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STILBENOID CHEMISTRY FROM WINE AND THE GENUS VITIS, A REVIEW Alison D. PAWLUS, Pierre WAFFO-TÉGUO, Jonah SHAVER and Jean-Michel MÉRILLON*
GESVAB (EA 3675), Université de Bordeaux, ISVV Bordeaux - Aquitaine, 210 chemin de Leysotte, CS 50008, 33882 Villenave d'Ornon cedex, France
Abstract Résumé Stilbenoids are of great interest on account of their many promising Les stilbénoïdes présentent un grand intérêt en raison de leurs nombreuses biological activities, especially in regards to prevention and potential activités biologiques prometteuses, en particulier dans la prévention et le treatment of many chronic diseases associated with aging. The simple traitement de diverses maladies chroniques liées au vieillissement. Le stilbenoid monomer, -resveratrol, has received the most attention due to -resvératrol, monomère stilbénique, a suscité beaucoup d'intérêt de par E E early and biological activities in anti-aging assays. Since ses activités biologiques et . Une des principales sources in vitro in vivo in vitro in vivo , primarily in the form of wine, is a major dietary source of alimentaires en stilbénoïdes est , principalement sous forme Vitis vinifera Vitis vinifera these compounds, there is a tremendous amount of research on resveratrol de vin. De nombreux travaux de recherche ont été menés sur le resvératrol in wine and grapes. Relatively few biological studies have been performed dans le vin et le raisin. À ce jour, relativement peu d'études ont été réalisées on other stilbenoids from , primarily due to the lack of commercial sur les stilbènes du genre autre que le resvératrol, principalement en Vitis Vitis sources of many of these compounds. The diverse stilbenoids from this raison de leur absence de commercialisation. Ce genre est une source economically important genus are an untapped source of health promoting inexploitée de stilbénoïdes d'intérêt potentiel pour la santé et c'est pourquoi compounds and because of this, numerous efforts for isolation, identification de nombreux efforts pour l'isolement, l'identification et la quantification and quantification of additional stilbenoids have been ongoing. Additionally, d'autres stilbénoïdes sont en cours. Comme les espèces proches sont due to their role as phytoalexins, stilbenoids play an important role in the susceptibles de présenter des voies métaboliques similaires, une meilleure defense against pathogens. Therefore, the compounds produced by highly connaissance de la diversité chimique du genre peut être utile dans Vitis resistant strains are of great interest for the development of resistant crops, cette tâche. Nous avons effectué une revue bibliographie des stilbénoïdes natural spray reagents, and as new dietary supplements or pharmaceuticals. de ce genre économiquement important afin de promouvoir la chimie des Since closely related species are likely to have similar metabolic pathways, stilbénoïdes du vin et des espèces de , plus particulièrement . Vitis V. vinifera a more thorough understanding of the chemical diversity of stilbenoids En outre, nous abordons la quantification et la distribution de tous ces within is useful in this endeavor. In this review, we focus on stilbenoids stilbénoïdes. Vitis found in the genus with the aim of aiding future stilbenoid chemistry, Vitis particularly in and wine. Additionally, we discuss the efforts : oligostilbénoïde, resvératrol, , , vin V. vinifera Mots clés Vitis Vitis vinifera to quantify stilbenoids in , with a focus on non-resveratrol stilbenoid Vitis compounds.
: oligostilbenoid, resveratrol, s, , wine Key words Viti Vitis vinifera
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(Bavaresco and Fregoni, 2001). Stilbenoids are, therefore, INTRODUCTION of great interest due to their activity against many Epidemiological studies have attributed moderate devastating vine diseases and pests. Multiple avenues consumption of red wine to numerous health benefits to exploit this activity are being investigated. One potential such as the prevention of age-related diseases, including use of stilbenoids is as a naturally occurring pesticide for some cancers, neurodegenerative diseases, and most non-resistant species, such as L., the major strongly, cardiovascular diseases (Anstey , 2009; Vitis vinifera et al. wine grape. Such usage could reduce reliance on traditional Chao , 2008; Larrieu , 2004; Orgogozo , et al. et al. et al. pesticides. In addition to producing stilbenoid rich products 1997; Renaud and de Lorgeril, 1992; Wang , 2006). et al. such as natural spray reagents, wine, or dietary What accounts for such activity? A single glass of wine supplements, another avenue of research involves the use contains the fermented extract of 100 to 140 grape berries, of known induction mechanisms to promote disease which produces, depending on variety and vinification resistance (Cantos , 2003). There is also interest in et al. methods, up to 500 mg of polyphenolic compounds selectively breeding high stilbenoid producing species Vitis (Lopez , 2001; Stervbo , 2007; Waterhouse and by crossing with disease resistant, wild et al. et al. V.vinifera Vitis Teissedre, 1997). These polyphenols include a number (Malacarne , 2011). of known beneficial compounds, the majority being et al. flavonoids, such as anthocyanins and tannins, phenolic In all, a more thorough knowledge of the chemistry acids and stilbenoids. While many of these compounds and biology of these molecules can provide multiple are found in widely consumed fruits and vegetables, wine health, environmental, and economic benefits. In this is the dominant dietary source of stilbenoids. review we summarize the current knowledge of stilbenoids found in the genus in addition to recent data on Vitis Stilbenoids have received considerable attention due stilbenoid quantitation in and wine. to their promising biological activities. The stilbenoid Vitis monomer, resveratrol , 3,5,4'-trihydroxy- -stilbene, (1) trans in particular, has undergone extensive biological testing. STILBENOIDS IN THE VITIS GENUS Both in vitro and in vivo animal studies of resveratrol Over 1000 stilbenoids have been structurally have demonstrated promising activities in regards to characterized throughout the plant kingdom and their disease prevention, progression, and treatment (Baur and distribution and structural variations have been reviewed Sinclair, 2006; Howitz , 2003; Jang , 1997; (Cichewicz and Kouzi, 2002; Lin and Yao, 2006; Shen et al. et al. , 2009; Sotheeswaran and Pasupathy, 1993). They Pezzuto, 2011). Due to these biological activities, it has et al. been concluded that resveratrol could be part of the are found in a number of plant families, including explanation for the French Paradox and other Celastraceae, Cyperaceae, Dipterocarpaceae, Fabaceae, epidemiological studies supporting the moderate Gnetaceae, Iridaceae, Moraceae, Paeoniaceae and consumption of red wine for the prevention of diseases Vitaceae. The Vitaceae family encompasses approximately such as cardiovascular disease (Renaud and de Lorgeril, 900 species within 14 to 17 genera, primarily in tropical 1992; Renaud , 1998; Sun , 2002). Since the regions (Keller, 2010; Soejima and Wen, 2006). Of these et al. et al. numerous biological activities reported for resveratrol are genera, stilbenoids have been found primarily in only five, the , , , outside the scope of this article, we refer the reader to Ampelopsis Cissus Cyphostemma Parthenocissus and genera. Due to their economic importance as the existing biologically focused reviews (Anekonda, 2006; Vitis Bishayee, 2009; Szkudelska and Szkudelski, 2010). More major table and wine making grape around the world, the species in the genus have been studied the most. recently, promising biological activities have been shown Vitis Species from also have a long history of use as with other stilbenoids found in species, including Vitis Vitis medicinal plants, particularly , , piceatannol , piceid , pterostilbene , scirpusin A V. amurensis V.coignetiae (2) (3) (4) and , the later also being used by the modern , vaticanol C, α-viniferin , and vitisin A . These V.vinifera (5) (6) (7) nutraceutical and cosmeceutical industries. has, until activities include mechanisms related to the prevention Vitis of cancers, neurological diseases, and cardiovascular recently, been divided into two subgenera, the Euvitis and diseases (Chung , 2010; Joseph , 2008; Oshima the Muscadinia. Muscadinia is composed of three et al. et al. , 1995b; Richard , 2011; Shibata , 2007; American species, including the species formerly known et al. et al. et al. Son , 2010; Tsukamoto , 2010), demonstrating as , the most important economic species et al. et al. V. rotundifolia potential health benefits of additional stilbenoids, many of Muscadinia. Due to differences in chromosome number of which are known constituents of wine. and other characteristics, Muscadinia is now considered its own genus and is now named V. rotundifolia As phytoalexins, stilbenoids are induced by infections (Michx.) Small (Bouquet , Muscadinia rotundifolia et al. and mechanical stress, such as that caused by UV damage 2008; Keller, 2010; Péros , 2011). Since it is still et al. or insects. Their production affords protection against of interest in the wine industry, we included this species many pathogens, such as in our review. Vitis Plasmopara viticola
