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Review

A Reference List of Phenolic Compounds (Including Stilbenes) in Grapevine (Vitis vinifera L.) Roots, Woods, Canes, Stems, and Leaves

by
Piebiep Goufo
1,*,
Rupesh Kumar Singh
2 and
Isabel Cortez
1
1
Centre for the Research and Technology of Agro-Environment and Biological Sciences, Departamento de Agronomia, Universidade de Trás-os-Montes e Alto Douro, Quinta de Prados, 5000-801 Vila Real, Portugal
2
Centro de Química de Vila Real, Universidade de Trás-os-Montes e Alto Douro, Quinta de Prados, 5000-801 Vila Real, Portugal
*
Author to whom correspondence should be addressed.
Antioxidants 2020, 9(5), 398; https://doi.org/10.3390/antiox9050398
Submission received: 15 April 2020 / Revised: 1 May 2020 / Accepted: 5 May 2020 / Published: 8 May 2020
(This article belongs to the Special Issue Phenolics as Antioxidant Agents)
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Abstract

:
Due to their biological activities, both in plants and in humans, there is a great interest in finding natural sources of phenolic compounds or ways to artificially manipulate their levels. During the last decade, a significant amount of these compounds has been reported in the vegetative organs of the vine plant. In the roots, woods, canes, stems, and leaves, at least 183 phenolic compounds have been identified, including 78 stilbenes (23 monomers, 30 dimers, 8 trimers, 16 tetramers, and 1 hexamer), 15 hydroxycinnamic acids, 9 hydroxybenzoic acids, 17 flavan-3-ols (of which 9 are proanthocyanidins), 14 anthocyanins, 8 flavanones, 35 flavonols, 2 flavones, and 5 coumarins. There is great variability in the distribution of these chemicals along the vine plant, with leaves and stems/canes having flavonols (83.43% of total phenolic levels) and flavan-3-ols (61.63%) as their main compounds, respectively. In light of the pattern described from the same organs, quercetin-3-O-glucuronide, quercetin-3-O-galactoside, quercetin-3-O-glucoside, and caftaric acid are the main flavonols and hydroxycinnamic acids in the leaves; the most commonly represented flavan-3-ols and flavonols in the stems and canes are catechin, epicatechin, procyanidin B1, and quercetin-3-O-galactoside. The main stilbenes (trans-ε-viniferin, trans-resveratrol, isohopeaphenol/hopeaphenol, vitisin B, and ampelopsins) accumulate primarily in the woods, followed by the roots, the canes, and the stems, whereas the leaves, which are more exposed to environmental stresses, have a low concentration of these compounds. Data provided in this review could be used as (i) a metabolomic tool for screening in targeted and untargeted analyses and (ii) a reference list in studies aimed at finding ways to induce naturally occurring polyphenols on an industrial scale for pant and human disease control.

1. Introduction

Grapevine (Vitis vinifera L.) is a perennial woody fruit crop used for wine, juice, fresh consumption (table grapes), dried fruit, and distilled liquor [1,2,3,4,5,6,7,8]. Most of the premium cultivars are highly susceptible to several pathogenic microorganisms [6,9,10,11,12,13]. In the past decades, the understanding of grapevine/pathogen interactions has focused on the molecular response of the host, and several metabolites, proteins, and gene/gene products have been identified as putative biomarkers of grapevine disease tolerance [14,15,16,17,18]. In particular, the importance of phenolic compounds as natural fungicides implicated in the resistance of some grapevine cultivars to fungi, oomycetes, bacteria, phytoplasma, and viruses have been highlighted by several authors; one of the most known properties of these compounds is their antioxidative activity, whereby they are able to scavenge free radicals and positively influence health outcomes [5,19,20,21,22,23,24,25,26,27,28,29,30,31]. Plants have evolved a variety of mechanisms using phenolic compounds, including the formation of a protective shield against ultraviolet (UV) radiation. Therefore, the compounds produced by highly resistant varieties are of great interest for the development of improved crops, natural spray reagents, and new dietary supplements or pharmaceuticals [5,19,32,33,34,35,36].
In V. vinifera, many studies have been published that reported on the concentration of phenolics in berry-containing foods and their impact on human health [18,35]. Indeed, several databases are available for the levels of phenolic compounds in the fruits (e.g., eBASIS, Phenol-Explorer), but none are available for non-edible parts of V. vinifera. Recently, the stems and canes of this economically important genus have been reported as an untapped source of health-promoting compounds [16,17,31,35,36,37,38,39]. Because of this, numerous efforts for isolation, identification, and quantification of phenolic compounds in the vegetative organs of grapevine have been ongoing. In order to properly design valorization strategies, the precise chemical composition of these vegetative materials has to be known. In this review, a more thorough understanding of the chemical diversity of polyphenols within V. vinifera vegetative organs is provided, which will be useful in this endeavor. The review includes an overview of compounds identified in the roots, cordon and trunk woods, canes, stems, and leaves with their mass and UV spectrum patterns, followed by an estimation of their levels. It concludes with a brief presentation of factors affecting the biosynthesis and accumulation of these compounds. The fallout of such data is multifaceted and will surely contribute to advancing the scientific knowledge in the field.

2. The Vegetative Organs of the Vine Plant

Grapevine is a climber whose growth in the vineyard is maintained with pruning in order to control the quantity and quality of the grapes [40]. Like any other plant, grapevine has vegetative and reproductive organs. The vegetative organs of vine include the roots and five parts extending from the root system and visible aboveground: trunk, cordons, canes, stems, and leaves. These organs play a key role in light energy capture via photosynthesis, as well as water and nutrient absorption as regulated by transportation.

2.1. Roots

The roots of a vine plant are multi-branched structures that grow to various depths into the soil on the basis of the variety (rootstock), and are responsible for anchoring the plant to the ground [12,23,29,30,41,42].

2.2. Woods

In the literature, the “wood” refers to samples obtained from the trunk and the cordons. The trunk is composed of sleeves of conductive tissues, most notably the phloem and the xylem [13,43,44,45]. Cordons or “arms” are extensions of the trunk and the parts where canes (one-year-old wood containing between 8 and 15 buds) and spurs (one-year-old wood containing between two and three buds) originate [12].

2.3. Canes

The terms “stems”, “canes”, “stalks”, and “shoots” are sometimes used interchangeably in the literature. For the purpose of this review and on the basis of the literature surveyed, the shoot is the new green growth that develops from buds located on the cordons [24,25,46,47,48,49]. Once the leaves fall from the vine at the beginning of the dormant season, the brown and harden/woody shoot is considered a cane, which represents a large source of waste derived from the wine industry [40,50,51,52].

2.4. Stems

The stem consists of the stalk extending out to hold the grape cluster (also known as the bunchstem) and the “stem” of the individual grape berry (also called the pedicel by some authors) [9,37,50,53,54,55,56,57,58].

2.5. Leaves

Leaves are the most visible parts of the canopy and consist of the blade (the broad, flat part of the leaf designed to absorb sunlight and CO2), and the petiole (the stem-like structure that connects the leaf to the shoot) [4,5,11,19,22,32,59,60,61,62,63,64].

