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(Last modification: 20. May 2010)

Resveratrol and derivatives in grapevine (Vitis vinifera)

From Wikipedia

Grapes of Vitis vinifera

Grapes of Vitis vinifera

Grapes of Vitis vinifera

Grapes of Vitis vinifera

Pictures taken from Wikipedia (German, English, Italian, and French versions).

 

Notes

  • This is not an attempt to be comprehensive; it just tries to summarize the stilbene secondary products in grapevine

  • 20.05.2010: addition of a page with stilbenes identified in Vitis vinifera in the period from 1995 to end of 2008: more...


   Resveratrol (cis- and trans-forms, with the trans-form more abundant than the cis-form) and the other major stilbene components, pterostilbene (3,5-dimethyl resveratrol), piceid (resveratrol glucoside), epsilon-viniferin (a resveratrol dimer), and alpha-viniferin (a resveratrol trimer) were first discovered as phytoalexins in leaves (Langcake and Pryce, 1976; Pryce and Langcake, 1977; Langcake and Pryce, 1977a; Langcake and Pryce, 1977b; Langcake et al., 1979; Blaich and Bachmann, 1980; Langcake, 1981). The structures are shown in Fig. 1.

Resveratrol (trans- and cis-forms) and its most often occurring derivatives
Fig. 1
Resveratrol (trans- and cis-forms) and its most often occurring derivatives. The colors mark the resveratrol monomers.

   All of them, in particular resveratrol, its glucoside piceid, and pterostilbene were found in all tissues investigated (e.g. Lamikanra et al., 1996; Adrian et al., 2000; Versari et al., 2001; Wang et al., 2009). Others were first identified in cell suspension cultures, e.g. piceatannol and its glucoside (astringin) (De Lima et al., 1999), delta-viniferin and pallidol (Fig. 2) (Waffo-Téguo et al., 2001; Pezet et al., 2003) ).

   Most of us, however, are interested in the presence in berries/grapes, and later in the wine produced from them. Generally, the substances described in Fig. 1 are also in the berries and in the wine (see for example Lamuela-Raventos and Waterhouse, 1993; Waterhouse and Lamuela-Raventos, 1994; Goldberg et al., 1995; Lamikanra et al., 1996; Sato et al., 1997; De Lima et al., 1999; Romero-Pérez et al., 1999; Versari et al., 2001; Cantos et al., 2002; Moreno-Labanda et al., 2004; Vitrac et al., 2005; Sun et al., 2006; Naugler et al., 2007).

 Resveratrol derivatives (piceatannol, astringin) usually present in lower concentrations, and some oligomers
Fig. 2.
Resveratrol derivatives (piceatannol, astringin), and some oligomers.
The colors mark the resveratrol monomers.  

    In addition to those, a number of resveratrol derivatives have been described; sometimes in fairly high concentrations. The structures are given in Fig. 2:
a) Pallidol and its glucosides (Baderschneider and Winterhalter, 2000; Naugler et al., 2007; He et al., 2009) (first identified in another member of the Vitaceae, Cissus pallida, Khan et al., 1986),
b)
Vitisin A (Schwarz et al., 2003; Seya et al., 2009), Ampelopsin B, a resveratrol dimer (Seya et al., 2009),
c)
Hopeaphenol (Guebailia et al., 2006; Seya et al., 2009) (two molecules of ampelopsin B; originally isolated many years ago from another plant (Coggon et al., 1965; Coggon et al., 1966)).
    I am sure that this list is not complete; in particular the variety Vitis vinifera 'Kyohou' and other Vitis species do contain additional oligostilbenes (see e.g. Ito et al., 1999). The pharmacology of most of these substances has not been thoroughly investigated, as far as I know.
The biosynthesis is not understood. It is not clear whether the resveratrol derivatives are synthesized enzymatically, or whether they are made during the fermentation or wine maturation by oxidative processes (see for example Cichewicz et al., 2000).

Some general comments on resveratrol in grapes/wine

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Enzymes of resveratrol biosynthesis and the derivatives

The biosynthesis of resveratrol is discussed elsewhere in much detail (more...), and therefore the focus here will be on Vitis.

   cDNAs for resveratrol synthase have been described (Melchior and Kindl, 1990; Sparvoli et al., 1994). The results indicate that this stilbene synthase (STS) is encoded in a large gene family in Vitis vinifera (Sparvoli et al., 1994).
     An interesting question is whether this enzyme is likely to use the aldol switch mechanism discovered with the stilbene synthase (STS) from Scots pine (Pinus sylvestris) (Austin et al., 2004). However, the amino acid residues characteristic for the aldol switch appear to be missing in the resveratrol synthase, and thus it may be possible that there may be alternative mechanisms for the STS-type ring-folding (more...).
   The functional analysis with recombinant enzymes showed that 4-coumaroyl-CoA is the preferred substrate, as would be expected from the abundance of resveratrol. However, piceatannol and astringin are probably synthesized from caffeoyl-CoA, the starter molecule containing already two vicinal hydroxyl groups. Interestingly, in humans resveratrol can be hydroxylated to piceatannol by cytochrome P450 CYP1B1 (Potter et al., 2002). This is probably the reason why some websites claim that piceatannol is a degradation product of resveratrol. A bit narrow-minded, it ignores the situation in the plants.
   The enzyme can be expressed in all plant tissues, and it is induced by a variety of stress conditions. Of particular interest is of course the situation in berries because they are the basis for the later amount of Resveratrol in the wine, and thus there are publications, e.g. on the localization in the berries (Fornara et al., 2008), the expression in healthy grapes (Gatto et al., 2008), on the expression during ripening, wilting, and UV-treatment: (Versari et al., 2001), and the induction by UV which could lead to a substantial increase in resveratrol yield (Bais et al., 2000; Cantos et al., 2002; Cantos et al., 2003).  

   The synthesis of pterostilbene (see Fig. 1) requires an O-methyltransferase (OMT), and a cDNA for such a protein has been described (Schmidlin et al., 2008). Indeed, the transgenic co-expression of the STS and this OMT in tobacco led to pterostilbene, the dimethylated product, suggesting that the OMT carries out both methylations.

   The formation of piceid (Fig. 1) and astringin (Fig. 2) requires a glucosyltransferase, and a cDNA for such protein has been described (Hall and De Luca, 2007). Interestingly, the analysis of a recombinant protein showed that it is poly-functional: it glucosylates resveratrol, flavonoids, and coumarins at higher pH (8 to 10), and hydroxybenzoic acids and hydroxycinnamic acids at a lower pH (5.5 to 7). The authors also showed that Vitis labrusca grape berries accumulated both stilbene glucosides and hydroxycinnamic acid glucose esters, consistent with the bi-functional role of this enzyme in stilbene and hydroxycinnamic acid modification.

Genome sequences

   There are large-scale efforts to establish the sequences of the complete genome (Jaillon et al., 2007; Velasco et al., 2007; Doddapaneni et al., 2008; Grimplet et al., 2009), and there is little doubt that this will greatly contribute to analyzing and understanding the genes controlling and catalyzing the biosynthesis of these interesting secondary products.

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