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Within , stilbenoids have been identified in around susceptible species have shown that disease resistant Vitis Vitis 20 species, including hybrid species, of the approximate species produce stilbenoids more readily and in higher 60 to 70 species found in . In table 1, we have listed concentration when exposed to pathogens such as downy Vitis the species and the specific plant parts the stilbenoids mildew, , and gray mold, Vitis Plasmopara viticola Botrytis were isolated from. The remaining two-thirds of the (Bavaresco , 1997; Bavaresco and Fregoni, Vitis cinerea et al. 2001; Pezet , 2004). Stilbenoid production can also species most likely contain stilbenoids, but have yet to be et al. examined for these compounds. Despite this lack of be induced by abiotic stress such as UV irradiation, research in all species, approximately 100 stilbenoid mechanical injury, and certain chemicals (Bavaresco and Vitis Fregoni, 2001; Bavaresco , 2009). In fact, the major monomers, dimers, and oligomers have been found, and et al. stilbenoids from were first identified in leaves nearly 20 are known constituents of wine. V.vinifera after induction by abiotic and biotic stresses (Langcake and Pryce, 1976; Langcake and Pryce, 1977a; Langcake STILBENOID PRODUCTION and Pryce, 1977b; Langcake and McCarthy, 1979; The metabolism of stilbenoids and regulatory Langcake, 1981). The production of stilbenoids is highly interactions are complex and not all mechanisms are variable among the different plant parts in regards to types currently understood. However, we do know that produced, concentrations, and response to outside stimuli. stilbenoids are downstream secondary metabolic products For example, resveratrol is induced in both leaves and of the phenylpropanoid pathway and diverge from the berries in response to external stimuli, but is constitutively flavonoid pathway through the stilbene synthase (STS) expressed and accumulated in stems and roots where it, enzymes. According to recent analysis of the grapevine along with other stilbenoids, are believed to protect against genome, there is an estimated 20 to 40 STS genes, many wood rot. Other stilbenoids, such as piceid, have been of which have shown to be expressed when exposed to shown to be constitutively expressed in various tissues, biotic stress (Chong , 2009). including berries (Gatto , 2008). et al. et al. Since a number of stilbenoids are induced by infections Due to their biological activities, both in the plant and and have antifungal activity, they are considered to be in humans, the possibility to artificially manipulate phytoalexins. Comparisons between disease resistant and stilbenoid levels is of great interest. Research into post-
Table 1. Vitis species and plant part where stilbenoids have been reported. References are found in Table 2. aPlant Species Plant Part(s) Studied Muscadinia rotundifolia (Michx.) Small Berries and wine (previously V. rotundifolia Michx.) V. acerifolia Raf. (reported as V. longii) Roots V. amurensis Rupr. Leaves, stems and roots V. berlandieri Planch. Roots V. betulifolia Diels & Gilg Stems V. chunganensis Hu Whole plant V. cinerea (Engelm.) Engelm. ex Millard Roots V. coignetiae Pulliat ex Planch. Berries, leaves, stems, and whole plant V. davidii (Rom. Caill.) Foëx Stems V. flexuosa Thunb. Stems V. heyneana Roem. & Schult. (also includes V. Stems pentagona Diels & Gilg) V. labrusca L. (Concord grape) Berries, stems, leaves and wine V. riparia Michx. Leaves and roots V. riparia x V. berlandieri SO4 (Oppenheim Roots selection no. 4) V. rupestris Scheele Roots V. solonis longii Roots V. solonis richter Roots V. thunbergii Sieb. & Zucc. Roots and stems V. vinifera L. Berries, cell suspension cultures, leaves, roots, stems and wine V. wilsoniae H. J. Veitch Stems ! aThis table is to meant to provide an up-to-date survey of which species stilbenoids have been reported from. In these studies, many Vitis different clones, cultivars, and hybrids have been used, particularly with . This information can be found in the original manuscript, V. vinifera however, in many studies, this information was lacking.
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harvest abiotic stresses, such as UV irradiation and ozone while only nine are currently known in wine. Among treatment, is currently ongoing for the production of high- these is the more unusual 2,4,6-trihydroxyphenanthrene stilbenoid containing wines and grape-derived products 2- -glucoside , isolated from a Riesling wine O (10) (Cantos , 2003; Gonzalez-Barrio , 2006; (Baderschneider and Winterhalter, 2000). There are et al. et al. Guerrero , 2010). Efforts are also being made to 35 reported dimers in , 24 having been identified in et al. Vitis utilize stilbenoid induction as natural pesticides through and its cell cultures, and nine in wine. The V. vinifera known elicitors, such as ethephon and methyl jasmonate dimers found in wine are mostly resveratrol dimers, (Belhadj , 2008a; Belhadj , 2008b; Faurie et al. et al. et derivatives of viniferin and pallidol, with ε-viniferin , 2009). This research could lead ways to safely induce (8) al. being the most common. naturally occurring stilbenoids on an industrial scale or There are 16 known trimers in species. Six of use them as spray reagents against disease, which could Vitis these trimers have been reported in various help reduce or eliminate the need for the currently used V. vinifera pesticides. plant parts, including the roots, leaves, and stems, although, to date, none of these have been reported in wine. The presence of trimers, based on molecular weight using STRUCTURAL DIVERSITY HPLC-MS-MS, has, however, been suggested in grapes OF VITIS STILBENOIDS treated with UV light and ozone (Gonzalez-Barrio , et al. Structural variations in stilbenoids typically involve 2006). Additionally, there are a total of 26 known stilbenoid monomer polymerization, glycosylation, tetramers, including a tetramer breakdown product, (-)- l . While only one of these compounds, prenylation, methoxylation, and various hydroxylation vinifera (11) hopeaphenol , has been reported in wine, 14 others patterns. There have been several attempts to delineate (12) are known plant part constituents. Finally, there and improve the classification of these various derivatives V.vinifera (Lin and Yao, 2006; Shen , 2009; Sotheeswaran and are two known stilbenoid pentamers and one et al. Vitis Pasupathy, 1993). The proposed classification initially hexamer, none of which have been found in wine or any separates the monomers from the oligomers. Oligomers plant part. V.vinifera undergo further classifications based on their monomer unit composition and heterogeneous coupling, i. e. Several notable points exist in the literature, relating resveratrol , piceatannol , gnetol (2,3', 5',6- to stilbenoid nomenclature and structure, which complicate (1) (2) tetrahydroxy- -stilbene), isorhapontigenin (3,4', 5- matters of identification and classification. There are a trans trihydroxy-3'-methoxy- -stilbene), and oxyresveratrol. number of instances where common names given to trans These are further separated into groups with oxygen particular stilbenoids can lead to confusion. In 2009, two independent research groups published the isolation and containing heterocycles (group A), such as ε-viniferin , or those without (group B), such as pallidol . The identification of two new different stilbenoid dimers, one (8) (9) from stembark and one from roots. few remaining compounds that do not fit within this V.vinifera V.thunbergii scheme are assigned to a small miscellaneous category. These groups published concurrently and chose the same Resveratrol is the predominant monomer subunit in , name for their newly identified compounds, vitisinol E Vitis (Chiou , 2009; Choi , 2009). The with multiple patterns of oligomerization and (13,14) et al. et al. glycosylation. The resveratrol dimer, -viniferin , is opposite situation occurred in 1999, when two groups ε (8) considered the major oligomer intermediate in isolated the same stilbenoid dimer but gave it two different Vitis common names, amurensin H and viniferifuran species. (15) (Huang , 1999a; Ito , 1999). Another area of et al. et al. In order to better understand the chemical diversity confusion with nomenclature comes from the use of the of stilbenoids in species, we have delineated the Vitis common name “vitisin” », which refers to either the well- known stilbenoid compounds with their plant name and characterized pyranoanthocyanin pigments in wine, vitisin part, including those found in wine, in Table 2. Of the A and B, or to a series of stilbenoid oligomers, vitisins A approximately 100 stilbenoids identified in , 18 are Vitis through E. monomers. These are primarily methoxylated and glycosylated derivatives of resveratrol and piceatannol Another potential point of confusion lies in the along with their (c ) and ( ) isomers. A large structure and naming of the -viniferins. The compound Z is E trans ε portion of these monomers are glycosides, many of which itself is a simple resveratrol dimer, however, there are two were isolated and identified in cell culture stereochemical centers, at positions 7a and 8a on the V. vinifera studies, a method developed in our laboratory for further dihydrofuran ring, allowing for four potential biological studies and potential industrial production of stereoisomers (see compound 8 in Table 2 for numbering). these compounds (Krisa , 1999; Waffo-Téguo , The configuration of the two hydrogens in this et al. et al. trans 1996a). Seventeen of these 18 monomers have been saturated ring system, meaning one alpha and one beta identified in parts of the vine or in cell cultures, hydrogen, is most common in . V.vinifera Vitis
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Table 2. Compounds reported in Vitis species.