3. Extraction, Separation, and Identification of Phenolic Compounds in Grapevine

In grapevine varieties, polyphenols are present as constitutive compounds of the lignified organs (roots, canes, seeds, stems, ripe cluster stems) and/or as induced substances in leaves and berries. In the frame of a long-term project aimed at investigating the physiological and molecular responses of grapevine to trunk diseases [15], several papers that contained the terms “grapevine, grape, vine, vineyard, or vitis” in their titles, plus one of the following terms: “phenolic, polyphenol, flavonoid, anthocyanin, proanthocyanidin, tannin, stilbene, stilbenoid, bioactive, bioactivity, antioxidant, antioxidative, metabolite, metabolic, metabolomic, metabolome, leaf, stem, root, wood, cordon, cane, trunk, phytoalexin, defense, resistance”, or terms related to the specific diseases and pathogens of grapevine, were retrieved from citation databases; 80 papers were analyzed that primarily reported on the presence and levels of polyphenols in the vegetative organs (Tables S1 and S2). The term “polyphenol” is used in this review to indicate both the compounds with a second aromatic ring and those arising from the polymerization of flavonoidic/catechin units. Despite their structural diversity, all polyphenols share a common structure element, which consists of a benzene ring to which more than one hydroxyl group is attached [65].
The surveyed literature shows that many extraction methods have been tested, and that several analytical methods using numerous techniques have been developed for the investigation of polyphenols in grapevine, including high-performance liquid chromatography (HPLC) coupled with diode array detection (LC–DAD), HPLC coupled with mass spectrometry (LC–MS, LC–MS/MS), and nuclear magnetic resonance (NMR) [24,28,36,66,67]. Different advantages and disadvantages are associated with each analytical system. Analysis by HPLC–DAD (or HPLC/UV–VIS) is limited by similar or identical absorption maxima of target compounds belonging to the same structural class of polyphenols. Other problems such as lack of baseline resolution, leading to overestimation of individual compound levels, may exist, along with poor sensitivity [16,17,36]. Because of its high selectivity, LC–MS/MS with electrospray ionization (ESI), atmospheric pressure photoionization (APPI), or chemical ionization (APCI) enables the sensitive and simultaneous detection and identification of a large number of (even co-eluting) compounds from a single chromatogram and is therefore the method of choice when libraries are available. MS also enables reductions in the process of sample preparation from extracts [10,68]. NMR, on the other hand, is a non-destructive high throughput method that allows metabolite identification and quantification. It is, however, significantly less sensitive than MS, although more reproducible, especially in long-term studies where samples collected and analyzed over different time periods have to be compared. NMR is also an invaluable tool for the de novo structure determination of compounds [16,59]. In all cases, however, precise conditions are required to achieve a complete qualitative survey of all metabolites over a significant dynamic range in a complex plant extract. Depending on the optimization of extraction and detection parameter settings, two large groups of chemical compounds with phenolic characteristics—that are classified into several structure classes—are clearly delineated in grapevine and are separately discussed in this paper.
The first group comprises phenolic acids (hydroxybenzoic and hydroxycinnamic acids), flavonoids (e.g., flavonols, anthocyanins, proanthocyanidins), and coumarins, which are usually present as preformed compounds in the tissues. Indeed, HPLC in gradient mode on reversed phase C18 columns provides a means to separate most of these compounds in a single chromatography run without the need for derivatization. Due to their structural complexity, however, proanthocyanidins are more easily separated alone by hydrophilic interaction liquid chromatography (HILIC) according their degree of polymerization, or by reverse-phase chromatography, although some of them coelute [69].
The second group is constituted of stilbenic compounds (stilbenes that bear the core structure of 1,2-diphenylethylene and stilbenoids that are hydroxylated derivatives of stilbenes). Several of these compounds are produced naturally by several plants upon attack by pathogens [8,14,70,71]. Because of their dynamic behavior as responses to stresses, the detection of stilbenes requires methods that can be used for monitoring their differential response in various phytopathologic situations [61,71]. Their extraction generally requires specialized instrumentation and expertise, for instance, sample cleaning techniques such as solid phase extraction (SPE), sample dilution, selective extraction, or use of stable isotopes. Most of the qualitative or quantitative analytical studies of stilbenes are performed with HPLC and in an increasing sensitivity order UV, fluorescence (FD), electrochemical (ECD), or MS detection [36,50,52]. A method for the simultaneous separation of proanthocyanidins and stilbenoids has been reported, using a comprehensive bi-dimensional chromatography, with a diol stationary phase in the first dimension and a C18 stationary phase in the second dimension [50,72].

4. Polyphenols (Excluding Stilbenes) Identified in the Vegetative Organs of Grapevine

Phenolic compounds produced by grapevine range from cell wall-thickening compounds such as lignin and tannins, to specialized compounds such as phenolic acids and flavonoids. The chemical characterization of these compounds is based on analysis of different groups of components individually by LC–MS, mainly in negative ionization mode, although some LC–MS methods in positive-ion mode have been reported [16]. With high-resolution MS, compounds are identified by processing raw data with specific algorithms to calculate molecular formulae on the basis of the monoisotopic mass of the [M–H]− ion and the relative abundances and distances (spacing) of m/z signals measured in the isotopic pattern. Metabolites are then identified by searching in the available MS databases, in comparison with UV spectra patterns reported in the literature [16]. In Table 1, a database specific to grapevine phenolics containing 105 metabolites, including their specific MS and UV information, is provided.

4.1. Hydroxycinnamic Acids

The phenylpropanoid pathway starts with the aromatic amino acid phenylalanine and leads to derivatives with one, two, or more aromatic rings (C6), each ring with a characteristic substitution pattern, and with different modifications of the propane residue of phenylalanine (C3) [35]. At least 15 hydroxycinnamic acids (moiety C6–C3) have been identified in the vegetative organs of grapevine, with different degrees of hydroxylation and methylation of C6. These include caftaric, coutaric, chlorogenic, chicoric, fertaric, caffeic, p-coumaric, ferulic, sinapic, and cinnamic acids, and some of their derivatives, that is, 1-O-sinapoyl-β-D-glucose, 1-O-(4-coumaroyl)-glucose, 1-caffeoyl-β-D-glucose (reported as caffeic acid derivative by some authors), ferulic acid pentose (reported as ferulic acid derivative by some authors), and a caftaric acid isomer (Table 1) [20,32,46,47,53,73,74].

4.2. Hydroxybenzoic Acids

The cleavage of a C2 fragment from the aliphatic side chain of p-coumaric acid leads to hydroxybenzoic acids (C6–C1) [35], and nine have been reported in the vegetative organs of grapevine: quinic, gallic, protocatechuic, p-hydroxybenzoic, gentisic, γ-resorcylic, vanillic, syringic, and ellagic acids, mostly detected in the leaves (Table 1) [4,32,47,73,75].

4.3. Flavan-3-Ols or Flavanols

The condensation of three C2 residues with an activated hydroxycinnamic acid produces metabolites with a second aromatic ring linked to the phenylpropanoid moiety, with a common C6-C3-C6 skeleton of flavonoids. The basic flavonoid chemical structure is the flavan nucleus, consisting of 15 carbon atoms arranged in two benzene rings (A and B) linked via a heterocyclic oxygen-containing pyran ring (C). The main classes of flavonoids differ in the level of oxidation and saturation of the C ring, the most relevant being flavan-3-ols including proanthocyanidins, anthocyanins, flavanones, flavonols, and flavones [35,65]. Flavan-3-ols exhibit a saturated C-ring hydroxylated in the 3-position. The A-ring of flavan-3-ols is generally hydroxylated in C5 and C7 and the B-ring in C4. Diversity arises from the substitution pattern of the B-ring and can be increased by galloylation and glucosylation of the 3-hydroxyl group [76]. The presence of two asymmetric carbons (in C2 and C3) opens the possibility for different stereoisomers, that is, 2R,3S (2,3-trans), 2R,3R (2,3-cis), 2S,3R (2,3-trans), and 2S,3S (2,3-cis) configurations. The following eight flavanol monomers are reported in grapevine leaves, stems, and canes: catechin, gallocatechin, epigallocatechin, epigallocatechin gallate, epicatechin, gallocatechin gallate, epicatechin gallate, and catechin gallate (Table 1) [32,59,69,73,77].

4.4. Proanthocyanidins

Proanthocyanidins, also known as condensed tannins, are both oligomeric and polymeric compounds arising from flavanol condensation. Linkages between constitutive flavan-3-ol units are found between C4 and C6 or C4 and C8 in the case of B-type proanthocyanidins. A-type are linked with additional C2-O-C7 or C2-O-C5 bonds. Substitution in the 4-position gives rise to another asymmetric center on extension and upper units, but the usual configuration is 3,4-trans (i.e., 3S,4S or 3R,4S). The chain length of one polymer is described by the degree of polymerization (DP), and the mean degree of polymerization (mDP) of a heterogeneous population of polymers [76]. The following nine proanthocyanidins are reported in grapevine leaves, stems, and canes: procyanidin A1, procyanidin B1, procyanidin B2, procyanidin B3, procyanidin B4, procyanidin C1, procyanidin T2, prodelphinidin A-type (reported as epigallocatechin-epicatechin dimer by some authors), and a procyanidin dimer gallate (Table 1) [33,50,53,69,76,77].

4.5. Anthocyanins

Anthocyanins share the same molecular structure of flavonoids composed by one heterocyclic benzopyran ring (as the C ring), one fused aromatic ring (as the A ring), and one phenyl constituent (as the B ring). Nevertheless, they differ on the basis of hydroxyl or methoxyl substitutions in the lateral phenyl B ring, and, in general, for glycosylations and esterifications. Anthocyanins of Vitis are structurally based on five aglycones/anthocyanidins—malvidin, cyanidin, delphinidin, peonidin, and petunidin—which differentiate on the basis of number and position of their hydroxyl groups and their degree of methylation. Acylation occurs at the C6 position of the glucose molecule by esterification with acetic, p-coumaric, and caffeic acids [77,78]. Anthocyanins have been mainly reported in the leaves of grapevine (at least 14) and include: delphinidin-3-O-glucoside, cyanidin-3-O-glucoside, cyanidin-3-(6-O-coumaroyl)glucoside, petunidin-3-O-glucoside, petunidin-3-(6-O-acetyl)glucoside, petunidin-3-(6-O-coumaroyl)glucoside, peonidin-3-O-glucoside, peonidin-3-(6-O-acetyl)glucoside, peonidin-3-(6-O-coumaroyl)glucoside, malvidin-3-O-glucoside, malvidin-3-(6-O-acetyl)glucoside, malvidin-3-(6-O-coumaroyl)glucoside, malvidin-3-(6-O-caffeoyl)glucoside, and malvidin-3-O-rutinoside (Table 1) [4,5,77,78,79].

