C H A P T E R

2
Composition of Grape Must
O U T L I N E
1. Grape Must 13
2. Chemical Families Present in Must 15
2.1. Sugars 15
Disaccharides 17
2.2. Organic Acids 17
2.3. Nitrogen Compounds 18
2.4. Minerals 19
2.5. Polyphenols 19
2.6. Vitamins 20
2.7. Aromatic Compounds 20
Terpenes 20
Carotenoids 21
Pyrazines 21
Alcohols and Aldehydes 21
1. GRAPE MUST
Grape must is the liquid obtained by the gentle crushing or pressing of grapes. Pressing
takes place once the grapes (either destemmed or still in clusters) have been gently crushed.
Even within the same winemaking region, must composition varies according to several
factors, including:
The type and variety of grapes used,
The ripeness and health of the grapes (ripeness depends on a range of factors, such as the
climate during the growing season, the type of soil, and the fertilizers used),
The pressure exerted on the grapes.
Musts are classied as free-run must (or juice), which is obtained by the simple crushing of
grapes, or press-fraction must, which is obtained by subjecting the grapes to increasing levels
of pressure. There are therefore many types of must.
13 Enological Chemistry. DOI: 10.1016/B978-0-12-388438-1.00002-9 Copyright 2012 Elsevier Inc. All rights reserved.
Quality white wines are made only from free-run must (known in Spain as mosto or or
mosto yema) or rst-press fractions. Subsequent fractions can be used to make other products,
such as the more intense, deeper-colored press wines.
As the press fractions, and logically, the pressure exerted on the grapes increase to
improve the yield, the resulting juice becomes increasingly rich in substances derived
from the solid parts of the grape, such as the stems (when the grapes are crushed in clusters),
the skins, and the pips.
Figure 2.1 shows variations in must pH and the concentration of several compounds
derived from grape solids over successive press fractions. As can be seen, polyphenol and
potassium levels increase after several presses, as the increased pressure on the solid parts
of the grape extracts a greater proportion of these compounds. The pH of successive press
fractions is related to the amount of free acids and acid salts in the different parts of the grape
and is therefore also a reection of the pHof the tissue of the solid parts of the grape (which is
higher than that of the pulp). pH is also inuenced by potassium levels, as potassium ions
neutralize most of the acids in the berry. Iron levels are also directly related to the number
of presses, but it should be noted that pressing equipment, which is generally made of
iron or stainless steel, can also contribute to these levels.
It is thus clear that there is no such thing as a single must, and that to understand must
composition we must take into account the different treatments that both the grape and its
juice undergo in order to obtain a reliable raw material for fermentation.
The following substances or groups of substances, shown in order of abundance, are
present in must:
Water
Sugars
Organic acids
Nitrogen compounds
Minerals
Polyphenols
Vitamins
Aromatic compounds
TABLE 2.1 Composition of Musts Obtained at Increasing Press Pressures
Liquid
Volume (%)
Dry Extract
(g/100 mL)
Sugars
(g/L)
Acidity
(g/L)
Ash
(g/L)
Alkalinity of
Ash (meq/L)
Tartaric
Acid (g/L)
Malic
Acid (g/L)
Free run 60 21 194 7.5 3.4 32 5.6 3.8
First press 25 22 192 7.7 3.4 34 5.8 4.0
Second press 10 22 191 6.5 3.8 34 4.4 4.2
Third press 4 25 187 5.4 4.9 40 3.6 4.3
Fourth press 1 31 176 5.1 5.6 46 3.7 4.3
Total 100 22 193 7.3 3.6 34 5.3 3.9
Adapted from De Rosa, 1988.
2. COMPOSITION OF GRAPE MUST 14
ENOLOGICAL CHEMISTRY
2. CHEMICAL FAMILIES PRESENT IN MUST
All chemical families are characterized by a functional group, which is a collection of one
or more atoms within a molecule that provide the molecule with a unique chemical function,
specic to the functional group.
2.1. Sugars
The sugars present in must are polyalcohols with a carbonyl group. These are organic
compounds that contain several OH groups along with an aldehyde or ketone group.
According to the established nomenclature, the sufx -ose should be used to refer to these
compounds, which can be aldoses or ketoses. The D and L prexes used in sugars are related
to the () or () enantiomer of the glyceraldehyde from which they are derived. Accordingly,
monosaccharides in which the chiral center that is furthest from the aldehyde or ketone group
has the same conguration as the corresponding D-glyceraldehyde are members of the D series,
while those with the opposite conguration are members of the L series. In a Fischer projection,
the OHgroup is to the right of the chiral center of D-glyceraldehyde. The D or L conguration
is not related to the ability of the enantiomers to rotate polarized light to the right or left.
The most abundant sugars found in must are monosaccharides with six carbon atoms:
Glucose: 6-carbon aldose (dextrose)
Fructose: 6-carbon ketose (levulose)
0
750
1500
2250
3000
3750
0
5
10
15
20
25
% of must in successive press fractions
P
o
l
y
p
h
e
n
o
l
s