Monomers
Compound aStructure M.W. Plant Name bReferences Name and Part Z-Astringin HO 406.38 V. vinifera cell (Buiarelli et al., suspension 2007; Waffo-Téguo cultures and et al., 1998) wine OGlc OH OH E-Astringin (18) OH 406.38 V. coignetiae (Buiarelli et al., OH berries 2007; Carando et al., V. vinifera cell 1999; Kim et al., HO suspension 2009; Krisa et al., cultures, and 1999; Naugler et al., red and white 2007; Ribeiro de wine Lima et al., 1999; OGlc Vitrac et al., 2002; Vitrac et al., 2005; Waffo-Téguo et al., 1996a; Waffo-Téguo et al., 1998) E-Piceatannol (astringinin) (2) OH 244.24 V. amurensis (Bavaresco et al., OH leaves and 2002; Buiarelli et stems al., 2007; Delaunay HO V. coignetiae et al., 2002; Ha et berries al., 2009b; Kim et V. vinifera al., 2009; Kulesh et stems, berries, al., 2006; Zga et al., OH and wine 2009) Z-Piceid HO 390.38 V. labrusca (Adrian et al., 2000; berries Baderschneider and M. rotundifolia Winterhalter, 2000; berries Buiarelli et al., OGlc V. vinifera 2007; Krisa et al., berries, leaves, 1999; Larronde et OH cell cultures al., 2005; Leblanc et and red and al., 2008; Mattivi et white wine al., 1995; Naugler et al., 2007; Pezet et al., 2003; Ribeiro de Lima et al., 1999; Santamaria et al., 2010; Vitrac et al., 2001; Vitrac et al., 2002; Waffo-Téguo et al., 1998)
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E-Piceid (3) OH 390.38 V. amurensis (Adrian et al., 2000; leaves and Baderschneider and HO stems Winterhalter, 2000; V. coignetiae Buiarelli et al., berries 2007; Guebailia et V. labrusca al., 2006; Ha et al., OGlc berries 2009a; Ha et al., M. rotundifolia 2009b; Jean-Denis et berries al., 2006; Kim et al., V. vinifera 2009; Krisa et al., berries, cell 1999; Landrault et suspension al., 2002; Larronde cultures, et al., 2005; Leblanc leaves, stems et al., 2008; Mattivi and red and et al., 1995; Naugler white wine et al., 2007; Ribeiro de Lima et al., 1999; Santamaria et al., 2010; Vitrac et al., 2001; Vitrac et al., 2002; Vitrac et al., 2005; Waffo-Téguo et al., 1996a; Waffo- Téguo et al., 1996b; Waffo-Téguo et al., 1998; Waterhouse and Lamuela- Raventós, 1994; Yan et al., 2001)
E-Pterostilbene (4) OH 256.30 V. coignetiae (Adrian et al., 2000; berries Kim et al., 2009; H3CO V. vinifera Langcake et al., leaves and 1979; Pezet and berries Pont, 1988; Pezet et OCH3 al., 2003) Z-Resveratrol HO 228.24 V. labrusca (Buiarelli et al., wine 2007; Delaunay et M. rotundifolia al., 2002; Jeandet et wine al., 1995; Krisa et OH V. vinifera al., 1999; Lamikanra leaves, stems, et al., 1996; Mattivi OH cell suspension et al., 1995; Naugler cultures and et al., 2007; Pezet et red and white al., 2003; Ribeiro de wine Lima et al., 1999; Vitrac et al., 2001; Vitrac et al., 2002; Vitrac et al., 2005)
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E-Resveratrol (1) OH 228.24 V. amurensis (Adrian et al., 2000; leaves, stems, Amico et al., 2009; HO and roots Baderschneider and V. betulifolia Winterhalter, 2000; stems Barjot et al., 2007; V. Bisson et al., 2011; OH chunganensis Buiarelli et al., whole plant 2007; Dourtoglou et V. coignetiae al., 1999; Ector et berries and al., 1996; Gambuti leaves et al., 2004; V. davidii Gerogiannaki- stems Christopoulou et al., V. labrusca 2006; Guebailia et berries, leaves, al., 2006; Ha et al., stems, and 2009a; Ha et al., wine 2009b; He et al., V. pentagona 2009; Huang and stems Lin, 1999; Jean- V. riparia Denis et al., 2006; leaves Jeandet et al., 1991; V. riparia x V. Jeandet et al., 1995; berlandieri Krisa et al., 1999; roots Kulesh et al., 2006; M. rotundifolia Lamikanra et al., berries and 1996; Landrault et wine al., 2002; Langcake V. thunbergii and Pryce, 1976; stems Langcake, 1981; V. vinifera Leblanc et al., 2008; berries, cell Li et al., 1996; Li et suspension al., 1998a; Lou et cultures, stems, al., 2004; Mattivi et leaves, and red al., 1995; Naugler et and white wine al., 2007; Pezet et al., 2003; Ribeiro de Lima et al., 1999; Siemann and Creasy, 1992; Vitrac et al., 2001; Vitrac et al., 2002; Vitrac et al., 2005; Wang et al., 2011; Waterhouse and Lamuela-Raventós, 1994)
Z-Resveratrol-3,4'-O-!- HO 552.52 V. vinifera cell (Decendit et al., diglucoside suspension 2002; Larronde et cultures al., 2005)
OGlc
OGlc
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E-Resveratrol-3,4!-O-!- OGlc 552.52 V. vinifera cell (Decendit et al., diglucoside suspension 2002; Larronde et (mulberroside E) HO cultures al., 2005)
OGlc E-Resveratrol 2-C-glucoside OH 390.38 V. vinifera (Baderschneider and stems and Winterhalter, 2000; HO wine, Riesling Yan et al., 2001)
Glc OH Z-Resveratrol GlcO 552.52 V. vinifera cell (Larronde et al., 3,5-O-!-diglucoside suspension 2005) cultures
OGlc
OH E-Resveratrol OH 552.52 V. vinifera cell (Larronde et al., 3,5-O-!-diglucoside suspension 2005) GlcO cultures
OGlc Z-Resveratrol GlcO 714.67 V. vinifera cell (Larronde et al., 3,5,4'-O-!-triglucoside suspension 2005) cultures OGlc
OGlc Z-Resveratroloside HO 390.38 V. vinifera cell (Krisa et al., 1999; suspension Waffo-Téguo et al., cultures 1998) OH
OGlc E-Resveratroloside OGlc 390.38 V. vinifera cell (Krisa et al., 1999; suspension Waffo-Téguo et al., HO cultures 1998)
OH E-Rhapontigenin OH 258.27 V. coignetiae (Adrian et al., 2000)
OCH3 berries
HO
OH 2,4,6-Trihydroxyphenanthrene OH 388.37 V. vinifera (Baderschneider and 2-O-glucoside (10) wine, Riesling Winterhalter, 2000) OH
OGlc
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!