4.6. Flavones

Flavones are the simplest members of the class of flavonoids and consist of 4H-chromen-4-one bearing a phenyl substituent at position 2 [65]. Among the flavonoids naturally occurring in grapevine, flavones represent the least common group of aromatic compounds with only apigenin-7-O-glucoside and luteolin-7-O-glucoside reported in the leaves (Table 1) [4].

4.7. Flavonols

Chemically, flavonols or 3-hydroxyflavones differ from many other flavonoids in that they have a double bond between positions 2 and 3 and an oxygen (a ketone group) in position 4 of the C ring, like flavones; however, they differ from flavones due to the presence of a hydroxyl group at the position 3. Most of the flavonols exist as O-glycosides and seldomly as C-glycosides, and their conjugated derivatives (glycones) are mainly bound to sugars, hydroxycinnamic acids, or organic acids [35]. Flavonols make up the largest group of flavonoid compounds encountered in grapevine leaves and stems, with at least 35 compounds reported in the literature (Table 1) [1,2,4,5,32,34,59,66,77,79,80] derived from four aglycones: myricetin, quercetin, kaempferol, and isorhamnetin:
-
Myricetin, myricetin-3-O-galactoside, myricetin-3-O-glucuronide, myricetin-3-O-glucoside, and myricetin-3-O-rhamnoside;
-
Quercetin, quercetin-3-O-rutinoside, quercetin-3-O-galactoside, quercetin-3-O-glucoside, quercetin-3-O-glucuronide, quercetin-3-O-rhamnoside, quercetin-3-(6-O-acetyl)glucoside, quercetin-3-(3-O-arabinosyl)glucoside, quercetin-3-(7-O-glucosyl)glucuronide, quercetin-3-O-arabinose (reported as quercetin-O-pentoside by some authors), quercetin-3-(3-O-rhamnosyl)glucoside-7-O-rhamnoside, quercetin-3-(6-O-rhamnosyl)galactoside, and diquercetin-3-(3-O-glucosyl)glucuronide;
-
Kaempferol, kaempferol-3-O-galactoside, kaempferol-3-O-rutinoside, kaempferol-3-O-glucuronide, kaempferol-3-O-glucoside, kaempferol-3-O-xyloside (or kaempferol-O-pentoside by some authors), kaempferol-3-O-rhamnoside, dihydrokaempferol-3-O-rhamnoside, kaempferol-3-(6-O-coumaroyl)glucoside, and kaempferol-3-(7-O-glucosyl)galactoside (or kaempferol-3,7-diglucoside by some authors);
-
Isorhamnetin-3-O-galactoside, isorhamnetin-3-O-glucoside, isorhamnetin-3-O-arabinose (or isorhamnetin-O-pentoside by some authors), isorhamnetin-3-O-glucuronide, isorhamnetin-3-O-rutinoside, isorhamnetin-3-(6-O-feruloyl)glucoside, and isorhamnetin-3-(4-O-rhamnosyl)rutinoside (or isorhamnetin diglycoside by some authors).

4.8. Flavanones

Flavanones (also called 2,3-dihydroxyflavones) lack the double bond between carbons 2 and 3 in the C-ring of the flavonoid skeleton, which is present in flavones and flavonols. Thus, flavanones are chiral at the C2 position, and are generally glycosylated by glucoside or disaccharide at position seven to give flavanone glycosides [65]. The following eight flavanones have been reported in the vine plant: taxifolin, taxifolin-O-pentoside, taxifolin-3-O-glucoside, taxifolin-3-O-rhamnoside, hesperetin, eriodictyol-7-O-glucoside, naringenin, and naringenin-7-O-glucoside (Table 1) [4,74].

4.9. Coumarins and Dihydrochalcones

Coumarins are 1,2-benzopyrones (fused benzene and α-pyrone rings) that are derived from the phenylpropanoid pathway, but can also be produced through the cleavage of O-hydroxycinnamic acid that exist in free or glycosylated forms. In studies aimed at identifying polyphenols in grapevine, the following compounds have been detected: aesculin, fraxin, aesculetin, umbelliferone (coumarins), and phlorizin (dihydrochalcone) (Table 1) [19,32,81,82].

4.10. Non-Phenolic Compounds

The literature surveyed reveals that at least eight non-phenolic compounds or volatile compounds are usually eluted with phenolic compounds, and these include pyrogallol and catechol (benzenediols), sinapaldehyde, syringaldehyde and coniferaldehyde (hydroxycinnamaldehydes), vanillin and acetovanillone (benzaldehydes), and arbutin (hydroquinone) (Table S1) [35,46,47,55,60,83]. Moreover, some still unknown compounds with phenolic characteristics have been reported, and their importance can be estimated only if their chemical structure is determined.

5. Stilbenic Compounds Identified in the Vegetative Organs of Grapevine

The condensation of three C2 residues with an activated hydroxycinnamic acid (as with flavonoids) produces stilbenes, which are metabolites with an essential structural skeleton of two aromatic rings joined by an ethylene bridge (C6–C2–C6) [31,50]. Stilbenes emit a blue fluorescence under UV light with excitation and emission peaks around 320 and 390 nm, respectively [52,63]; in fact, the name “stilbene” derives from the Greek word “stilbos”, which is translated as “shining” [16,36]. The chemical structure of stilbenes in both the monomeric and oligomeric states is constituted by a diphenylethylene group oriented in trans or cis. The presence of a cis-stilbenic chromophore gives rise to different spectra, with an absorption maximum of lower intensity and of shorter wavelength compared with that of the trans-isomer [61]. Light exposition of trans-stilbene solutions has been shown to partially photoisomerize stilbenes into cis forms [7,59,61]. There are several areas of confusion with stilbene nomenclature. According to current practice however, the trans/cis nomenclature is used to describe the stereochemistry at saturated rings, whereas the Z/E nomenclature is used to describe the stereochemistry of double bonds [8,13,61,64]. In this review, the trans/cis nomenclature is used, although at least two compounds have been reported with other nomenclatures, namely, miyabenol C and ε-viniferin. Both trans-E-miyabenol C and trans-Z-miyabenol C are reported in the literature [61]. In the case of ε-viniferin, there are two stereochemical centers, at positions 7a and 8a on the dihydrofuran ring, allowing for four potential stereoisomers: (+)-trans-ε-viniferin, (-)-trans-ε-viniferin), (+)-cis-ε-viniferin, and (-)-cis-ε-viniferin) [8].
Most stilbenes have been identified using NMR and MS, which are the most informative techniques. Using MS, the initial identification of compounds is performed on the exact mass measurement of the monoisotopic ion and isotopic pattern, enabling the molecular formula to be identified with a high-confidence score and low mass error. Exact mass measurements of MS/MS fragments either confirm or deny the putative structure. Because MS/MS cannot distinguish between isomeric compounds, tentative assignment is also based on comparisons with data found in the literature [13,16] and NMR profiles. In addition, UV−VIS data based on λmax and UV spectrum when available are compared with those in the literature [12,61]. With this approach, a total of 78 stilbenes have been successfully identified in the vegetative tissues of the vine plant. A database of these stilbenes is provided in Table 2; the masses, when available, are those derived from the negative ion LC−MS datasets. Mass data are usually in agreement among publications, with minor changes in product ions owing to different fragmentation conditions.
The basic simple structure of stilbenes gives rise to a wide array of compounds that primarily vary in the number and position of hydroxyl groups and various substitutions with sugars, methyl, and methoxy groups, in addition to the structural conformations of the molecules and oligomerization patterns [8,31,39,68].

5.1. Monomeric Stilbenes

Of the total known V. vinifera stilbenes, 23 are monomers: trans-astringin, cis-astringin, trans-resveratroloside, cis-resveratroloside, trans-resveratrol-2-C-glucoside, trans-resveratrol-10-C-glucoside, trans-resveratrol-O-glucoside, cis-resveratrol-O-glucoside, trans-piceid, cis-piceid, trans-piceatannol, trans-isorhapontin, trans-resveratrol, cis-resveratrol, 2,4,6-trihydroxyphenanthrene-2-O-glucoside, trans-isorhapontigenin, cis-isorhapontigenin, trans-pinostilbene, cis-pinostilbene, trans-pinostilbene-4′-O-glucoside (or trans-pinostilbene-3-O-glucoside by some authors), trans-pterostilbene, cis-pterostilbene, and trans-rhaponticin (or trans-rhapontin by some authors) (Table 2) [7,31,40,50,53].

5.2. Dimeric Stilbenes

The majority of the stilbenoids in grapevine vegetative organs are dimers (30 in total): leachianol G, leachianol F, restrytisol A, ampelopsin A, ampelopsin D, ampelopsin F, pallidol, caraphenol B, quadrangularin, (+)-trans-ε-viniferin (and occasionally (-)-trans-ε-viniferin), (+)-cis-ε-viniferin (and occasionally (-)-cis-ε-viniferin), viniferifuran (reported as amurensin H by some authors), diptoindonesin A (reported as ε-viniferin-C-glucoside by some authors), trans-ω-viniferin, cis-ω-viniferin, trans-δ-viniferin, cis-δ-viniferin, a dimethylated derivative of trans-ε-viniferin, a dimethylated derivative of trans-δ-viniferin, trans-scirpusin A, maackin A, a derivative of trans-ε-viniferin with γ-lactam ring, a derivative of trans-resveratrol with γ-lactam ring, malibatol A, viniferal, vitisinol C, vitisinol E, vitisinol B, viniferether A, and viniferether B (Table 2). It is important to note that there are a number of instances where common names given to particular stilbenoids can lead to confusion. For instance, the name vitisinol E has been given to two different stilbenoid dimers by different authors [8,25,26,27,28,62].

