coutaric acids was a natural phenomenon and the cis-form varieties was catechin (10–20 mg/kg), followed by

was the product of UV-induced isomeritation. The main
acid is normally the trans-caftaric acid, except in the
Moscatel de Grano Menudo, Cencibel and Shiraz varieties,
in which the main acid is trans-coutaric. Other authors
consider that the trans-coutaric acid/trans-caftaric acid ratio
may characterize wines according to their varietal origin
(Andre´s-Lacueva, 2002). White grape skins normally
contain higher concentrations. This is the case of trans-
caftaric acid, with high concentrations (30 mg/kg) in
Riesling, average concen-trations (10–20 mg/kg) in
Chardonnay, Gewurztrami-ner, Moscatel and Cabernet
Sauvignon and low concentrations (less than 10 mg/kg) in
the rest.
As regards the family of flavanols, it was observed that
the main monomer compound in the skins of white grape
epicatechin (0–10 mg/kg), which in some cases was below
the quantification level. No quantifiable quanti-ties of
procyanidin B2 were found and the concentra-tions of
procyanidins B1 and B3 varied between 12 and 48 mg/kg;
concentrations of procyanidin B3 were slightly higher, with
the exception of Gewu¨rztraminer. It is important to
highlight that the skins of the Viogner variety contained no
quantifiable amounts of any of the monomers and dimers
of this group of compounds and no quantifiable amounts of
epicatechin were found in those of the Riesling variety.
The concentrations of flavan-3-ol in red grape skins
were of the same order as those in white grape skins; these
findings coincide with those reported by other

Table 1
Polyphenolic compounds (mg/kg of fresh grape) in the skins of white grape varieties (mean value7SD)

Chardonnay Sauvignon Moscatel Gewu¨rztraminer Riesling Viogner

(n ¼ 10) Blanc (n ¼ 6) (n ¼ 4) (n ¼ 2) (n ¼ 2) (n ¼ 2)
cis-Caftaric 0.8570.561 0.3970.170 0.6270.213 0.7070.222 1.370.50 Traces
trans-Caftaric 20721.4 5.272.93 1473.7 1375.5 31716.4 2.471.22
cis-Coutaric 2.9a70.96 2.5a71.42 5.9b71.63 2.1a70.29 2.5a70.75 1.6a70.51
trans-Coutaric 7.9a74.34 4.9a73.36 18b75.26 6.1a71.75 7.0a73.75 1.9a70.91
trans-Fertaric 1.171.55 0.3070.091 0.6170.174 0.8770.082 2.670.79 Traces
Catechin 23b76.0 9.5a73.22 16a.b75.9 19a.b76.5 14a.b72.2 Traces
Epicatechin 5.8a.b72.48 3.4a70.27 2.6a70.00 8.3b70.55 Traces Traces
Procyanidin B3 37716.3 2578.2 2376.4 2174.4 2976.1 Traces
Procyanidin B1 23729.7 16712.2 21713.9 4876.2 1271.6 Traces
Quercetin glucuronide 25a716.1 12a73.9 54b77.0 17a78.4 30a71.5 67b720.3
Quercetin glucoside 17a77.4 8.9a73.79 20a78.8 24a70.4 22a73.8 66b712.9
Kaempferol glucoside 8.4a75.09 2.0a70.97 17b77.9 6.7a71.44 2.9a71.61 26c70.3
Isorhamnetin glucoside 0.4870.001 0.78a70.232 0.72a70.360 2.3b70.46 Traces Traces
Total hydroxycinnamates 33721.9 1374.7 3876.6 2275.8 45716.9 5.871.89
Total monomers flavan-3-ol 2876.5 1273.2 1975.9 2876.5 1472.2 9.770.00
Total dimers flavan-3-ol 60734.9 41714.7 44715.3 6977.6 4176.3 Traces
Total flavan-3-ols 89734.5 54715.0 63716.4 97710.0 5576.7 9.770.00
Total flavonols 53718.5 2575.6 98714.0 5078.6 5674.4 170724

Different superindexes a,b,c on the same line indicate statistically significant differences in the content of the compound among the different varieties
according to the Student–Newman–Keuls test (Po0.05).
690 R. Rodrı´guez Montealegre et al. / Journal of Food Composition and Analysis 19 (2006) 687–693