Dimers
Compound aStructure M.W. Plant Name bReferences Name and Part
(+)-Ampelopsin A HO 470.47 V. amurensis (Chen and Wang, H leaves, stems, and 2009; Chiou et al., O OH roots 2009; Ha et al., V. betulifolia stems 2009a; Ha et al., HO V. coignetiae 2009b; Huang and H whole plant Lin, 1999; Kulesh et OH V. heyneana stems al., 2006; Li et al., V. thunbergii roots 1996; Li et al., OH and stems (var. 1998b; Lou et al., taiwaniana) 2004; Oshima et al., V. vinifera stems 1995b; Reniero et al., 1996; Wang et OH al., 2011; Yan et al., 2001; Zga et al., 2009)
Ampelopsin D OH 454.47 V. amurensis roots (Huang and Lin, V. vinifera leaves 1999; Mattivi et al., OH 2011) H HO
OH H HO
HO (+)-Ampelopsin F 454.47 V. amurensis (Chiou et al., 2009; HO OH leaves and stems Ha et al., 2009a; Ha V. coignetiae et al., 2009b; whole plant Oshima et al., HO OH V. thunbergii roots 1995b; Yan et al., V. vinifera stems 2001)
OH OH Amurensin A HO 472.49 V. amurensis roots (Huang and Lin, HO OH 1999) H H H HO HO
OH OH
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Betulifol A OH 452.45 V. betulifolia stems (Li et al., 1998b) H O HO
H H OH O H HO Gnetin A OH 454.47 V. flexuosa stems (Li et al., 1998c; Li V. wilsoniae stems et al., 1998d)
OH
H HO O
H O HO Isoampelopsin F HO OH 454.47 V. amurensis stems (Kulesh et al., 2006)
HO OH H
OH OH (-)-Malibatol A HO 468.45 V. vinifera stems (Yan et al., 2001)
H OH OH HO
O HO
HO Pallidol (9) OH 454.47 cV. amurensis (Delaunay et al., OH stems 2002; Guebailia et V. vinifera cell al., 2006; Kulesh et H suspension al., 2006; Landrault HO cultures, leaves, et al., 2002; Mattivi OH stems and red wine et al., 2011; Naugler H (Bergerac) et al., 2007; Vitrac et al., 2001; Vitrac et al., 2002; Waffo- HO OH Téguo et al., 2001)
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Pallidol 3,3!- OH 778.75 V. vinifera wine, (Baderschneider and OGlc diglucoside Riesling Winterhalter, 2000)
HO OH
HO OGlc Pallidol 3-O- OH 616.61 V. vinifera wine, (Baderschneider and OH glucoside Riesling Winterhalter, 2000)
HO OH
HO OGlc Parthenocissin A HO 454.47 V. vinifera wine, (Vitrac et al., 2001) OH H red Bergerac
HO OH H H OH
OH Quadrangularin A HO 454.47 V. vinifera leaves (Mattivi et al., 2011) OH H
HO OH H H OH
HO Scirpusin A (5) OH 470.47 V. vinifera stems (Kong et al., 2010) HO
O OH
HO
OH
OH
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(+)-Viniferether A OH 486.51 V. vinifera roots (Fujii et al., 2005)
OH H HO
OH H H HO H3CO H OH (+)-Viniferether B OH 486.51 V. vinifera roots (Fujii et al., 2005) OH H HO
OH H H HO H H3CO OH Viniferifuran (15) HO 452.45 V. amurensis roots (Chiou et al., 2009; (Amurensin H) V. thunbergii roots Huang et al., 1999a; O OH V. vinifera stems Ito et al., 1999) HO
OH
OH
E-"-Viniferin (19) HO 454.47 V. vinifera cell (Breuil et al., 1998; (E-Resveratrol suspension Jean-Denis et al., dehydrodimer) O cultures, leaves, 2006; Pezet et al., and wine 2003; Vitrac et al., HO 2005; Waffo-Téguo OH et al., 2001)
OH OH E-"-Viniferin 11- HO 616.61 V. vinifera cell (Waffo-Téguo et al., H suspension cultures 2001) O-!-D- O glucopyranoside (resveratrol HO OH dehydrodimer 11- H O-!-D- glucopyranoside) OGlc OH E-"-Viniferin 11!- HO 616.61 V. vinifera cell (Waffo-Téguo et al., H suspension cultures 2001) O-!-D- O glucopyranoside (E-Resveratrol HO OH dehydrodimer 11!- H O-!-D- glucopyranoside) OH OGlc
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Z-"-Viniferin HO 454.47 V. vinifera leaves (Pezet et al., 2003) after UV- O irradiation HO HO
OH OH Z-#-Viniferin HO 454.47 V. vinifera leaves (Amira-Guebailia et H and wine al., 2009; Mattivi et O OH al., 2011; Pezet et HO OH al., 2003) H
OH (+)-E-#-Viniferin HO 454.47 V. heyneana stems (Huang and Lin, H V. vinifera stems 1999; Ito and Niwa, O OH and leaves 1996; Li et al., 1996; HO Mattivi et al., 2011) H
OH
OH
E-#-Viniferin (8) HO 454.47 V. amurensis (Amico et al., 2009; leaves, stems, Amira-Guebailia et O OH and roots al., 2009; Barjot et V. berlandieri roots al., 2007; Bisson et HO V. betulifolia stems al., 2011; Chiou et V. chunganensis al., 2009; Guebailia whole plant et al., 2006; Ha et OH V. cinerea roots al., 2009b; He et al., V. coignetiae 2009; Huang et al., whole plant 2005; Jean-Denis et V. davidii stems al., 2006; Kulesh et OH V. flexuosa stems al., 2006; Landrault V. longii roots et al., 2002; V. riparia leaves Langcake and Pryce, and roots 1977a; Langcake, V. riparia x V. 1981; Li et al., berlandieri roots 1998a; Li et al., V. rupestris roots 1998b; Li et al., V. solonis longii 1998c; Li et al., roots 1998d; Mattivi and V. solonis richter Reniero, 1992; roots Oshima et al., V. thunbergii roots 1995b; Ourtoule et and stems (var. al., 1996; Pezet et taiwaniana) al., 2003; Vitrac et V. vinifera leaves, al., 2005; Wang et roots, stems, and al., 2011; Yan et al., red wine 2001; Zga et al., V. wilsoniae stems 2009)
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Z-$-Viniferin HO 454.47 V. vinifera leaves (Mattivi et al., 2011) (7a,8a-cis-Z-#- H viniferin 17) O OH HO H OH OH E-$-Viniferin HO 454.47 V. vinifera leaves (Mattivi et al., 2011) (7a,8a-cis-E-#- viniferin 16) H O OH
HO H
OH
OH Z-#-Viniferin HO 778.75 V. vinifera wine, (Baderschneider and diglucoside Riesling Winterhalter, 2000) O OH
GlcO OH
OGlc E-#-Viniferin HO 778.75 V. vinifera wine, (Baderschneider and diglucoside Riesling Winterhalter, 2000) O OH
GlcO
OGlc
OH #-Viniferin diol HO 488.49 V. betulifolia stems (Li et al., 1998b; (Betulifol B) H V. coignetiae stems Oshima et al., O OH 1995a) HO H HO OH OH
OH
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Vitisinol A HO H H OH 452.45 V. thunbergii roots (Huang et al., 2005) O
H H
HO OH
O Vitisinol B HO 574.58 V. thunbergii roots (Huang et al., 2005) H O OH
HO OH H
OH CHO
OH Vitisinol C HO 428.48 V. thunbergii roots (Huang et al., 2005) O
H H
HO OH OH Vitisinol D HO 454.47 V. thunbergii roots (Huang et al., 2005) O
O HO
OH
OH (+)-Vitisinol E O 486.51 V. vinifera (Choi et al., 2009) (13) HO H stembark
H HO O OCH 3 OH OH Vitisinol E (14) OH 444.48 V. thunbergii roots (Chiou et al., 2009)
HO O HO
OH
OH
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Vitisinol G 452.45 V. thunbergii roots (Chiou et al., 2009) HO O OH
HO
OH OH !
Trimers
Compound aStructure M.W. Plant Name bReferences Name and Part Ampelopsin C OH OH 680.70 V. betulifolia stems (Chiou et al., HO V. coignetiae 2009; Huang et HO whole plant al., 2005; Li et H V. davidii stems al., 1996; Li et V. heyneana stems al., 1998a; Li et H H HO V. thunbergii roots al., 1998b; OH and stems (var. Oshima et al., H H taiwaniana) 1995b; Wang et al., 2011) HO O H
HO Ampelopsin E HO OH 680.70 V. amurensis roots (Huang and Lin, H H V. davidii stems 1999; Li et al., O O V. wilsoniae stems 1998a; Li et al., 1998d) HO OH H H
OH OH
OH OH Z-Ampelopsin E HO 680.70 V. thunbergii roots (Chiou et al., 2009) H H O O OH HO H H OH OH OH
Z-Amurensin B HO OH 680.70 V. amurensis (Ha et al., H H leaves and stems 2009a) O O
HO OH H H
OH OH OH
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E-Amurensin B HO OH 680.70 V. amurensis (Ha et al., H H leaves, stems, and 2009a; Ha et al., O O roots 2009b; He et V. chunganensis al., 2009; HO OH whole plant Huang and Lin, H H 1999)
OH OH
OH Amurensin C HO OH 678.68 V. amurensis roots (Huang et al., H 2000) O O
HO OH H
OH OH
OH Amurensin D OH 678.68 V. amurensis roots (Huang et al., OH 2000) H O O HO OH H HO OH
OH Amurensin G HO OH 680.70 V. amurensis (Ha et al., leaves, stems, and 2009b; He et OH roots al., 2009; V. chunganensis Huang et al., OH H whole plant 1999b) H H H OH HO OH H O H HO
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Gnetin H HO OH 680.70 V. amurensis (Ha et al., H H leaves and stems 2009a; Ha et al., O O V. berlandieri 2009b; He et roots al., 2009; HO OH V. chunganensis Mattivi and H H whole plant Reniero, 1992) V. cinerea roots OH OH V. longii roots V. riparia roots V. rupestris roots V. solonis longii OH roots V. solonis richter roots V. vinifera roots E-trans- OH 680.70 V. vinifera leaves (Barjot et al., Miyabenol C and stems 2007; Mattivi et HO al., 2011) H O OH
HO H H
HO O OH H HO E-cis- OH 680.70 V. vinifera leaves (Mattivi et al., Miyabenol C 2011) HO H O OH
HO H H
OH O OH H HO ! Z-trans- HO 680.70 V. vinifera leaves (Mattivi et al., Miyabenol C H 2011) O OH
HO H H OH
HO O OH H HO
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%-Viniferin (6) OH 678.68 V. riparia leaves (Langcake, V. vinifera leaves 1981; Mattivi et al., 2011; Pryce H and Langcake, O OH 1977) H HO H O H HO H H O
OH OH (+)-Viniferol D OH 680.70 V. vinifera stems (Takaya et al., 2003) OH
OH H H H OH H HO H O OH OH H HO Vitisin E OH 680.70 V. coignetiae (Shinoda et al., stems 1997)
OH OH H H H HO OH
O O H H HO OH Vitisinol F HO 654.70 V. thunbergii roots (Chiou et al., H 2009) O OH OH
HO H H H OH O
OH
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!