5.3. Trimeric Stilbenes

There are eight trimers in V. vinifera vegetative organs: ampelopsin B, ampelopsin C, ampelopsin E, trans-miyabenol C, cis-miyabenol C, davidiol A, α-viniferin, and viniferol D (Table 2) [9,31,56,57,67].

5.4. Tetrameric Stilbenes

Among stilbene tetramers, the following 16 compounds are reported in the vegetative organs of grapevine: hopeaphenol, isohopeaphenol, ampelopsin H, vaticanol C-like isomer (or vaticanol C by some authors), vitisin A (r2-viniferin), vitisin B (r-viniferin), vitisifuran A, vitisifuran B, vitisin C, viniferol A, viniferol B, viniferol C, viniferol E, wilsonol C, heyneanol A, and stenophyllol C (reported as napalensinol B by some authors) (Table 2) [7,25,28,29,31,41,67].

5.5. Pentameric Stilbenes

Two stilbenes pentamers have been reported in the Vitis genus [39]. However, none have been detected in the vegetative organs.

5.6. Hexameric Stilbenes

Viniphenol A, a new resveratrol hexamer, is the only hexameric stilbene isolated from V. vinifera leaves (Table 2) [26].

6. Levels of Phenolic Compounds in the Leaves, Stems, Canes, Woods, and Roots of the Vine Plant

Several phenolic compounds have been quantified in grapevine, although absolute quantification is currently not available for many of them [9,55,59]. Most authors have reported their data on either a fresh or dry weigh basis (Tables S1 and S2). In analyzing the data for this review, mean values were first calculated using fresh and dry weight values separately, and then together. Although the separate analysis proved challenging because of few data points available for many of the compounds, the final ranking of phenolics was not affected by the method of calculation.
On another note, many of the compounds are quantified as equivalents of the most similar chemicals [12,13,51]. Comparison of the calibration curves showed that assays of content determination in vine of stilbenes in which equivalent chemicals are used as standards lead to a severe underestimation of the oligomer concentration. For example, the quantification of ε-viniferin using trans-resveratrol as standard underestimated its concentration by a factor > 2 in the study by [24]. Therefore, caution is required when interpreting the data presented in Table 3, Table 4, Table 5, Table 6, Table 7, Table 8, Table 9 and Table 10, taking into consideration the water status of the samples analyzed as reported by the different authors, and the number of studies and data points used in the calculation of mean values (Tables S1 and S2).

6.1. Phenolic Compounds in Grapevine Leaves

A total of 132 phenolic compounds have been reported in grapevine leaves (Table 3 and Table 4).
Eighty-seven phenolic acids and flavonoids, and five coumarins have been identified in the leaves of grapevine, with the highest level recorded for quercetin-3-O-glucuronide (10,305.10 mg/kg on average), followed by quercetin-3-O-galactoside (7436.94 mg/kg), quercetin-3-O-glucoside (7256.42 mg/kg), caftaric acid (4151.97 mg/kg), quercetin-3-O-rhamnoside (2708.60 mg/kg), kaempferol-3-O-glucoside (1730.09 mg/kg), kaempferol-3-O-glucuronide (662.34 mg/kg), coutaric acid (635.81 mg/kg), myricetin-3-O-glucoside (291.23 mg/kg), quercetin-3-O-rutinoside (257.51 mg/kg), and kaempferol-3-O-rutinoside (200.34 mg/kg) (Table 3). Among compounds with levels between 10 and 100 mg/kg are five favan-3-ols (gallocatechin gallate, 49.40 mg/kg; gallocatechin, 40.20 mg/kg; epigallocatechin, 23.77 mg/kg; epigallocatechin gallate, 10.69 mg/kg; and catechin; 10.62 mg/kg), and two phenolic acids (fertaric acid, 85.48 mg/kg; and p-hydroxybenzoic acid, 83.40 mg/kg) (Table 3). These levels in general agree with reports that grapevine leaves are rich sources of flavonols. In their studies, [2,20,22,79,84,85] found that the predominant phenolics in the leaves are quercetin-3-O-glucuronide, quercetin-3-O-glucoside, caftaric acid, and kaempferol-3-O-glucoside; total amounts of quercetin derivatives were significantly higher than total amounts of kaempferol derivatives in the studies [2,79,85].
The 40 stilbenes reported in the leaves of V. vinifera are eminently less abundant than the phenolic acids and flavonoids. The most predominant stilbenes in the leaves with levels superior to 50 mg/kg are trans-resveratrol (137.88 mg/kg), vaticanol C-like isomer (96.85 mg/kg), cis-piceid (78.38 mg/kg), trans-piceatannol (78.04 mg/kg), ampelopsin H (76.08 mg/kg), α-viniferin (71.61 mg/kg), and cis-miyabenol C (50.37 mg/kg) (Table 4). All these compounds are often undetected in healthy leaves. For example, in two grapevine varieties grown in Serbia, the total stilbene content was 45% higher in infected than in healthy leaf extracts [73]. Interestingly, some leaf samples have been found to contain cis-resveratrol-3-O-glucoside instead of the expected trans-resveratrol as their predominant stilbene [59,60,84].

6.2. Phenolic Compounds in Grapevine Stems

Literature data have revealed the presence of 88 phenolic compounds (of which 47 were stilbenes) in the stems of grapevine. Although the most abundant compound is the flavonol quercetin-3-O-galactoside (17,403.61 mg/kg), flavan-3-ols constitute the majority of compounds in the stems and in the order catechin (14,900.45 mg/kg) > gallic acid (10,307.36 mg/kg) > epicatechin (9251.64 mg/kg) > procyanidin B1 (9216.18 mg/kg) > procyanidin T2 (9100.99 mg/kg) > procyanidin B3 (8724.23 mg/kg) > epicatechin gallate (6362.96 mg/kg) > procyanidin C1 (5007.76 mg/kg) > procyanidin B4 (2243.10 mg/kg) > procyanidin dimer gallate (2234.08 mg/kg) > procyanidin B2 (2056.93 mg/kg) > procyanidin A1 (1254.38 mg/kg) (Table 5). The high level of flavan-3-ols in the stems agrees with several reports [33,34,37,54,69]. Among other compounds with average values superior to 900 mg/kg are the phenolic acid caftaric acid (3373.18 mg/kg) and the flavonols quercetin (4266.04 mg/kg), quercetin-3-O-glucoside (1785.38 mg/kg), quercetin-3-O-rhamnoside (1570.10 mg/kg), kaempferol (950.35 mg/kg), and quercetin-3-O-glucuronide (908.82 mg/kg), which are also abundant compounds in the leaves. In the stems, two anthocyanins are reported with average values superior to 500 mg/kg, namely, malvidin-3-O-rutinoside (539.89 mg/kg) and malvidin-3-O-glucoside (513.13 mg/kg) (Table 5). In the stems from seven cultivars grown in northern Portugal, caftaric acid, quercetin-3-O-glucuronide, malvidin derivatives, and epicatechin were the main metabolites, representing from 54% to 75% of the total phenolic content [33].
Only a few of the 47 stilbenic compounds identified in the stems of grapevine have been quantified [58]: trans-resveratrol (506.41 mg/kg), (+)-trans-ε-viniferin (433.49 mg/kg), ampelopsin D (65.00 mg/kg), vitisin B (33.95 mg/kg), trans-piceid (14.52 mg/kg), trans-isorhapontigenin (9.90 mg/kg), trans-piceatannol (7.42 mg/kg), and trans-δ-viniferin (4.86 mg/kg) (Table 6).

6.3. Phenolic Compounds in Grapevine Canes

Compared to leaves and stems, fewer studies have been conducted on the phenolic composition of grapevine canes, which explains the report of only 49 phenolic compounds for the organ. These data indicate that canes have substantial quantities of valuable health-promoting stilbenes [7,12,40,46,51,52,58]. Compounds usually present in the cane extracts Table 7) are trans-resveratrol (2797.17 mg/kg), (+)-trans-ε-viniferin (2449.25 mg/kg), isohopeaphenol (851.43 mg/kg), vitisin B (668.08 mg/kg), trans-piceatannol (583.88 mg/kg), trans-ω-viniferin (556.41 mg/kg), and hopeaphenol (511.39 mg/kg); the remaining compounds are with levels below 500 mg/kg.
Other compounds identified in the canes with significant amounts are catechin (1747.01 mg/kg), sinapic acid (1154.81 mg/kg), procyanidin B1 (511.12 mg/kg), epicatechin (269.40 mg/kg), ferulic acid (165.63 mg/kg), gallic acid (165.06 mg/kg), prodelphinidin A-type (160.17 mg/kg), and protocatechuic acid (103.31 mg/kg) (Table 8). Ferulic acid, for example, has been reported as the major compound in the shoots of various grapevine cultivars [47,83].