Table 2
Polyphenolic compounds (mg/kg of fresh grape) in the skins of red grape varieties (mean value7SD)

Cencibel (n ¼ 12) Cabernet Sauvignon (n ¼ 12) Merlot (n ¼ 13) Shiraz (n ¼ 7)

Protocatechic acid 1.5a70.51 2.4b71.15 1.7a.b70.63 2.4b71.75
cis-Caftaric 0.2570.081 0.4470.241 0.4670.174 0.1770.053
trans-Caftaric 5.7a72.51 9.5b73.71 7.0a.b73.77 4.9a71.04
cis-Coutaric 2.7c71.07 2.0b70.54 0.94a70.523 1.5a.b70.48
trans-Coutaric 10c74.1 5.8b71.77 3.2a71.94 6.1b71.69
Catechin 2279.6 1777.7 25717.9 8.573.94
Epicatechin 8.473.78 6.273.71 13710.2 6.974.8
Procyanidin B3 39711.1 2779.3 35716.5 1674.3
Procyanidin B1 22b79.4 12a.b76.8 21b713.9 8.4a73.76
Procyanidin B2 1.5a.b70.67 0.99a70.641 2.2b71.46 0.75a70.214
Myricetin glucuronide 10b72.7 10b73.2 5.8a72.53 7.3a73.01
Myricetin glucoside 26b711.4 22b75.2 13a75.7 21b79.2
Quercetin glucuronide 29a719.1 59b731.8 43a.b718.9 35a78.0
Quercetin glucoside 32b717.3 48a.b720.4 31a713.5 55b714.2
Quercetin glucosylxyloside 12a74.0 12a73.1 9.0a73.45 18b78.6
Kaempferol glucoside 1478.9 1375.4 8.072.93 1378.3
Isorhamnetin glucoside 1170.4 2875.9 1775.7 48722.1
Total hydroxycinnamates 1974.9 1874.2 1274.3 1372.0
Total monomers flavan-3-ol 30710.4 2378.6 38720.6 1576.2
Total dimers flavan-3-ol 63714.6 40711.6 58721.6 2575.7
Total flavan-3-ols 92.83717.86 63.03714.38 96.28729.85 40.7778.42
Total flavonols 130730 190739 130725 200731

Different superindexes a,b,c on the same line indicate statistically significant differences in the content of the compound among the different varieties
according to the Student–Newman–Keuls test (Po0.05).

Table 3
Polyphenolic compounds (mg/kg of fresh grape) in the seeds of white grape varieties (mean value7SD)

Chardonnay Sauvignon Moscatel Gewurztraminer Riesling Viogner

(n ¼ 10) blanc (n ¼ 6) (n ¼ 4) (n ¼ 2) (n ¼ 2) (n ¼ 2)
Protocatechic acid 4.871.64 4.471.10 3.672.23 6.071.37 Traces Traces
Procyanidin B3 52716.4 52714.2 39712.7 5672.3 4375.9 51712.1
Procyanidin B1 380a.b775 250a783 330a.b793 460b731 620c7176 200a742
Procyanidin B4 71720.5 54727 40713.6 7077.7 95722.7 53710.4
Procyanidin B2 33b75.8 19a73.0 15a75.1 22a70.8 33b73.9 19a70.9
Catechin 3907166 2007148 3507135 50076 4007196 12075
Epicatechin 3107122 130768 120772 15071 160776 11075
Epicatechin gallate 39725.0 27715.6 67743.4 66724.2 42730.5 1374.9
Total mon. flavan-3-ol 7307207 3507164 5307159 720725 6007212 24079
Total dimers flavan-3-ol 540780 370788 420795 610732 7907178 330745
Total flavan-3-ols 12707223 7307186 9507185 1340740 13907278 560746
No. of seeds/berry 1.770.20 1.570.13 2.071.00 2.0070.08 1.870.09 1.970.28
Weight (g)/berry 0.870.13 1.070.19 1.070.36 1.070.16 0.870.16 0.970.28

Different superindexes a,b,c on the same line indicate statistically significant differences in the content of the compound among the different varieties
according to the Student–Newman–Keuls test (Po0.05).