Tetramers
Compound aStructure M.W. Plant Name bReferences Name and Part Ampelopsin H OH 906.93 V. vinifera leaves (Mattivi et al., H HO HO O 2011) H OH OH H H H H HO H HO O OH OH H
HO Amurensin I HO H 902.89 V. amurensis roots (Huang et al., O OH HO 2001)
HO H H O H H H HO OH HO OH HO HO Amurensin J HO OH 906.93 V. amurensis roots (Huang et al., H H 2001) O O
HO OH H H
H OH HO O H
OH OH OH Amurensin K OH 920.91 V. amurensis roots (Huang et al., 2001) H HO O
OH O H
OH OH HO H H HO O H HO H
OH OH
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Amurensin L HO 904.91 V. amurensis roots (Huang et al., 2001) O OH HO
OH OH HO HO H H H O O H
OH OH Amurensin M OH 902.89 V. amurensis roots (Huang et al., 2001)
HO
OH
HO HO O O OH OH HO
OH
OH OH HO Davidol A O O 906.93 V. davidii stems (Li et al., (hypothesized HO OH 1998a) structure)
HO OH HO OH
OH OH Flexuosol A OH 906.93 V. flexuosa stems (Li et al., 1998c) HO H HO O OH
HO H OH H H
OH O O H H HO OH
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Heyneanol A OH 906.93 V. amurensis roots (Huang et al., HO H HO O H V. betulifolia stems 2001; Jang et O OH OH V. heyneana stems al., 2007; Li et HO H al., 1996; Li et H H al., 1998b; Li et OH OH al., 2000) H O HO Hopeaphenol HO 906.93 V. amurensis roots (Guebailia et (12) H OH V. betulifolia stems al., 2006; He et O OH V. chunganensis al., 2009; whole plant Huang et al., HO H HO V. flexuosa stems 2001; Ito et al., H V. vinifera leaves, 1997; Li et al., H stems, roots, and 1998b; Li et al., OH OH H red wine 1998c; Reniero et al., 1996; OH Yan et al., HO O H 2001) OH Isohopeaphenol HO 906.93 V. amurensis roots (Huang et al., H OH V. vinifera leaves 2001; Ito et al., O OH and stems 1997; Mattivi et al., 2011; Yan HO H et al., 2001) H HO H OH OH H
OH HO O H OH Miyabenol A HO 922.92 V. thunbergii roots (Chiou et al., 2009; Huang et HO al., 2005) H H O OH O OH HO H H H
OH HO H O OH
OH Vaticanol C HO 906.93 V. vinifera leaves (Mattivi et al., OH isomer 2011) HO H (tentative O structure) OH H OH H H H H HO H OH O OH H OH HO
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(+)-Viniferol A OH 906.93 V. vinifera stems (Yan et al., OH 2001)
HO H OH O H
OH H H OH H
H H HO OH
O OH H HO (+)-Viniferol B OH 906.93 V. vinifera stems (Yan et al., OH HO 2002)
OH OH H H OH H H HO H H H O
O OH H HO OH (+)-Viniferol C HO 906.93 V. vinifera stems (Yan et al., H 2002) O OH
HO OH H H H OH O HO H H H H OH HO HO OH (+)-Viniferol E HO OH 924.94 V. vinifera roots (Fujii et al., OH H H OH O 2005) H H HO H H OH O OH HO O H H HO OH (+)-Vitisifuran HO 904.91 V. amurensis roots (Huang et al., A O OH V. vinifera stems 2001; Ito et al., 1999) HO OH
OH HO H H
H OH OH
HO O H OH
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(-)-Vitisifuran B HO 904.91 V. vinifera stems (Ito et al., 1999) O OH
HO OH HO OH
OH H H H O O H
OH
OH Vitisin A (r-2- HO 906.93 V. amurensis (Chen and H Viniferin) (7) O OH leaves, roots, and Wang, 2009; stems Chiou et al., HO V. betulifolia stems 2009; Ha et al., H OH V. chunganensis 2009b; He et whole plant al., 2009; OH V. coignetiae Huang et al., OH H stems and whole 2001; Huang et H plant al., 2005; Ito et H OH V. davidii stems al., 1998; Jang HO V. flexuosa stems et al., 2007; O OH V. thunbergii roots Korhammer et H and stems al., 1995; Li et HO V. vinifera stems al., 1998a; Li et V. wilsoniae stems al., 1998b; Li et al., 1998c; Li et al., 1998d; Oshima et al., 1993; Oshima et al., 1995b; Wang et al., 2011; Yan et al., 2001)
Z-Vitisin A HO OH 906.93 V. coignetiae (Ito et al., 1998; OH stems and whole Oshima et al., H plant 1993; Oshima et al., 1995b) OH H O
OH H H OH H OH HO
O OH H HO
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E-Vitisin B HO 906.93 V. amurensis roots (dBisson et al., H (r-Viniferin) O OH V. berlandieri 2011; Chen and HO roots Wang, 2009; Ito dV. riparia x V. and Niwa, 1996; H berlandieri roots Korhammer et OH HO OH V. cinerea roots al., 1995; Lou et V. coignetiae al., 2004; H OH stems Mattivi and H O V. longii roots Reniero, 1992; H H O V. riparia roots Oshima et al., V. rupestris roots 1995a; Wang et HO V. solonis longii al., 2011; Zga et roots al., 2009) OH V. solonis richter roots V. thunbergii var. taiwaniana stems and roots V. vinifera stems and roots Z-Vitisin B OH 906.93 V. amurensis roots (Lou et al., HO OH V. coignetiae 2004; Oshima et H O OH stems al., 1995a) H HO HO H O H H OH OH O H OH E-Vitisin C HO 906.93 V. thunbergii roots (Huang et al., H O OH V. vinifera stems 2005; Ito and HO Niwa, 1996)
H
HO HO OH
H OH H O H H O
HO OH
However, a recent study found the configuration dihydrobenzofuran form were isolated with both ( ) cis cis Z in downy mildew infected leaves, meaning and ( )-double bond configurations. The authors V. vinifera trans E both hydrogens arein the alpha or both in the beta position named these two -dihydrobenzofuran forms, - - cis E ω (Mattivi , 2011). This naming of and viniferin and - -viniferin , despite having et al. cis trans (16) Z ω (17) conformation for these hydrogens is an area of confusion the same planar structure as ε-viniferin, while other authors when dealing with stilbenoids, which often contain a trans have referred to this compound as 7a, 8a- -ε-viniferin ( ) or ( ) double bond as well. The nomenclature, cis E cis Z E/Z (Huang , 2000; Lin and Yao, 2006; Mattivi , for the and double bond, respectively, is more et al. et al. trans cis 2011). It should also be noted that in the relative precise, yet less commonly used in stilbenoid literature. conformation, the difference between the - The study by Mattivi (2011) illustrates this problem, cis et al. dihydrobenzofuran form and the -dihydrobenzofuran where both the - -viniferin and the - trans trans ε cis form can be determined by comparison of their NMR
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Vitisin D OH 906.93 V. coignetiae (Shinoda et al., H stems 1997) HO O
OH H OH H OH
OH H OH H HO
O OH H HO !
Breakdown Product from Tetramer
Compound aStructure M.W. Plant Name bReferences Name and Part (-)-Viniferal HO 574.58 V. thunbergii roots (Chiou et al., (11) V. vinifera stems 2009; Huang et H O OH al., 2005; Ito and Niwa, HO 1996) OH H H
H OH O
OHC !
data. Determining the absolute configuration, however, is more challenging, i. e. the difference between (+) and QUANTIFICATION OF STILBENOIDS (-)-ε-viniferin. For known compounds, their [α]D values 1 Quantification methods can be compared with the literature. Currently, only the Numerous techniques have been used for the (+)- -viniferin form has been proven to be in Vitaceae, ε quantification of stilbenoids with varying degrees of whereas (-)-ε-viniferin can be found in other plant families (Lin and Yao, 2006). Nevertheless, there have been success. The primary techniques used include liquid isolated reports of (-)- -viniferin in , though the chromatography with ultraviolet detection (LC-UV), LC- ε Vitis complete spectroscopic data set was not provided (Amico fluorescence detection, gas chromatography-mass , 2009; Kulesh , 2006). A careful discussion on spectrometry (GC-MS) and LC-MS, in conjunction with et al. et al. the difficulties in determining the relative and absolute numerous sample preparation techniques, see Table 3. configurations of the viniferins and other stilbenoids, is The majority of the initial studies utilized GC-MS, provided in the publication by Mattivi (2011). Due however, this method has drawbacks, such as derivation et al. to the difficulties in assigning absolute configurations to requirements and destruction of oligomers and glycosides stilbenoid oligomers, many compounds have been prior to detection. These properties have a tendency to reported with only their relative configurations assigned. promote artificially high aglycone monomer levels and to -isomer conversions (Flamini, 2003; Soleas , However, since (+)-ε-viniferin is considered a major E Z et al. stilbenoid intermediate for larger oligomers, the structures 1997). While HPLC-UV analysis does not have the same containing viniferin moieties are normally presented as problems as GC-MS, other problems such as lack of containing the same configuration when not otherwise baseline resolution, leading to overestimation of individual determined. In the reports of many complex oligomers, stilbenoid levels, may exist, along with poor sensitivity. only the relative configuration has been assigned. More selective techniques such as fluorescence detection
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!