6.4. Phenolic Compounds in Grapevine Woods

No report was found related to the identification of phenolic acids and flavonoids in the woods (trunk and cordons) of the vine plant. All the 23 stilbenes identified in the woods of various cultivars have been quantified, as shown in Table 9, and with generally high levels ranging from 13.28 mg/kg for trans-astringin to 8263.87 mg/kg for (+)-trans-ε-viniferin [12,13]. The most abundant compounds are (+)-trans-ε-viniferin (8263.87 mg/kg), (+)-cis-ε-viniferin (3851.97 mg/kg), isohopeaphenol (2429.69 mg/kg), α-viniferin (2366.03 mg/kg), and trans-resveratrol (2195.12 mg/kg). Eight compounds are with levels between 1000 and 2000 mg/kg, seven with levels between 100 and 1000 mg/kg, and three with levels between 10 and 50 mg/kg.

6.5. Phenolic Compounds in Grapevine Roots

As with the woods, there are no reports on the phenolic acid and flavonoid profiles of grapevine roots. The 24 stilbenes in the roots [12,30,41,42,62] can be ranked, on the basis of abundance, in the following order: (+)-trans-ε-viniferin (6475.95 mg/kg) > vitisin B (6420.48 mg/kg) > hopeaphenol (1814.90 mg/kg) > ampelopsin A (1096.92 mg/kg) > vitisin A (1090.12 mg/kg) > isohopeaphenol (529.54 mg/kg) > trans-resveratrol (503.25 mg/kg) (Table 10).

7. Distribution of Phenolic Compounds in the Vegetative Organs of Grapevine

A mapping of the distribution of phenolic compounds in grapevine shows that composition and levels greatly vary according to the organ investigated (Figure 1 and Figure 2). In general, flavonoids constitute the largest group of phenolics. From an anatomical point of view, these compounds localize specifically in the stems, with lower amounts in the leaves and the canes (Figure 1).
The overall data obtained through adding together the available individual compound means (not shown) indicate that the total amount of phenolics in the stems is on average 114,415.68 mg/kg. Flavan-3-ols constitute the most abundant group of compounds in the stems (61.63%; catechin, epicatechin, and procyanidin B1 with the highest levels), followed by flavonols (23.75%; quercetin-3-O-galactoside with the highest level), hydroxybenzoic acids (9.03% with a high abundance of gallic acid), hydroxycinnamic acids (3.66%), anthocyanins (0.99%), and stilbenes (0.94%). From an industrial point of view, stems seem to be an important source of proanthocyanidins for potential use as nutraceutical, enological products, chemical standards, or even in winemaking to regulate the composition of flavonoids in wine [69].
Flavonols are quantitatively the most abundant phenolic class in the leaves (83.43% of the total amount of phenolics, i.e., 37,052.70 mg/kg) with a high abundance of quercetin-3-O-glucuronide, quercetin-3-O-galactoside, and quercetin-3-O-glucoside; flavonols are followed by hydroxycinnamic acids (13.19%, of which caftaric acid and coutaric acid have the highest levels), stilbenes (2.63%), flavan-3-ols (0.41%), and hydroxybenzoic acids (0.26%). Coumarins, flavones, anthocyanins, and flavanones are found in minor amounts. The spatial distribution of phenolic compounds in grapevine leaves evaluated by matrix-assisted laser desorption/ionization (MALDI) showed the specific colocation of trans-resveratrol, pterostilbene, and viniferins around the veins in healthy leaves [68]. It is reported that the leaf blade is more abundant in phenolic compounds than the petiole, and much less than the pedicel [75,84].
There are very few reports on flavonols, flavones, flavanones, anthocyanins, and coumarins in the canes. Phenolic groups identified (on average 14,477.42 mg/kg) can be classified in terms of abundance as stilbenes (69.00% of the total) > flavan-3-ols (18.56%; catechin, procyanidin B1 and epicatechin with the highest levels as with the stems) > hydroxycinnamic acids (9.63% of which sinapic acid and ferulic acid) > hydroxybenzoic acids (2.80% of which gallic acid). Indeed, in the comparison of phenolics in the skins, pulps, seeds, canes, and leaves of six cultivars grown in Iran, it was found that the canes usually contained the highest amounts of flavonoids and stilbenes [87].
The data also show that stilbenes accumulate primarily in the woods (34,390.90 mg/kg; ε-viniferin, isohopeaphenol, trans-resveratrol, α-viniferin, and ampelopsin H with the highest levels), followed by the roots (18436.44 mg/kg; ε-viniferin, hopeaphenol, vitisin B, and ampelopsin A with the highest levels), the canes (9989.50 mg/kg; ε-viniferin, trans-resveratrol, isohopeaphenol, vitisin B, and trans-piceatannol with the highest levels), and the stems (1075.55 mg/kg; ε-viniferin, trans-resveratrol, vitisin B, and ampelopsin D with the highest levels), whereas leaves, which are more exposed to environmental stresses [23,40], have a low concentration of these compounds (972.97 mg/kg; trans-resveratrol, vaticanol C-like isomer, piceid, trans-piceatannol, and ampelopsin H with the highest levels) (Figure 2).
Stilbenes are more constitutively expressed in the woods, roots, canes, and stems, where they are believed to help in the prevention of wood rot [12,39,62]. This constitutive expression might explain the more consistent and greater levels of compounds in these plant parts, in contrast to the leaves in which stilbene production is mostly induced to provide enhanced protection against pests and diseases [12,23,65,85]. Levels of stilbenes were compared in the wood, roots, and canes by [12]; grapevine canes usually had ε-viniferin and trans-resveratrol as their main compounds, and woods had more ε-viniferin and isohopeaphenol, whereas roots were generally rich in vitisin B, ampelopsin A, and vitisin A [12]. The authors concluded that the degree of oligomerization of stilbenes increases from the aerial organs to the root system. After manual dissection of the cortex, pith, and conducting tissues of grape canes, the evaluation of the spatial distribution of stilbenes suggested a predominance of monomers in conducting tissues and oligomers in cortex and pith [52].

8. Factors Affecting the Biosynthesis and Levels of Phenolic Compounds in the Vegetative Organs of Grapevine

Grapevine phenolics occur in large concentration ranges, as attested by standard deviation values presented in Table 3, Table 4, Table 5, Table 6, Table 7, Table 8, Table 9 and Table 10. There are a number of factors that interact together, so as to result in such wide range of phenolic variations. Some of these factors are well documented in the literature and include cultivars, climate, cultural practices, and biotic and abiotic stresses.

8.1. Grapevine Cultivars and Rootstocks

Grapevine cultivars are not genetically homogeneous, and most of them are multiplied by vegetative propagation. A collection of vines propagated from the same mother vine make up a clone; clonal selection is routinely carried out in viticulture with the purpose of creating disease-free or high-yielding populations. Progressively, criteria such as the levels of grape sugar and skin phenolic compounds have been integrated in clonal selection programs. Moreover, these clones are often grafted on different rootstocks [2,9,90]. These factors could explain why the contents of polyphenols are subject to such severe variations [6,32,58,59,89]. For instance, plants of Pinot blanc grafted on three different rootstocks—Kober 5B, S04, and 1103P—accumulated resveratrol differentially in the leaves [14]. According to some authors, the best resveratrol-producing cultivars are Pinot noir and Cabernet Sauvignon, depending on the clones investigated [5,6,51]. A comparison of the phenolic profile of canes of the cultivars Chardonnay, Cabernet Sauvignon, Shiraz (Syrah), Merlot, Sauvignon blanc, and Pinot noir showed that Pinot noir had very high levels of trans-resveratrol and trans-ε-viniferin [51]. In several studies, quantitative analyses showed that the stems and leaves of red cultivars are richer in proanthocyanidins, flavonols, hydroxycinnamic acids, anthocyanins, and stilbenes than those of white cultivars [33,53,54,91]. The biosynthesis of phenolic compounds is also closely dependent on plant developmental stages. It has indeed been reported that very young and very old leaves do not synthesize high stilbene and anthocyanin levels, probably because of the incomplete development of the stomata [9,69,77,79,84]. In the study by [89], however, the intensity of stilbene induction did not show a clear and homogeneous correlation with the position of leaves along the shoot. The total viniferin content was generally highest in the second, third, and fourth leaves for the 21/103 genotype. Moreover, [25] did not find a homogeneous trend of change in stilbenoid levels in the stems during the growth cycle.