(
m
g
/
L
)
p
H
P
o
t
a
s
s
i
u
m

(
m
g
/
L
)
I
r
o
n

(
m
g
/
L
)
% of must in successive press fractions
% of must in successive press fractions % of must in successive press fractions
2.75
3.25
3.75
4.25
0
0
0.4
0.8
1.2
1.6
0 20 40 60 80 100
20 40 60 80 100
0 20 40 60 80 100
0 20 40 60 80 100
FIGURE 2.1 Must composition according to number of presses.
2. CHEMICAL FAMILIES PRESENT IN MUST 15
ENOLOGICAL CHEMISTRY
The chemical structures for D-glucose and D-fructose are shown below:
The most relevant 5-carbon monosaccharides are the D-aldoses:
CH
2
OH
C
C
C
C
CH
2
OH
O
H HO
OH H
OH H
C
C
C
C
C
CH
2
OH
O H
OH H
H HO
OH H
OH H
Glucose Fructose
C
C
C
C
CH
2
OH
O
H
OH H
H HO
OH H
C
C
C
C
CH
2
OH
O
H
OH H
OH H
OH H
C
C
C
C
CH
2
OH
O
H
H HO
OH H
OH H
Xylose Ribose Arabinose
C
1
O C
CH
2
H
H
O H
H
OH
OH
H
H
OH
OH
C
1
O
C
CH
2
H
H
O H
H
OH
OH
H
OH
H
OH
C
1
OH C
CH
2
6
H
H
O H
H
OH
OH
H
H
O
OH
C
1
OH
C
CH
2
6
H
H
O H
H
OH
OH
H
H
O
OH
C
1
C
C
C
C
O
H
H
H
H
CH
2
6
OH
O H
OH
OH
OH
H
D-Glucose
(Fischer projection)
-Glucopyranose
-Glucopyranose
D-Glucose
(Haworth projection)
FIGURE 2.2 Haworth projection of glucose.
2. COMPOSITION OF GRAPE MUST 16
ENOLOGICAL CHEMISTRY
Disaccharides
Disaccharides are formed by joining pairs of various monosaccharides via a- or
b-glycosidic bonds. A hemiacetal hydroxyl group formed from the oxygen of the carbonyl
group (CO) always participates in the formation of these bonds. In certain cases, all the
carbonyl groups in the molecule are used. This means that the resulting product (e.g.,
sucrose) lacks reducing power, because the two monosaccharide units are linked by the
hemiacetal hydroxyls of the two molecules, hence both are blocked.
In the case of maltose, which is a disaccharide formed by two glucose molecules, only one
hemiacetal hydroxyl group is blocked, meaning that the second one retains the reducing
properties characteristic of aldehydes.
Glycosidic bonding of these disaccharides to other monosaccharides gives rise to
polysaccharides.
2.2. Organic Acids