Pentamers
Compound aStructure M.W. Plant Name bReferences Name and Part
Amurensin E OH 1132.14 V. amurensis roots (Huang et al., OH 2000) H O O HO OH H HO HO OH
H H OH HO OH H
HO O H
HO Amurensin F OH 1132.14 V. amurensis roots (Huang et al., OH 2000) H O O HO OH H HO OH OH
HO H O H H HO H O
OH OH !
can help overcome these drawbacks, whereas the high incomplete extraction due to poor solvent choice. selectivity of LC-MS techniques can eliminate this Comparisons of multiple solvent extraction efficiencies problem. However, matrix effects offer a particular have shown that 50 to 60 % ethanol in water was more effective for -resveratrol and - -viniferin extraction in challenge in the quantitation of individual compounds in E E ε complex samples such as wine. This may be overcome vine canes than a wide-range of other solvent systems and ratios tested (Karacabey and Mazza, 2008; Rayne by sample cleaning techniques such as solid phase et , 2008). In another study, comparing extraction rates extraction (SPE), sample dilution, selective extraction, or al. use of stable isotopes (Careri , 2004; Stark , of solvents with grape skins, a different set of solvents et al. et al. 2011; Zotou and Frangi, 2008). The comparison of LC- was tested and acidified methanol was shown to be most effective for resveratrol and piceid extraction (Sun , UV with LC-MS-MS has shown the later to have higher et al. sensitivity and selectivity (Careri , 2004). 2006). Higher temperatures and ultrasonication also et al. improve extraction efficiencies, but decomposition or We have compiled quantitation studies of stilbenoids isomer conversion may occur more readily. Therefore, in species, including wine, in Table 3. While useful, Vitis differences between studies may represent differences in comparison between quantitation studies has some extraction efficiencies or changes occurring during the drawbacks since additional, non-detector variables exist, extraction procedures. Additionally, there are variations particularly when comparing solid materials such as grape in the preparation of plant material that need to be skins or stems. One important problem may involve considered when comparing mul≤tiple studies. Some
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!
Hexamer
Compound aStructure M.W. Plant Name bReferences Name and Part
Chunganenol HO HO 1372.40 V. chunganensis (He et al., 2009) OH whole plant HO OH H HO H H H HO H OH O H HO H
O HO HO H H HO O H HO
OH
OH
!aMany reports of previously isolated known compounds were not confirmed using all spectroscopic techniques required for unambiguous assignments. We included these to have a more complete list where stilbenoids have been identified. Additionally, due to the challenge of assigning absolute stereochemistry to complex oligomers, only the relative configuration was reported in some cases. We drew the structures as reported, but these may only reflect relative configurations. In the case of common compounds such as - -viniferin, we attempted to E ε differentiate between reports where the configuration was determined from those where only the planar structure was determined. bAll or most of the spectroscopic information can be found in underlined references. cThis report of pallidol from (Kulesh ., 2006) has recently been disputed due to discrepancies in NMR data (Mattivi , V. amurensis et al et al. 2011). dThis report of vitisin B had an error in the original publication, the name of the structure was erroneously given as vitisin C.
researchers have used the fresh weight of the plant material isomer, -resveratrol, in addition to their glycosides, - Z Z whereas others have used the dry weight, making and -piceid, have become more common. The majority E comparison between these studies difficult. Using the of research has been performed on wine made from fresh weight for quantitation studies may also be different cultivars of , including comparisons V.vinifera complicated by amount of rainfall or lack of rainfall levels of wines made in different years, geographic locations, immediately prior to collection. Due to the role of micro-climates, and using different methods of vinification, stilbenoids as phytoalexins, quantitation of stilbenoids see Table 3 (Bavaresco, 2003; Moreno-Labanda , et al. has been performed on different parts of infected 2004). A 2007 review by Stervbo summarized the et al. grapevines. However, even within these studies, variations findings from 31 papers on the quantitation of -resveratrol E exist in sample material. For example, some studies levels in a total of 511 individual monovarietal red wines, examined only the infected parts of the leaves and others including 21 different varieties from 18 regions around extracted the entire leaf that showed some degree of the world. Not all of these studies examined -resveratrol Z infection. We have therefore attempted to include all and the piceids, but the authors included these data when relevant information available in Table 2. available. The overall levels of -resveratrol ranged from E undetectable levels to 14.3 mg/l, with an average of 2 Quantitation results 1.9 mg/L. In this review no variety or region was found A tremendous effort has been made to quantify levels to be clearly superior. Interestingly, varieties such as Pinot of stilbenoids in wine of multiple varieties, vintages, noir tend to have higher levels, though this higher level terroir, and growth conditions. Since the initial quantitation was not ubiquitous with every Pinot noir tested. No distinct trends were observed with -resveratrol, which ranged of resveratrol in wine by Siemann and Creasy in 1992, Z the quest to find which variables may produce wines with from undetectable levels to 5.1 mg/L, averaging 1.0 mg/L. high concentrations has been ongoing (Siemann and The piceid isomers, which were typically higher than Creasy, 1992). While -resveratrol concentrations have resveratrol levels, averaged 5.4 and 1.4 mg/L for - and E E been the most widely reported, efforts to quantify its -piceid, respectively. A slight trend appeared when Z
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Table 3 - Summary of recent quantitation studies of different stilbenoids, in Vitis species. !"#$%& -./(.0$1& !"#$%&!#2%3&4#2+)%5672+8+$3&-.$*)$%2#%+.$3& #=+$)& F);)2)$*),& '()*+),& 9)%:.1&.;&<0#$%+%#%+.$& -.$*)$%2#%+.$,3& +$&/86>& ?@A)2#8),3& B:)$&#A#+"#C")3& #$1&,#/(")& ,+D)E& !"#$%&'()*+*# ,-!"#$"%&'%()* '%)/,+*&$"%&,"*(-*.&'&*-%(/*!"#$%&'()*+**&0.* * CDE&0,#(0#$1"+* !"#$%&'()*+**1*!"#.+)+/('$+*23456789* ?FGGH* ::;<=±>?
!"#1$3'&*4$# 56!"#$"%&'%()* =+$)+*K56LM* G
,6!"#$"%&'%()# >)#A),+#/,@,*.B+*23456789* * CR&0P#(0#$1"+* F<=GI±F =+$)+*K56LM* G 3PQ"P.* QG)225&,H+$,+*23456789* * CS&'"%E(T#"* VR* &0.*4&/T")&6 !&$"0'U#+* G;;IH* !"# ,-!"#$"%&'%()# '%)/,+*5EP0"#"+*.P--"%"0'*%",P(0#*"$&)T&'".+* * CDE&0,#(0#$1"+* 6()0$78)$# 23456789* ?FGGH* =FF<>±>I<;6:J:<:±JF<;*/,@A,*-B# 9"# 5-!"#$"%&'%()* =+$)+*W/"%PQ&0+*K56LM9* ;H* C/T#Q&.P0"H* LT#Q&.P0"*Y(%'* J , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 85 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page86 A.D. PAWLUS et al. ,6W#'%P0,P0* =+$)+*`%"0QE*Ca"%,"%&QH+*%".*&0.*BEP'"+*45* !".9*VR6J: , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 86 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page87 V"%(*.fW$()&9*VR* L"%)('9*'%&Q"* V"%(*.fW$()&^V"%"))(^L&#Q&)"#"^3P,0&'"))(9* VR* W,)P&0PQ(9*G =+$)+*V(%'E*W-%PQ&0+*23456789* !".9*VR6= , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 87 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page88 A.D. PAWLUS et al. =+$)+*5&0&.P&0+*23456789* F ,63PQ"&'&00()* =+$)+*e'&)P&0+*456LM6LM9* !".9*'%&Q"6N6F<:F*C0O?H* L(0'"YT)QP&0(*F<;J6N=*C0O?H* V"%(*.fW$()&9*G L(T%$j.%"*CL(0&#'%"))H+*MY&0P#E+*2345678* FJ±F:±F*CN , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 88 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page89 >)),9*F =+$)+*`%"0QE*Ca"%,"%&QH+*%".*&0.*BEP'"+*45* !".9*VR6?I , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 89 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page90 A.D. PAWLUS et al. =+$)+*MY&0P#E+*L(T%$j.%"*CL(0&#'%"))H+* VR6GI<:F* CL(%"0(6 23456789* C0OINH* 4&X&0.&#(0#$1"+* k(T0,9*VR6=*C0OG?H* MB""'9*VR*C0OJH* l%,&0PQ9*J<=?6GG =+$)+*`%"0QE*Ca"%,"%&QH+*%".*&0.*BEP'"+*45* !".9*F , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 90 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page91 =+$)+*V(%'E*W-%PQ&0+*23456789* ; , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 91 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page92 A.D. PAWLUS et al. =+$)+*MY&0P#E+*L(T%$j.%"*CL(0&#'%"))H+* VR6?;>+*0O?GH* ?FFIH* l&A6&,".9*> G)225&,H+$,+*`%"0QE+*BP'E*$&%]P0,*.",%""#*(-* * CW.%P&0#(0#$1"+* ;"#4+)('($*P0-"Q'P(0+*?I*&0.*I:*E(T%#*&-'"%*78* ?FFFH* )P,E'*'%"&'/"0'+*2345*BP'E*-)T(%"#Q"0Q"* ."'"Q'P(0+*/,@A,*-B9* K&/&]9* V(0P0-"Q'".9*J=<=*C78+*?IEO=;<=+*I:EO=N , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 92 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page93 >)#A),+*:"#.