authors (Cheynier et al., 1998; Pen˜a-Neira et al., 2004; De
Freitas et al., 2000). In the case of the dimers, the
concentration of procyanidin B3 was slightly higher and
with similar concentrations to those found in white grape
skins. Moreover, small amounts of procyanidin B2 were
quantified in red grape skins.
Only glycosides were quantified in the group of
flavonols. No flavonol aglycones present in wine as a
consequence of progressive hydrolysis of same were
detected.
The total contents of these compounds in white grape
skins was lower than in red grape skins, ranging from 25
mg/kg in Sauvignon Blanc to 97 mg/kg in Moscatel, with
the exception of the Viogner variety in which this was 166
mg/kg. This was mainly because myricetin glucuronide
and glucoside and quercetin
 R. Rodrı´guez Montealegre et al. / Journal of Food Composition and Analysis 19 (2006) 687–693 691

Table 4
Polyphenolic compounds (mg/kg of fresh grape) in the seeds of red grape varieties (mean value7SD)

Cencibel (n ¼ 12) Cabernet Sauvignon (n ¼ 12) Merlot (n ¼ 13) Shiraz (n ¼ 7)

Gallic acid 7.3a72.40 9.0b71.50 9.8b72.12 6.8a71.35
Protocatechuic acid 3.3a71.30 7.1b71.93 8.7b72.04 6.2b71.25
Procyanidin B3 43a77.6 50a.b722.2 64b712.3 55a.b717.5
Procyanidin B1 74a740.4 150b754 170b760 100a713
Procyanidin B4 39a712.2 57b79.8 80c719.7 33a74.6
Procyanidin B2 21a75.4 41b74.4 37b77.0 23a71.1
Catechin 82a762.6 270b780 240b798 120a719
Epicatechin 60a733.2 130b725 210c772 130b734
Epicatechin gallate 13a77.1 25a77.8 70b741.1 32a711.8
Total monomers flavan-3-ol 150771 430785 5207128 280741
Total dimers flavan-3-ol 180743 300759 350765 210722
Total flavan-3-ols 330783 7207103 8707144 500746
No. of seeds/berry 2.070.61 1.670.10 1.670.24 1.770.17
Weight (g)/berry 1.470.44 0.870.12 0.870.18 1.070.27

Different superindexes a,b,c on the same line indicate statistically significant differences in the content of the compound among the different varieties
according to the Student–Newman–Keuls test (Po0.05).