Organic acids possess a COOH functional group. In must, however, acids also possess
other groups, such as the OH group of alcohols.
C
1
C
1
O
C
CH
2
OH
H
H
OH
H
OH
OH
Maltose
H
H
H
O
C
O
CH
2
OH
H
H
OH
OH
H
OH
H
C
1
O
C
CH
2
OH
H
H
OH
H
OH
OH
H
H
O
C
2
O
CH
2
OH
6
HO
OH
CH
2
OH
Sucrose
CH
2
C
CH
2
OH
COOH
COOH
HOOC
C
C H
COOH
HO
OH H
COOH
C
C OH
COOH
H
H H
COOH
Malic acid Citric acid Tartaric acid
2. CHEMICAL FAMILIES PRESENT IN MUST 17
ENOLOGICAL CHEMISTRY
Other sugar-related compounds are uronic acids, which are the result of the oxidation of
the OHgroup on carbon 6 of a sugar to form a carboxyl group, and aldonic acids, which are
formed by the oxidation of the aldehyde group of an aldose. Other acids of interest are gal-
acturonic acid, which is the main component of grape pectins, and gluconic acid, which is
highly abundant in rotten grapes. Must produced from rotten grapes can also contain large
quantities of acetic acid.
2.3. Nitrogen Compounds
The main nitrogen compounds found in must are amino acids, either in free form or as
polypeptides or proteins.
The characteristic functional group of amino acids is shown below:
All naturally occurring amino acids are a-amino acids, because the amine group (NH
2
) is
bound to the carbon immediately adjacent to the one bearing the acid group (which is pref-
erentially used to name these compounds). Amino acids are joined by peptide bonds to form
peptides and proteins.
Nitrogen in the formof ammoniumions is the most assimilable formof nitrogen for yeasts,
and its decit in must can cause stuck fermentation.
C
C
C
C
OH H
H HO
H HO
OH H
COOH
COOH
C
C
C
C
OH H
H HO
H HO
OH H
COOH
CH
2
OH
Galacturonic acid Gluconic acid
C C
O
OH
H
NH
2
R
R1 C C
O
OH
NH
2
H
R2
C C
O
OH
N
H
2
H
R1 C C
O
N
H
NH
2
H
C
R2
C
H
OH
O
+
H
2
O
Peptide bond
2. COMPOSITION OF GRAPE MUST 18
ENOLOGICAL CHEMISTRY
2.4. Minerals
The mineral content of must and wine refers to the cations and elements that these contain.
Musts contain many mineral substances, which can be classied according to their electric
charge and abundance.
Cations
Abundant: K