+0+481$*P0-"Q'".+*&$"%&,".*($"%*J* * C8%E($#"A#(0# ]"&%#+*>*.&]#*Y(#'6P0-"Q'P(0+*Z,@,*-B9* $1"+*?FGGH* `G*,"0(']Y"*?G@GFJ9*N 3'"%(#'P)X"0"* G)225&,H+$,+*`%"0QE+*BP'E*$&%]P0,*.",%""#*(-* * CW.%P&0#(0#$1"+* ;80'<0+*#4+)('($*P0-"Q'P(0+*?I*&0.*I:*E(T%#* ?FFFH* &-'"%*78*)P,E'*'%"&'/"0'+*2345*BP'E* -)T(%"#Q"0Q"*."'"Q'P(0+*/,@A,*-B9* K&/&]9* V(0P0-"Q'".9*F*C78+*?IEOF , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 93 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page94 A.D. PAWLUS et al. =+$)+*`%"0QE*Ca"%,"%&QH+*%".*&0.*BEP'"+*45* !".9*VR6F<;*CF , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 94 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page95 4"/X"%,"%+*?FF:9*F<=:nF =+$)+*MY&0P#E+*2345*BP'E*-)T(%P/"'%PQ* !".9*VR6F+*0O?IH* ?FF:H* * SEP'"9*VR6F6F*CF , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 95 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page96 A.D. PAWLUS et al. bP0'"'9*J<>F* V"%(0"'9*;<;F* L"%)('9*= =+$)+*W/"%PQ&0+*2345678*BP'E*LM* !".9*VR6J '%)/,+*3P0('*V(P%+*23456789** * C!&]0"#(0#$1"+* J '%)/,+*45678*_T&0'P'&'P(0*BP'E*456LM* * C3r##&#(0#$1"+* ."'"Q'P(0+*/,@,*.B9* ?FF>H* 2&#&P0"*M)&.AP9*JH* DP),&9*? , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 96 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page97 '%)/,+&\#'(0P&0+&45678*_T&0'P'&'P(0*BP'E*456 * CW&$PA#&&%#(0# LM*."'"Q'P(0+*/,@,*.B9& $1"+*?FFJH* !"#.+)+/('$*Q$<+*0('*#Y"QP-P".9*G* DP),&9*F , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 97 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page98 A.D. PAWLUS et al. V"%(*.fW$()&9*G;* M&0,P($"#"^5P)P",P()(^5&0&P()(9*? , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 98 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page99 G#'*B""A9*F*CF '%)/,+*bT%AP#E*'&X)"*,%&Y"#+*2345678+*/,@A,* * Cu"'P0#(0#$1"+* .B9* ?FGGH* W)YE(0#"*4&$&))h"9*?nF , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 99 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page100 A.D. PAWLUS et al. LP).)]*P0-"Q'".9*J =+$)+*a%&[P)P&0+*23456789* F , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 100 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page101 b"/Y%&0P))(9*F '%)/,+*3P0('*V(P%+*23456789** * Cd&%&Q&X"]* ? L(T%$j.%"*CL(0&#'%"))H+*MY&0P#E+*2345678* * C5&0'(##(0#$1"+* BP'E*LM*P."0'P-PQ&'P(0+*Y%"*&0.*Y(#'*7865* ?FFJH* P%%&.P&'P(09* M()P.#*P0*/,@A,*-B*C0OJH9* G)22+),9*> , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 101 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page102 A.D. PAWLUS et al. >)#A),+*5E&##")&#+*P0-"Q'".*BP'E*:"#.+0+481$*-(%* * C3"["'#(0#$1"+* =*.&]#*(%*=?*E(T%#*&-'"%*7865*P%%&.P&'P(0+* ?FFJH* /,@,*-B9* :"#.+0+481$9*:><:GnG: looking at latitude in the northern hemisphere, where also ambiguous, since levels between thin and thick varied more northern locations contained higher resveratrol unpredictably (Stervbo , 2007). content. One example of this is the higher concentrations et al. in Canadian red wines than those found in Greece or Additional efforts to quantify resveratrol in wine have Japan. The authors also looked to see if a trend was occurred, which we included in Table 3. In addition to apparent with thick and thin skinned grapes. This was examining wine samples, studies have quantified , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 102 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page103 stilbenoids in separate plant parts, the berries themselves, - and -resveratrol concentration in the berries of E Z and wine during the vinification process in order to gain Mencia, Albarello and Merenzao grapes. In this study, a better understanding of the stilbenoid level dynamics. Mencia berry skins had approximately 10 times the For example, in a study by Gatto (2008), the et al. concentrations of -resveratrol than the other two varieties -resveratrol and - and -piceid levels were examined E E Z E tested (Moreno , 2008). These high levels of - in 78 white and red grape varieties grown in et al. E V.vinifera resveratrol in Mencia wine and grapes warrant further the same research station in three different years. This investigation. It would also be interesting to determine if study controlled for influences such as climate variability the levels of other stilbenoids were also high in this variety and differences in vinification methods by studying the or if this monomer dominates. berries directly, allowing genetic influences and ripening phases on stilbenoid levels to be examined. The authors The main purpose of these quantitation studies has evaluated the grapes at three different time points to generally been to determine the amount of these determine the levels of the three different stilbenoids at biologically important molecules in wines and grapes veraison, at technological ripeness, and at a post-ripening currently being consumed. Additional studies have aimed phase, 20 days later. They simultaneously monitored at determining which factors, such as specific vinification genetic expression between high and low resveratrol processes, variety used, and location, may contribute to producers. The authors demonstrated that in high higher levels. However, this has proved challenging since resveratrol producers, such as Pinot noir, Tarrango, stilbenoid content varies significantly in wines, even the Franconia, Alicante Bouquette, and Carmenere, there was same types of wine produced in the same region can stilbenoid accumulation in the berries throughout contain nontrivial differences. Numerous studies have development. Both - and -piceid were constitutively found that stilbenoid levels in grapes and leaves are E Z expressed, whereas resveratrol was confirmed to be an influenced by a number of factors, including genetic, inducible stilbenoid (Gatto , 2008). They also nutritional, climatic, disease status, altitude, and latitude et al. (Bavaresco, 2003; Bavaresco , 2007; Deluc , supported the reoccurring finding that Pinot noir is one et al. et al. of the varieties with higher levels of resveratrol (Lamuela- 2011; Tinttunen and Lehtonen, 2001). For example, since Raventos , 1997; Melzoch , 2001). In another resveratrol is induced in berries, levels of disease pressure et al. et al. recent study, 186 Portuguese red wines of different varieties in the vineyard may influence resveratrol levels. This and vintages were evaluated for their - and -resveratrol relationship is not linear however, as a small amount of E Z content using HPLC-UV. -resveratrol levels ranged from disease pressure increases stilbenoid production, while E 0.05 to 10.9 mg/L, while the concentrations of - highly infected berries have lower levels (Adrian , Z et al. resveratrol ranged from 0.04 to 8.7 mg/L. The identity of 2000). Similar non-linearity has been seen in resveratrol levels and increasing altitudes (Bavaresco , 2007). all the varieties tested was not provided, since many were et al. blended wines, but wine made from Touriga Nacional In other studies, incubation of resveratrol and pterostilbene with , the causative organism of gray variety in the Beira Interior denomination of origin Botrytis cinerea contained the highest resveratrol content (Paulo , mold, showed oxidative dimerization of both compounds, et al. 2011). demonstrating disease status may also influence overall stilbenoid profiles (Breuil , 1998; Breuil , 1999). et al. et al. Most studies have not been able to single out a wine Controlled studies using infected leaves showed P. viticola variety with consistently higher stilbenoid levels, with the high year-to-year variability of a number of stilbenoids, possible exception of Pinot noir, which many studies have demonstrating a need for multi-year studies (Vrhovsek shown to have the highest average, and a lesser known , 2011). These factors, that play a role in stilbenoid et al. variety, Mencia. In a recent study focusing on resveratrol synthesis, have been reviewed and updated by Bavaresco isomers, involving wines from 5 different Galician (Bavaresco and Fregoni, 2001; Bavaresco , et al. et al. Controlled Denomination of Origin regions in 2009). Other factors such as influence of phylloxera Northwestern Spain, the Mencia variety from Valdeorras resistant rootstock have yet to be evaluated. Furthermore, had one of the highest -resveratrol concentrations E the process of vinification has influences on wine currently known. In one monovarietal wine sample, the stilbenoids, both qualitatively and quantitatively. Known -resveratrol concentration was 36.1 mg/L. Mencia E influential factors include maceration and fermentation containing wines from Ribeira Sacra also contained high time and temperature, yeast and bacteria used for alcoholic levels, up to 31.4 mg/L. However, the Mencia grown in and malolactic fermentation, and post-processsing factors Ribeiro CDO were much lower, with levels ranging from such as wine bottle aging (Monagas , 2005; Poussier 2.5 to 5.8 mg/L. The concentration of -resveratrol in all et al. Z , 2003; Vitrac , 2005). wines was very low, with a