glucosylxyloside appear in red grape skins but are not
present in white grape skins. Isorhamnetin glucoside is also
found in very low concentrations in white grape skins, in
most cases below the quantification level. Different authors
have shown that myricetin and isorhamnetin glycosides are
specific to red grape varieties (Cheynier and Rigaud,
1986).
The main glycosides in the skins of white grapes were
quercetin glycosides, normally glucuronide, notably in the
Moscatel and Viogner varieties with 54 and 67 mg/ kg,
respectively, the exception being the Gewu¨rztrami-ner
variety in which quercetin glucoside was more abundant.
Red grape skins also presented noteworthy levels of
quercetin glycosides, the main glycosides being glucoside
in Cencibel and Shiraz and glucuronide in Cabernet
Sauvignon and Merlot.
3.2. Polyphenols in grape seeds
Tables 3 and 4 show that the phenolic content of the
seeds consisted almost exclusively of flavan-3-ols. Low
concentrations of protocatechic and galic acid were also
obtained in red grape seeds.
The total concentrations of flavanols in seeds were
higher than those in skins; this coincides with the findings
described previously by other authors (Cheynier et al.,
1998). As reported by Souquet et al. (2000), more or less
significant quantities of epicatechin galate were found in
grape seeds that were not detected in skins.
In general, and as described by other authors (Guendez
et al., 2005), the main compound was catechin, with the
exception of Riesling and Viogner seeds in which
procyanidin B1 was more abundant and Shiraz seeds in
which the main compound was epicatechin. These results
coincide with those reported
by other authors (Kennedy et al., 2000); other red grape
varieties, such as Castelao Franceˆs, Touriga Nacional and
Touriga Francesa, also present this unique char-acteristic
(Jordao et al., 2001; Mateus et al., 2001).
Seeds noteworthy for their high flavanol content were, in
terms of white grape varieties, Riesling, Gewu¨rztra-miner
(as reported by Revilla et al., 1995) and Chardonnay; as
regards red grape varieties, Cabernet Sauvignon and Merlot
grape seeds presented the highest flavanol contents.
As can be observed, the amounts of flavanols present in
white grape seeds were higher than those in red grape seeds.
However, this result must not be considered in absolute
terms because the white grape samples analysed in this
study were approximately one degree Baume´ lower than
red grape samples and it is known that the concentration of
polyphenols in seeds diminishes during the ripening period
(Kennedy et al., 2000).
It must also be borne in mind that berry size indirectly
affects the final concentration of phenolic compounds
contributed by seeds and skins and this size, in addition to
being determined by genetic factors, is hugely influenced
by the water deficit to which the plant is subjected during
its vegetative period (Ojeda et al., 2002). Consideration
must also be given to another factor: the number of seeds
contained in each berry is a variable that influences the
amount of polyphenols contributed by the berry to the
whole of the grape. This is illustrated in Tables 3 and 4,
which present the values corresponding to the mean
number of seeds per berry and the mean weight of berries
in each grape variety.
Finally, we must make a final comment on the results
obtained in this study in terms of the concentrations of
procyanidins. Some authors have reported that the main
procyanidin in grape skins is B1 and B2 in seeds; this
seems to contradict our results. Any quantification
692 R. Rodrı´guez Montealegre et al. / Journal of Food Composition and Analysis 19 (2006) 687–693
errors should be ruled out since this quantification was
performed using commercial standards of known purity for
procyanidins B1 and B2. In the case of procyanidins B3
and B4, certain deviation in the results obtained is possible,
since these were quantified with the response factor of
procyanidin B1 given the lack of commercial standards.
This response factor in the HPLC method used here varied
between 25018 and 33137 area/ concentration units in
mg/L for standard procyanidins B1 and B2, respectively,
and therefore a similar variation would be likely for the
response factor of procyanidins B3 and B4.
Furthermore, the extraction method used in this study
was compared to those employed by De Freitas et al.
(2000) and Mateus et al. (2001). No significant differences
were observed in the concentrations of these procyanidins
in terms of these extracts (we continued to obtain a higher
concentration of PB1 than PB2).
It is very likely that the climate factor was the cause of
this apparent discrepancy. When analysing the results for
grape polyphenols in studies carried out by other authors in
regions with very hot summers such as our own, we
discovered that the main compound found in Monastrell
grape skins from the wine growing region of Jumilla
(Spain), an area with similar weather conditions to those in
our area of study, was procyanidin B3 (Go´mez-Plaza et
al., 2001); and in seeds of eight red grape varieties grown
in Greece, the main procyanidin compound in terms of
concentration was B1 (Guendez et al., 2005). In contrast, in
areas with less extreme summers, such as Navarre
(Northern Spain) (Monagas et al., 2003) and Bordeaux
(France) (De Freitas et al., 2000), the main procyanidin in
seeds was B2.
4. Conclusions
The phenolic composition of grapes depends on multiple
factors, including climate, degree of ripeness, berry size
and grapevine variety. However, it may be concluded that
the skins and seeds of white grape varieties present a very
similar qualitative and quanti-tative composition to that of
red grape varieties in terms of non-anthocyanic
polyphenols. The only qualitative difference was observed
in the skins of white grape varieties that lacked the
myricetin glycosides present in the skins of red grape
varieties. White grape varieties must therefore be
considered a good source of non-anthocyanic phenols for
their use in co-fermentations with red grape musts, or as a
source of natural antioxidant compounds of growing
industrial impor-tance.
This study has also shown that Viogner grape skins have
a very unique polyphenolic profile, with relatively high
concentrations of flavonols and very low concen-trations of
other flavonoids and non-flavonoids.
Acknowledgements
The authors would like to express their gratitude to the
Consejeria de Ciencia y Tecnologı´a of the Junta de
Comunidades de Castilla-La Mancha (Project PCC-02-
003) for its financial support.
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