8.2. Geographical Location and Climate (Shading, Temperature, Irrigation)

The geographical location of the vineyard (especially latitude and elevation) and the seasonal meteorological variability in the area are known to influence the phenolic composition of grapevine organs. Meteorological variability, including light, temperature, and water, represents one of the main environmental factors responsible for phenolic biosynthesis. Clear separation was demonstrated between the phenolic profile of leaves [32,79,86] and stems [40] of grapevine cultivars of different geographical origins. A higher variation of stilbene levels between years as compared to variation between plants of the same year have also been reported [89]. Different light exposures of the vine demonstrated that shading decreases the flavonoid content of the leaves, a result that is consistent with the role these molecules play in protecting tissues from UV light [85,91]. In the study by [59], accumulation of quercetin-3-O-glucoside, kaempferol-3-O-glucoside, and quercetin-3-O-galactoside was the most prominent in full sunlight-exposed leaves compared with half-shaded leaves. Furthermore, the biosynthesis of phenolics is sensitive to diurnal differences in temperature, although with different temporal patterns. Indeed, a decrease of flavonoid biosynthesis has been observed when the temperature is limiting or excessive [92]. Extreme weather conditions with prolonged dry periods as well as heavy rain events can severely influence grapevine physiology [2,86]. Water deficit has been reported to upregulate the expression of genes of the anthocyanin pathway [77] and to increase the levels of most polyphenols in the leaves, in particular cis-resveratrol-3-O-glucoside, kaempferol-3-O-glucoside, and quercetin-3-O-glucoside [60]. Recent results show that, during water stress, the synthesis of anthocyanins is paralleled by an increase of the expression of flavonoid transporters [65]. On the other hand, it is reported that excessive water application could induce a decrease in proanthocyanidin levels [92].

8.3. Vinicultural Practices

There are many cultural practices that affect the production and accumulation of phenolic compounds in grapevine organs. However, many of these factors seem to act in a typical bell-shaped manner, where they could improve the final levels of compounds only when present at optimal levels. For instance, pruning greatly influences the levels of stilbenoids in the canes, leaves, and stems of grapevine, but the effect depends on the number of branches removed and the duration of the treatment [40,50]. In canes remaining on the plant 30 days after pruning, only a minor increase of total stilbenoid levels was observed, whereas in canes stored at room temperature after pruning, a twofold increase occurred [40]. In general, practices that increase plant vigor, such as fertilizer application, are reported to negatively influence the biosynthesis of phenolics in grapevine. Less trans-resveratrol was accumulated in the leaves when increasing nitrogen doses were applied to one-year-old potted vines, whereas the opposite was observed with increased potassium doses; when nitrogen and potassium were supplied together, potassium did not balance the negative effect of nitrogen [14]. Iron deficiency stimulated anthocyanin accumulation in grapevine apical leaves [78]. The application of other agrochemicals (e.g., plant hormones and chitosan) with the aim of enhancing vegetative growth and grape quality also affects phenolic biosynthesis in a complex way [18]. Typically, it has been reported that abscisic, auxin, and ethylene application lead to an increase in the levels of flavonoids, whereas the opposite has been observed with the application of gibberellic acid and inhibitors of the ethylene receptor [65]. Indirectly, fertilizer and hormone application could also lead to low levels of polyphenols because they induce the production of especially dense foliage that limits the exposure of some organs to sunlight. Grapevine is susceptible to various pests and diseases usually controlled by chemical and biological treatments that can introduce additional variability in the data. High amounts of stilbenoids were produced in grapevine plants that were mycorrhized with Rhizophagus irregularis, as well as an up-regulation in the leaves of genes involved in the stilbene biosynthesis pathway [70].

8.4. Outside and Biotic Stimuli

High variability in phenolic levels in grapevine is best explained by biotic stresses and mechanical injuries. In most studies, it was found that the infection status of the plant influences phenolic profiles much more than other factors [9]. Indeed, following pathogen attacks and insect bites, all the vegetative organs of grapevine undergo modifications in terms of their polyphenol composition and contents. For phenolic acids, flavonoids, and coumarins, the literature is contradictory regarding the relationship between level and disease susceptibility [15]. This might be due to the fact that these compounds are part of the constitutive metabolome in lignified tissues. In the study by [77], the expression of flavonoid pathway genes was detected in both healthy and diseased leaves, confirming that the pathway is active in control conditions [77]. These polyphenols that are present prior to an attempted infection of the plant are known as preformed, and are part of a passive resistance mechanism [14,36]. A mechanism of active resistance is the synthesis, degradation, or metabolism to a different compound in response to attacks by pathogens; de novo synthesized compounds are called phytoalexins [71]. An induction in the synthesis of stilbenic compounds in photosynthetic tissues has been considerately reported in response to the main grapevine pathogens, namely, Botrytis cinerea of grey mould [70], Plasmopara viticola of downy mildew [6,10,12,52,61,62,64,68,70,73,82,89], Erysiphe necator of powdery mildew [11,88], fungi associated with grapevine trunk diseases [3,13,15,43,44,45,86], Rhizopus stolonifera of berry rot [14], Grapevine leafroll-associated virus 3 of Grapevine leafroll disease [77], Xylella fastidiosa of Pierce’s disease [9,55], and Aspergillus carbonarius of sour rot [71]. The increment can be as high as 100-fold, and has a biosynthetic origin attributable to stilbene synthase induction. Interestingly, it was found that downy mildew affects the spatial repartition of stilbenoids in the cane, with an increase in the cortex (a tissue notably involved in protection against mechanical damage and microbial attack) and conducting tissues, and a decrease in the pith [52]. Mechanical stress on freshly pruned canes and leaves have also been reported to overinduce the biosynthesis of trans-resveratrol and trans-piceatannol within a short period after pruning [23,40].

9. Concluding Remarks

Several compounds with phenolic characteristic have been detected in the leaves, stems, canes, woods, and roots of the grapevine plant. An effort is still needed to identify and quantify several of these compounds. It is clear that several factors affect the biosynthetic pathways, leading to the accumulation of phenolic compounds in grapevine. The patterns of gene expression show significant differences between organs and cultivars, especially for genes involved in stilbene synthesis. In the leaves in particular, random inductions in the synthesis of these compounds have been observed, which is understandable given their higher exposure to the environment and resulting susceptibility to attack by pests and diseases. An understanding of the different roles of these factors is crucial because only with this information will it be possible to develop cultural practices aimed at improving phenolic levels in the plants and in the derived products. Moreover, unexplored areas of research related to this topic will most certainly constitute a basis for future improvement of grapevine disease tolerance.

Supplementary Materials

The following are available online at https://www.mdpi.com/2076-3921/9/5/398/s1, Table S1: Reference source for phenolic acids, flavonoids and coumarins identified in the vegetative organs of grapevine (Vitis vinifera L.). Table S2: Reference source for stilbenes identified in the vegetative organs of grapevine (Vitis vinifera L.).

Author Contributions

Conceptualization, P.G. and I.C.; methodology, P.G. and R.K.S.; software, P.G.; validation, P.G., I.C., and R.K.S.; formal analysis, P.G.; investigation, P.G. and R.K.S.; resources, I.C.; data curation, P.G. and R.K.S.; writing—original draft preparation, P.G.; writing—review and editing, P.G., I.C., and R.K.S.; visualization, P.G.; supervision, I.C.; project administration, I.C.; funding acquisition, I.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the R&D project “INNOVINE & WINE –Vineyard and Wine Innovation Platform (NORTE-01-0145-FEDER-000038)”, co-supported by Fundo Europeu de Desenvolvimento Regional (FEDER) and Norte 2020 (Programa Operacional Regional do Norte 2014/2020), and the project UIDB/04033/2020 supported by FCT – Fundação para a Ciência e a Tecnologia.