maximum -resveratrol et al. et al. Z concentration of 0.25 mg/L (Feijóo , 2008). The To further complicate matters, there is an observable, et al. relatively high concentration of resveratrol in Mencia dynamic relationship between the resveratrol monomers berries was also demonstrated in a study comparing the with their corresponding glycosides and oligomers. For , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 103 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page104 A.D. PAWLUS et al. example, a study involving the UV irradiation of leaf Burgundy and a range of North African wines, with discs showed resveratrol levels peaking at 18 hours, then concentrations up to 2.1 mg/L. Taken together, these decreasing as ε-viniferin levels increased, peaking at studies show that the range of concentrations among and 36 hours (Langcake and Pryce, 1977b). This gradual between these compounds in different wines varies accumulation of viniferins after exogenous induction has significantly, from below detectable levels to tens of been confirmed in grape skins as well (Gonzalez-Barrio mg/mL, see Table 3 for references. , 2006). During the wine making process itself, et al. glycoside levels typically fall while monomer levels rise. In addition to studies involving the quantitation of This is due to the alcoholic and, to a lesser extent, the stilbenoids in wine and berries, there is a growing interest malolactic fermentation processes, causing a decrease in in evaluating the stilbenoids in other parts of the grapevine. glycoside levels via deglycosylation reactions, in addition Since roots, stems, canes, and rachis are a byproduct of to increases in extraction efficiency of the aglycones from the wine industry, they are an untapped source of these the grape skins as alcohol levels increase (Bavaresco biologically active molecules (Bisson , 2011; Rayne et et al. , 1999; Vian , 2005; Vrhovsek , 1997). , 2008; Zhang , 2011). A recent comparison al. et al. et al. et al. et al. However, as seen in the review article by Stervbo of plant parts, examining resveratrol levels in et al. V.vinifera (2007), many wines still contain high levels of glycosides the shoot tips, petiole, leaves, stem phloem, stem xylem, and low levels of aglycones. In the 2005 study by Vitrac and roots demonstrated highest levels in the stem phloem, , a 1999 Brazilian Merlot contained 23 mg/L of axillary bud, and roots (Wang , 2010). Additionally, et al. et al. -astringin, a glycoside of piceatannol, and no detectable species other than have different stilbenoid E Vitis V.vinifera quantities of -resveratrol (Vitrac , 2005). This profiles and may be rich sources of biologically active E et al. suggests that in studies where only the levels of resveratrol stilbenoids. For example, in our laboratory, we found the aglycones in wines have been determined, a substantial roots of a phylloxera resistant grapevine rootstock, x SO4A, had significant levels amount of glycosides may exist, however the reason is V.riparia V. berlandieri not known (Goldberg , 1995; Waterhouse and of the stilbenoid tetramer, -vitisin B. The levels of et al. E Lamuela-Raventós, 1994). In another example, wine stilbenoids in stems and roots also appear to be seasonally made from Cabernet Franc has been reported in several dependent. For example, a 2002 study comparing the studies to have one of the lowest levels of -resveratrol concentrations of -viniferin and -resveratrol in the stems E ε E when compared to others such as Pinot noir, Cabernet- showed that there were significantly higher levels of these Sauvignon, and Merlot (Gatto , 2008; Nikfardjam two compounds in October than in July and January et al. , 2006). However, in a study comparing several (Aaviksaar , 2003). Plant part, variety, and disease et al. et al. Merlot and Cabernet-Sauvignon wines with a Cabernet pressure can influence the type and quantity of stilbenoids Franc, -astringin (18) was highest in Cabernet Franc, at E found. a concentration of 23.1 mg/L, which made its overall stilbenoids quantity comparable to the other wines (Vitrac , 2005). This demonstrates the usefulness of CONCLUSION et al. We have reviewed the current state of stilbenoid quantifying a greater range of stilbenoids in wine when Vitis trying to determine stilbenoid levels. chemistry and show that it is a very active area of research. Eighteen of the approximately 60 species in have at Vitis So far, of the 19 currently known stilbenoids in wine, least one reported phytochemical study with a current 12 have been quantified in at least one study, as referenced total of around 100 known stilbenoids. The most studied in Table 3. These compounds include the and forms species is the primary wine producing species, E Z Vitis of astringin, piceid, resveratrol, and ε-viniferin, in addition , followed by other minor species used for wine, to hopeaphenol, pallidol, -piceatannol, and - -viniferin V.vinifera E E δ species used as phylloxera resistant rootstock for (19). The piceatannol glycoside, -astringin, was , and species used as medicinal plants. Sixty- E V.vinifera quantified in wines from France, Brazil, Canada, Italy, one stilbenoids have been identified in various plant and Portugal, where levels ranged from undetectable to tissues, cell cultures, and wine of with only 19 V.vinifera 38.1 mg/L, in a French Bergerac wine. Its isomer, currently known constituents of wine. The isolation and -astringin was quantified in a number of Italian wines Z structure elucidation of stilbenoids is not trivial, particularly where it was found to have levels up to 1.3 mg/L, similar as the determination of absolute configurations becomes to -astringin levels which ranged from undetectable to E more difficult as oligomer sizes and complexities increase. 1.8 mg/L. Several dimers, including pallidol, - and Z - -viniferin, and - and - -viniferin were also Due to the interest in the health promoting and E ε Z E δ examined, of these, δ-viniferin was found to have the antifungal properties of stilbenoids, we summarized recent highest levels, 22.4 mg/L in a Brazilian Merlot. The only studies pertaining to their quantitation in different plant known tetramer to be unambiguously identified in wine, parts and wine. The majority of studies have focused on hopeaphenol, was quantified in Pinot noir wines from resveratrol and piceid levels, with more recent research , 2012, , n°2, 57-111 J. Int. Sci. Vigne Vin 46 ©Vigne et Vin Publications Internationales (Bordeaux, France) - 104 - 06àutiliser-mérillonbis_05b-tomazic 27/06/12 21:23 Page105 Anstey K.J., Mack H.A. and Cherbuin N., 2009. Alcohol quantifying additional monomers, dimers and complex consumption as a risk factor for dementia and cognitive decline: Meta-analysis of prospective studies. oligomers. The metabolic pathways for stilbenoid synthesis Am. J. Geriatr. , , 542-555. are complex and the relationship between stilbenoids is Psychiatry 17 dynamic since they are influenced by multiple Baderschneider B. and Winterhalter P., 2000. Isolation and environmental and genetic factors. Wine presents an even characterization of novel stilbene derivatives from Riesling wine. ., , 2681-2686. more complex case as viticultural and vinification J. Agric. Food Chem 48 techniques may vary widely between varieties and regions. Balík J., Kyselákova M., Vrchotová N., Tríska J., Kumsta M., Therefore, studies quantifying only a small number of Veverka J., Híc P., Totusek J. and Lefnerová D., 2008. stilbenoids may be misleading in regards to overall Relations between polyphenols content and antioxidant activity in vine grapes and leaves. , , stilbenoid content. Czech J. Food Sci. 26 S25-S32. The multiple techniques for quantitation studies, Barjot C., Tournaire M., Castagnino C., Vigor C., Vercauteren J. pertaining to the plant preparation, extraction, and and Rossi J.-F., 2007. Evaluation of antitumor effects of experimental methods, vary considerably in the literature, two vine stalk oligomers of resveratrol on a panel of complicating comparisons between studies. A uniform lymphoid and myeloid cell lines: Comparison with resveratrol. ., , 1565-1574. examination of plant material, including wine, using Life Sci 81 validated, rigorous methods for a complete stilbenoid Baur J.A. and Sinclair D.A., 2006. Therapeutic potential of resveratrol: The evidence. , profile will provide useful information in regards to in vivo Nat. Rev. Drug Discov. , 493-506. stilbenoid levels and allow better comparisons between 5 species and varieties. Bavaresco L., Petegolli D., Cantü E., Fregoni M., Chiusa G. and Vitis Trevisan M., 1997. Elicitation and accumulation of stilbene phytoalexins in grapevine berries infected by A more thorough understanding of the stilbenoid Botrytis profile within individual economically valuable . , , 77-83. Vitis cinerea Vitis 36 species, in addition to wine, will be extremely valuable Bavaresco L., Fregoni C., Cantu E. and Trevisan M., 1999. 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