, Ca
2
, Mg
2
, Na

, and Si
4
(plant macronutrients)
Less abundant: Fe
3
, Mn
2
, Zn
2
, Al
3
, Cu
2
, Ni
2
, Li

, Mo
4
, Co
2
, and V
3
(micronutrients)
Trace levels: Pb
2
, As
3
, Cd
2
, Se
4
, Hg
2
, and Pt
2
(ppb)
Anions
Abundant: PO
4
3
, SO
4
2
, Cl

Less abundant: Br

, I

2.5. Polyphenols
Grapes acquire their color from different compounds in the berries. The most noteworthy
of these are:
Chlorophyll
Carotenoids
Betalains
Polyphenols
Anthocyans 0red
Yellow avonoids 0yellow
Tannins 0brown
Polyphenolic compounds play an essential role in both grapes and wine, as they
are responsible for a range of sensory properties, such as appearance (color), taste
(astringency, bitterness), and aroma (volatile phenols). They can be classied as
follows:
Simple (non-avonoid) polyphenols
Flavonoids
Tannins
Others (stilbenes)
O H COOH
R1
R2
C
O
C
Simple phenol Flavonoid phenol
2. CHEMICAL FAMILIES PRESENT IN MUST 19
ENOLOGICAL CHEMISTRY
2.6. Vitamins
Grapes contain approximately 90 mg of vitamin C (ascorbic acid) per kilogram, as well as
small quantities of B-group vitamins (of which there are 10). Vitamins are particularly impor-
tant in wine making as they are very useful to yeasts and therefore essential for successful
alcoholic fermentation.
2.7. Aromatic Compounds
Two types of compounds confer aroma to must: grape-derived compounds (terpenes,
carotenoids, and pyrazines) and compounds that arise during avor extraction and pre-
fermentation treatments (alcohols and C
6
-aldehydes).
Terpenes
Terpenes are derived from isoprene units (2-methyl butadiene).
HO
HO
HO HO
HO
Linalool Diendiol I Diendiol II
TABLE 2.2 Vitamin Content of Grapes and Must
Grapes (mg/1000 grapes) Must (mg/L)
Thiamin 253 160e450
Riboavin 3.6 3e60
Pantothenic acid 660 0.5e1.4
Nicotinamide 700 0.68e2.6
Pyridoxine 260 0.16e.50
Biotin 2.2 1.5e4.2
Myo-inositol 297 380e710
Aminobenzoic acid 14 15e92
Folic acid 1.3 0e1.8
Choline 24 19e45
Cyanocobalamin 0e0.2
Ascorbic acid 30,000e50,000
2. COMPOSITION OF GRAPE MUST 20
ENOLOGICAL CHEMISTRY
Carotenoids
The main carotenoids found in must are b-carotene and lutein. When the grape berry
bursts, they can break down into compounds with 9, 10, 11, or 13 carbon atoms that are
more powerful odorants than their precursors. Of particular note are the C
13
-norisoprenoid
derivatives. These are divided into two groups: megastigmane forms and non-megastigmane
forms.
Pyrazines
Methoxypyrazines are nitrogen heterocyclic compounds with the following general
structure:
They are responsible for the vegetal aroma of certain grape varieties, such as Cabernet Sau-
vignon, Sauvignon Blanc, and Merlot.
Alcohols and Aldehydes
The most important aromatic alcohols and aldehydes are those with 6 carbon atoms (satu-
rated and unsaturated). These compounds originate enzymatically during prefermentation
Megastigmane forms
Non-megastigmane forms
-Damescenone
-Ionone
Trimethyldihydronaphthalene Vitispirane
O O
O
O
OH
Actinidol
N
N
O
CH
3
R
2. CHEMICAL FAMILIES PRESENT IN MUST 21
ENOLOGICAL CHEMISTRY
treatments via the aerobic oxidation of linoleic and linolenic acid (C
18:2
and C
18:3
). The
following compounds have been identied: hexanal, (E)-2-hexenal, (Z)-3-hexenal, hexanol-1,
(E)-2-hexen-1-ol, and (Z)-3-hexen-1-ol.
The list below shows the average quantitative composition of must, shown by groups of
compounds:
pH 3e4.5
Water 700e850 g/L
Sugars* 140e250 g/L
Organic acids 4e17 g/L
Nitrogen compounds 4e7 g/L
Polysaccharides 3e5 g/L
Minerals 0.8e2.8 g/L
Polyphenols 0.5 g/L
Vitamins 0.25e0.8 g/L
Aromatic compounds <0.5 g/L
* These levels can be much higher in certain musts, such as those made from raisined grapes or grapes with noble rot.
Other compounds of interest in musts are the wax and oleanolic acid present in the grape
bloom. This bloom retains traces of products used during the wine-growing process, such as
pesticides and other mineral compounds, e.g., copper sulfate. The bloom also contains yeasts
that participate in alcoholic fermentation.
H
3
C
CH
2
OH
Hexanol-1 (Z)-3-hexen-1-ol (E)-2-hexen-1-ol
H
3
C
CH
2
OH
H
3
C
CH
2
OH
2. COMPOSITION OF GRAPE MUST 22
ENOLOGICAL CHEMISTRY