Conflicts of Interest

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

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Antioxidants 09 00398 g001 550
Figure 1. Distribution of the major phenolic acids and flavonoids in the vegetative organs of the vine plant: mean values (y-axis; mg/kg) + standard deviations as error bars divided by 10 for better visualization.
Figure 1. Distribution of the major phenolic acids and flavonoids in the vegetative organs of the vine plant: mean values (y-axis; mg/kg) + standard deviations as error bars divided by 10 for better visualization.
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Antioxidants 09 00398 g002 550
Figure 2. Distribution of the major stilbenic compounds in the vegetative organs of the vine plant: mean values (y-axis; mg/kg) + standard deviations as error bars divided by 10 for better visualization.
Figure 2. Distribution of the major stilbenic compounds in the vegetative organs of the vine plant: mean values (y-axis; mg/kg) + standard deviations as error bars divided by 10 for better visualization.
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Table
Table 1. Polyphenols (excluding stilbenes) in the vegetative organs of the grapevine plant.
Table 1. Polyphenols (excluding stilbenes) in the vegetative organs of the grapevine plant.
ID 1Compound GroupCompound
Name 1		Chemical Formula 2MW (g/mol)[M–H]–Main MS/MS Fragments (m/z) 3,4λmax (CH3OH) (nm)Detection Mode 5Tissue Distribution 6
LEAVES STEMS CANES WOODSROOTS
1Hydroxybenzoic acidQuinic acidC7H12O6192.167191111, 173, 85, 127308, 280MS ✓
2Hydroxybenzoic acidGallic acidC7H6O5170.120169125, 124, 79, 51278, 214MS, NMR, DAD ✓ ✓ ✓
4Hydroxybenzoic acidProtocatechuic acid C7H6O4154.121153109, 108297, 258MS ✓ ✓
7Hydroxybenzoic acidp-Hydroxybenzoic acidC7H6O3138.12213793, 60, 79, 108, 118, 137272, 310shMS ✓ ✓
8Hydroxybenzoic acidGentisic acid C7H6O4154.121153109, 81, 42, 108281, 228, 330shMS ✓
9Hydroxybenzoic acidγ-Resorcylic acid C7H6O4154.121153109, 136, 154, 110, 52, 80, 137, 39, 155313, 245MS ✓
30Hydroxybenzoic acidVanillic acid C8H8O4168.149167123, 152, 108, 91292, 260MS, NMR, DAD ✓ ✓
36Hydroxybenzoic acidSyringic acid C9H10O5198.174197182, 153, 167, 138276MS, NMR, DAD ✓ ✓ ✓
50Hydroxybenzoic acidEllagic acidC14H6O8302.194301284, 300, 257, 229, 184367, 256, 301shMS ✓ ✓
14Hydroxycinnamic acid 1-O-Sinapoyl-β-D-glucose C17H22O10386.353385223, 205, 341, 265, 190, 179, 119, 247282MS ✓
16Hydroxycinnamic acid 1-O-(4-Coumaroyl)-glucose C15H18O8326.301325163, 145, 119, 187, 265, 205322MS ✓ ✓
20Hydroxycinnamic acid 1-Caffeoyl-β-D-glucose C15H18O9342.300341179, 161, 143, 149, 131, 135290, 304sh, 328MS ✓ ✓
21Hydroxycinnamic acid Ferulic acid pentose NANA325149, 178, 193326, 275MS ✓ ✓
22Hydroxycinnamic acid Caftaric acid isomer C13H11O9311.224311179, 135, 149325, 286MS ✓
24Hydroxycinnamic acid Caftaric acid C13H12O9312.230311179, 135, 149, 267, 161, 237326, 298sh, 243MS, NMR, DAD ✓ ✓ ✓
27Hydroxycinnamic acid Coutaric acid C13H12O8296.231295163, 149, 119316, 234, 300shMS, DAD ✓ ✓
28Hydroxycinnamic acid Chlorogenic acid C16H18O9354.311353191, 179, 135, 161, 335, 172, 284328, 244, 303shMS, DAD ✓
31Hydroxycinnamic acid Chicoric acid C22H18O12474.374473311, 293, 179, 149, 135, 219328, 305sh, 279MS ✓
32Hydroxycinnamic acid Fertaric acid C14H14O9326.259325193, 175, 149, 281, 134314, 279MS ✓
35Hydroxycinnamic acid Caffeic acid C9H8O4180.159179135, 134, 96324, 299sh, 240MS, NMR, DAD ✓ ✓ ✓
43Hydroxycinnamic acid p-Coumaric acid C9H8O3164.160163119, 104, 93310, 225, 211, 310shMS, NMR, DAD ✓ ✓ ✓
46Hydroxycinnamic acid Ferulic acid C10H10O4194.186193134, 149, 178, 116323, 289, 238shMS, NMR, DAD ✓ ✓ ✓
48Hydroxycinnamic acid Sinapic acid C11H12O5224.212223164, 149, 208, 164, 193, 179318, 238MS ✓ ✓
83Hydroxycinnamic acidCinnamic acidC9H8O2148.161147103, 77, 87, 129276, 215, 203DAD ✓
3Flavan-3-olGallocatechinC15H14O7306.270305179, 221, 219, 165, 261, 125, 137274, 370MS ✓
6Flavan-3-olProcyanidin B1C30H26O12578.526577425, 407, 289, 451, 287, 245, 451275, 322MS, NMR, DAD ✓ ✓ ✓
10Flavan-3-olProcyanidin A1 C30H24O12576.501575449, 289, 423, 539, 477, 407, 441280MS ✓ ✓ ✓
15Flavan-3-olEpigallocatechin C15H14O7306.270305179, 165, 219, 221, 261, 125, 261, 125274, 212, 235MS ✓
18Flavan-3-olProcyanidin C1 C45H38O18866.778865695, 407, 577, 287, 713, 739, 575, 425, 289279MS, DAD ✓ ✓
19Flavan-3-olProcyanidin T2 C45H38O18866.778865577, 713, 289, 287, 425, 575, 695, 407, 739280MS, DAD ✓ ✓
23Flavan-3-olCatechin C15H14O6290.271289245, 203, 179, 205, 227, 109, 123, 165, 125, 151275, 222MS, NMR, DAD ✓ ✓ ✓
25Flavan-3-olProcyanidin B3 C30H26O12578.526577425, 407, 289, 151, 559, 445270, 330MS, NMR, DAD ✓ ✓
26Flavan-3-olProcyanidin B4 C30H26O12578.526577425, 407, 289280, 240MS, DAD ✓ ✓
29Flavan-3-olProcyanidin B2 C30H26O12 578.526577425, 407, 289, 451, 287, 245, 125280, 240, 370MS, NMR, DAD ✓ ✓ ✓
37Flavan-3-olEpigallocatechin gallate C22H18O11458.375457305, 219, 261, 221, 359, 169, 305, 289, 271, 125, 331274, 238MS, DAD ✓
38Flavan-3-olProdelphinidin A-type C30H26O13594.527593425, 441, 573, 423, 407, 289, 531, 273, 339, 245, 177, 161276, 228, 320MS ✓ ✓
39Flavan-3-olProcyanidin dimer gallate NANA729577, 407, 559, 451, 711, 289, 593, 437, 425280MS, DAD ✓ ✓
40Flavan-3-olEpicatechin C15H14O6290.271289245, 203, 109, 179, 205, 123, 125, 151277, 226MS, NMR, DAD ✓ ✓ ✓
42Flavan-3-olGallocatechin gallateC22H18O11458.375457169, 161, 359, 331, 169, 305, 193276, 240MS ✓
47Flavan-3-olEpicatechin gallate C22H18O10442.376441289, 245, 205, 169, 125, 331, 271, 179278, 240MS, NMR, DAD ✓ ✓
61Flavan-3-olCatechin gallateC22H18O10442.376441289, 245, 205, 331, 169, 125, 425, 271, 395, 169, 193, 405278MS ✓ ✓
33AnthocyaninDelphinidin-3-O-glucoside C21H21O12+465.387463301, 300, 271, 125526, 361, 277, 402shDAD ✓
34AnthocyaninCyanidin-3-O-glucoside C21H21O11+449.388447284, 211, 285, 255, 147, 227516, 262, 301shMS, DAD ✓
44AnthocyaninPetunidin-3-O-glucosideC22H23O12+479.414477314, 315, 299, 300526, 344sh, 277DAD ✓
45AnthocyaninPeonidin-3-O-glucosideC22H23O11+463.415461299, 298, 284, 255, 227, 211517, 280, 330sh, 421shMS, DAD ✓
52AnthocyaninMalvidin-3-O-glucosideC23H25O12+493.441491329, 314, 299528, 348sh, 288MS, DAD ✓ ✓
59AnthocyaninPetunidin-3-(6-O-acetyl)glucosideC24H25O13+521.451519315, 302, 274, 149528, 270, 350shDAD ✓
62AnthocyaninPeonidin-3-(6-O-acetyl)glucosideC24H25O12+505.452504301, 286, 230, 258, 268522, 280DAD ✓
67AnthocyaninMalvidin-3-(6-O-acetyl)glucosideC25H27O13+535.478533329, 315522, 344, 278DAD ✓
72AnthocyaninCyanidin-3-(6-O-coumaroyl)glucoside C30H27O13+595.533593287, 259, 231, 213, 259524, 314, 284, 449shDAD ✓
80AnthocyaninPetunidin-3-(6-O-coumaroyl)glucosideC31H29O14+625.553624317, 302, 274, 218, 228, 246534, 282, 313DAD ✓
81AnthocyaninPeonidin-3-(6-O-coumaroyl)glucoside C31H29O13+609.554608301, 286, 230, 258, 268522, 312MS, DAD ✓
