohol dehydrogenases


(Fig 8D.8). The production of methionol is likely to be regulated in a similar man-


ner to that of other higher alcohols, that is, higher concentrations are formed in


low to moderate nitrogen musts (Hern ́andez-Orte et al. 2005). Both methionine and


-keto--(methylthio)butyric acid can act as a source of methanethiol through a


demethiolase step, which also produces alpha-ketobutyric acid (Perp`ete et al. 2006).


Yeast strains with intense H 2 S production also produce higher amounts of thioacetic


acid esters of methanethiol and ethanethiol (Rauhut et al. 1996); it is likely that these


thiols are esterified by alcohol acetyltransferase in the same way as ethyl acetate is


formed from and acetic acid. The formation of acetic acid esters is a major problem


in winemaking since these compounds are not removed from wine during fining

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