Pascal Ribéreau-Gayon - Handbook of Enology - Volume 1

The production of higher alcohols by yeasts appears to be linked not only to the catabolism of amino acids but also to their synthesis via the corresponding keto acids. These acids are derived from the metabolism of sugars. For example, propan‐1‐ol has no corresponding amino acid. It is derived from α ‐ketobutyrate that can be formed from pyruvate and acetyl‐CoA. α ‐Ketoisocaproate is a precursor of isoamyl alcohol and an intermediate in the synthesis of leucine. It too can be produced from α ‐acetolactate, which is derived from pyruvate. Most higher alcohols in wine can also be formed by the metabolism of glucose, without the involvement of amino acids.

FIGURE 2.27 Deamination of serine by a dehydratase.

FIGURE 2.28 Formation of higher alcohols from amino acids (Ehrlich reactions).

The physiological function of higher alcohol production by yeasts is not clear. It may be a simple waste of sugars, a detoxification process of the intracellular medium, or a means of regulating the metabolism of amino acids.

With the exception of phenylethanol, which has a rose‐like fragrance, higher alcohols smell bad. Most, such as isoamyl alcohol, have heavy solvent‐like odors. Methionol is a peculiar alcohol because it contains a sulfur atom. Its cooked‐cabbage odor has the lowest perception threshold (1.2 mg/l). It can be responsible for the most persistent and unpleasant off‐odors of reduction, especially in white wines (Volume 2, Section 8.6.2). In general, the winemaker should avoid excessive higher alcohol odors. Fortunately, their sensory impact is limited at their usual concentrations in wine, but it depends on the overall aroma intensity of the wine. Excessive yields and rain at the end of ripening can dilute the must, in which case the wine will have a low aroma intensity and the heavy, common character of higher alcohols can be pronounced.

The winemaking parameters that increase higher alcohol production by yeasts are well known: high pH, high fermentation temperature, and aeration. In red winemaking, the extraction of pomace constituents and the concern for rapid and complete fermentations impose both aeration and high temperatures. In this case, the production of higher alcohols by yeast cannot be limited. In white winemaking, a fermentation temperature between 20 and 22°C limits the formation of higher alcohols.

Ammonium and amino acid deficiencies in must lead to an increased formation of higher alcohols. Under these conditions, the yeast appears to recuperate all of the available amino nitrogen by transamination. It releases the unused carbon skeleton in the form of higher alcohols. Settling of white must for clarification purposes also limits the production of higher alcohols (Section 13.5.2).

The nature of the yeast (species and strain) responsible for fermentation also affects the production of higher alcohols. Certain species, such as Hansenula anomala , have long been known to produce a lot of these compounds, especially under aerobic conditions (Guymon et al ., 1961). However, production by wine yeasts is limited, even in spontaneous fermentation. More recently, various researchers (Kishimoto, 1994; Masneuf, 1996; Masneuf‐Pomarède et al ., 2010) have shown that most Saccharomyces bayanus strains (formerly called uvarum ) produce considerably more phenylethanol than does S. cerevisiae . Lastly, the production of higher alcohols in S. cerevisiae depends on the strain. Limited production of higher alcohols (with the exception of phenylethanol) should be among the selection criteria for wine yeasts.

TABLE 2.4 The Principal Higher Alcohols Found in Wine and Their Amino Acid Precursors

Higher alcohol	Concentration in wine (mg/1)	Amino acid precursor
3‐Methylbutan‐1‐ol orisoamyl alcohol	80–300	Leucine
2‐Methylbutan‐2‐ol oractive amyl alcohol	30–100	Isoleucine
2‐Methylpropan‐1‐ol orisobutyl alcohol	50–150	Valine
Phenylethanol	10–100	Phenylalanine
Tyrosol	20–50	Tyrosine
Propan‐1‐ol	10–50	?
Butan‐1‐ol	1–10	?
Tryptophol	0–1	Tryptophan
γ ‐Butyrolatone	0–5	Glutamic acid
Methionol	0–5	Methionine

Due to their esterase activities, yeasts form various esters (a few milligrams per liter). The most important acetates of higher alcohols are isoamyl acetate (banana aroma) and phenylethyl acetate (rose aroma). Although they are not linked to nitrogen metabolism, ethyl esters of medium‐chain fatty acids are also involved. They are formed by the condensation of acetyl‐CoA. These esters have more interesting aromas than the others. Hexanoate has a flowery and fruity aroma reminiscent of green apples. Ethyl decanoate has a soap‐like odor. In white winemaking, the production of these esters can be increased by lowering the fermentation temperature and increasing must clarification. Certain yeast strains (71B) produce large quantities of these compounds, which contribute to the fermentation aroma of young wines. They are rapidly hydrolyzed during their first year in bottle and have no long‐term influence on the aroma of white wines.