Wine Chemistry and Biochemistry

440 M. Monagas and B. Bartolom ́e

R 3 = -CO-CH -CO-CH=CH

OH

(-acetyl) (-p (-caffeoyl)

H

OH

H

OH

+O

O

OH

R 1

HO

OH

R 2

O OH

OR 3

R 3 = -CO-CH 3 -CO-CH=CH OH -CO-CH=CH

OH

(-acetyl) (- -coumaroyl)

Anthocyanidin R 1 R 2

Cyanidin OH

OH

OCH 3

OCH 3

OCH 3

OCH 3

Delphinidin

Peonidin

Petunidin

Malvidin

+

O

OH

R 1

HO

OH

OH

R 2

O

HO

OH

OR 3

OH

Fig. 9A.1Chemical structures of anthocyanins

confirmation of the 3-O-glucosides, 3-O-acetylmonoglucosides and 3-O-p-coum-

aroylmonoglucosides of delphinidin, cyanidin, petunidin, peonidin and malvidin

as well as the 3-O-caffeoylmonoglucosides of malvidin and peonidin in grapes

and wines (Baldi et al. 1995; Giusti etal. 1999; Revilla et al. 1999; Wang and

Sporns 1999; Favretto and Flamini 2000; Monagas et al. 2003; Wang et al. 2003b;

N ́u ̃nez et al. 2004). Recently, the 3-O-caffeoylmonoglucosides of cyanidin, del-

phinidin and petunidin have also been identified in grape skin (Vidal et al. 2004)

and wine (Alcalde-Eon et al. 2006) fractions. The occurrence of thecisisomer of

malvidin-3-(6-p-coumaroyl)-glucoside has also been confirmed in grapes and wine

fromVitis vinifera(Monagas et al. 2003; N ́u ̃nez et al. 2004). Later on, Alcalde-Eon

et al. (2006) also detected in red wines thecisisomer of delphinidin, cyanidin-

and petunidin-3-(6-p-coumaroyl)-glucosides together with the possiblecisisomer
of malvidin-3-(6-caffeoyl)-glucoside.

Although originally thought to be present only in grapes from nonV. vinifera

spp., the use of modern and more sensitive analytical techniques has allowed con-

firmation of the occurrence of anthocyanidin-3,5-diglucosides inV. viniferagrape

skin extracts (Baldi et al. 1995; Vidal et al. 2004) and wines (Heier et al. 2002;

Alcalde-Eon et al. 2006). Recently, the presence of 3,7-diglucosides has also been

proposed (Alcalde-Eon et al. 2006). Finally, Vidal et al. (2004) has confirmed for

the first time the existence of anthocyanin oligomers up to trimers in grape skin

extracts. Oligomers were possibly linked by either an A-type (carbon-carbon and

ether bonds) or B-type (carbon-carbon bond) linkages.

Varietal characteristics. The distribution and concentration of grape anthocyanins

depends on the cultivar, maturity, climaticconditions, production area and fruit yield

(Roggero et al. 1986a; Gonz ́alez-San Jos ́e et al. 1990; Vivas et al. 2001). In general,

malvidin is the major anthocyanidin in red grape varieties, representing up to 90%

in Grenache and less than 50% in Sangiovese. However, the amount of acylated

anthocyanins is largely influenced by the grape variety and they could be absent

from some varieties such as Pinot noir (Rib ́ereau-Gay ́on et al. 2000).

The anthocyanin profile has been used as chemotaxonomy criteria to estab-

lish differences between grape varieties. Relationships between the individual or

the total concentration of the different anthocyanidins have been proposed for