85AnthocyaninMalvidin-3-(6-O-coumaroyl)glucosideC32H31O14+639.586637329, 299, 281534, 318DAD ✓
86AnthocyaninMalvidin-3-(6-O-caffeoyl)glucosideC32H31O15+655.581655331, 299, 637, 315, 475532, 324, 284MS ✓
87AnthocyaninMalvidin-3-O-rutinosideC29H35O16+639.583637331526, 288MS ✓
41Flavanone TaxifolinC15H12O7304.254303285, 125, 177, 275, 151, 259, 217290, 326shMS ✓
55FlavanoneTaxifolin-O-pentosideC20H20O11436.371435303, 285, 399, 151, 241, 217, 175274, 317MS ✓
56FlavanoneTaxifolin-3-O-glucosideC21H22O12466.395465285, 303, 151, 339, 177, 259, 447290MS ✓
57FlavanoneTaxifolin-3-O-rhamnoside C21H22O11450.396449303, 285, 151, 323, 431292, 235MS ✓
88FlavanoneHesperetin C16H14O6302.282301258, 143, 157, 137, 286284, 324sh, 221MS ✓
95FlavanoneEriodictyol-7-O-glucoside C21H22O11450.396449287, 269, 151, 135, 259, 225, 209, 431281, 327MS ✓
103FlavanoneNaringeninC15H12O5272.256271151, 177, 119, 165, 125, 107, 227, 191289, 228, 336shMS ✓
104FlavanoneNaringenin-7-O-glucoside C21H22O10434.397433271, 269, 313, 177, 151, 119, 107282, 222MS ✓
49Flavonol Myricetin-3-O-galactoside C21H20O13480.378479317, 316, 178, 271360, 265MS, DAD ✓
51FlavonolMyricetin-3-O-glucuronide C21H18O14494.361493317353, 300sh, 261MS, DAD ✓
53FlavonolMyricetin-3-O-glucosideC21H20O13480.378479317, 316, 169, 271, 303, 227, 179, 151362, 298sh, 260MS, DAD ✓
54FlavonolQuercetin-3-O-rutinoside C27H30O16610.521609301, 300, 271, 255, 179, 343, 151353, 256, 294shMS, NMR, DAD ✓ ✓
58FlavonolQuercetin-3-O-galactoside C21H20O12464.379463301, 300, 179, 273, 257, 151362, 256, 301shMS, NMR, DAD ✓ ✓ ✓
60FlavonolQuercetin-3-O-glucoside C21H20O12464.379463301, 300, 271, 161, 179, 255, 151358, 256, 300shMS, NMR, DAD ✓ ✓
63FlavonolQuercetin-3-O-glucuronideC21H18O13478.362477301, 179, 151, 283, 459, 431, 501356, 254, 300shMS, NMR, DAD ✓ ✓
65FlavonolMyricetin-3-O-rhamnosideC21H20O12464.379463317, 316, 271, 300, 179, 287, 151372, 302sh, 248MS ✓
68FlavonolMyricetin C15H10O8318.237317151, 179, 137, 287, 271, 109, 192372, 253, 303sh, 207MS, NMR, DAD ✓
69FlavonolQuercetin-3-O-rhamnosideC21H20O11448.380447301, 300, 179, 151, 271, 257354, 258, 307shMS, NMR, DAD ✓ ✓
70FlavonolKaempferol-3-O-galactoside C21H20O11448.380447285, 255, 227, 327361, 260MS ✓
71FlavonolKaempferol-3-O-rutinoside C27H30O15594.522593285, 257, 151, 447, 199, 241, 93354, 274MS, DAD ✓ ✓
73FlavonolKaempferol-3-O-glucuronide C21H18O12462.363461285, 267, 443, 417, 257, 229348, 265MS, DAD ✓
74FlavonolQuercetin-3-(6-O-acetyl)glucoside C23H22O13506.416505301, 300, 463, 271, 255354, 256, 267sh, 298shMS ✓
75FlavonolQuercetin-3-(3-O-arabinosyl)glucoside C26H28O16596.493595301, 517, 151, 300, 463, 179, 445, 271, 255354, 260, 231MS ✓
76FlavonolQuercetin-3-(7-O-glucosyl)glucuronideC27H28O18640.503639477, 301, 179, 151361, 300, 268, 256DAD ✓
77FlavonolQuercetin-3-O-arabinose C20H18O11434.350433301, 179, 151, 300, 283358, 311MS ✓ ✓
78Flavonol C33H40O21772.662771609, 301355, 259, 299sh, 204NMR, DAD ✓
79FlavonolKaempferol-3-O-glucoside C21H20O11448.380447285, 255, 151, 227, 327, 243348, 263, 297shMS, DAD ✓ ✓
82FlavonolQuercetin C15H10O7302.239301151, 179, 273, 193, 257, 229372, 255, 202sh, 300shMS, NMR, DAD ✓ ✓
84FlavonolKaempferol C15H10O6286.239285187, 117, 211, 127, 257, 151, 169, 241369, 258, 390MS, NMR, DAD ✓ ✓
89FlavonolKaempferol-3-O-xyloside C20H18O10418.354417285, 255, 227350MS ✓
90FlavonolKaempferol-3-O-rhamnoside C21H20O10432.381431285351, 264, 202, 294shMS ✓
91FlavonolDihydrokaempferol-3-O-rhamnoside C21H22O10434.397433269, 287, 259, 180, 151, 368286, 230MS ✓
92FlavonolIsorhamnetin-3-O-galactoside C22H22O12478.406477315,.314 271, 300, 357366, 289, 259MS ✓
93FlavonolIsorhamnetin-3-O-glucoside C22H22O12478.406477315, 314, 285, 357, 271354, 265shMS, DAD ✓
94FlavonolQuercetin-3-(6-O-rhamnosyl)galactosideC27H30O16610.517609301, 541, 463, 300, 271, 255, 179, 447, 151356, 256, 300NMR, DAD ✓
96FlavonolIsorhamnetin-3-O-arabinose C21H20O11448.381447315, 314, 271, 243345, 258MS ✓
97FlavonolIsorhamnetin-3-O-glucuronide C22H20O13492.389491315, 255, 151355, 265shMS ✓
98FlavonolIsorhamnetin-3-O-rutinosideC28H32O16624.548623315, 300, 468354, 256MS ✓
99FlavonolIsorhamnetin-3-(6-O-feruloyl)glucosideC32H30O15654.577653315320, 274MS ✓
100FlavonolIsorhamnetin-3-(4-O-rhamnosyl)rutinosideC34H42O20770.685769461, 623, 163354, 256MS, DAD ✓
101FlavonolKaempferol-3-(6-O-coumaroyl)glucoside C30H26O13594.525593285, 227, 255317, 265, 356sh, 310shMS ✓
102FlavonolKaempferol-3 (7-O-glucosyl)galactoside C27H30O16610.521609447, 489, 285343, 300sh, 265DAD ✓
105FlavonolDiquercetin-3-(3-O-glucosyl)glucuronide C42H36O24924.722923765, 755, 837, 903, 935, 808374MS ✓
64FlavoneApigenin-7-O-glucoside C21H20O10432.381431269, 283, 311, 413, 231, 225, 201, 197, 149335, 269, 253MS, NMR, DAD ✓
66FlavoneLuteolin-7-O-glucoside C21H20O11448.380447285, 226, 257, 217, 241, 198349, 254sh, 205MS, NMR, DAD ✓
5CoumarinAesculinC15H16O9340.282339133, 177, 150346, 289MS ✓
11DihydrochalconePhlorizin C21H24O10436.413435273, 167, 229, 297285, 230shMS ✓
12CoumarinFraxinC16H18O10370.310369207, 192, 354, 149, 123332, 308shMS ✓
13CoumarinAesculetin C9H6O4178.143177149, 133, 105, 91, 115, 89, 65334, 288shMS ✓
17CoumarinUmbelliferone C9H6O3162.144161133, 117, 105, 51, 78323, 236MS ✓
1 Other reported names are found in Table S1, where compounds are numbered (ID) according to their elution patterns. 2 NA = not available or not applicable, MW = Molecular Weight. 3 MS-MS values in italic (compounds 62, 72, 80, 81) are reported in positive mode. 4 The most abundant fragments are highlighted in bold. 5 MS = mass spectrometry detection, NMR = nuclear magnetic resonance detection, DAD = diode array or ultraviolet detection. 6 In blue with √ are detected compounds; in light red are undetected compounds or unavailable information.
Table
Table 2. Stilbenic compounds in the vegetative organs of the grapevine plant.
Table 2. Stilbenic compounds in the vegetative organs of the grapevine plant.
ID 1Compound GroupCompound Name 1,2Chemical Formula 3MW (g/mol)[M–H]– Precursor IonMain MS/MS Fragments (m/z) 4λmax (CH3OH) (nm)Detection Mode 5Tissue Distribution 6
LEAVES STEMS CANES WOODSROOTS
106Monomerstrans-Astringin C20H22O9406.383405243, 225, 201, 322, 159, 199, 173331, 305MS ✓ ✓ ✓
107Monomers trans-Resveratroloside C20H22O8390.388389227, 185, 179, 269, 143, 305, 371, 209311MS ✓ ✓
108Monomerstrans-Resveratrol-2-C-glucoside NANA389269, 241, 299, 175, 163326MS, NMR ✓ ✓
109Monomerstrans-Resveratrol-10-C-glucosideNANA435389, 227315MS, NMR ✓
110Monomerstrans-Resveratrol-O-glucosideC20H22O8390.388389227, 305, 175, 185321MS, NMR ✓ ✓ ✓
183Monomerscis-Resveratrol-O-glucosideC20H23O8391.391389227319, 306MS✓
113Monomerstrans-PiceidC20H22O8390.383389227, 185, 251, 269, 209, 371, 143318, 306, 229MS, NMR, DAD ✓ ✓ ✓ ✓ ✓
117Monomerscis-AstringinC20H22O9406.383405243, 225, 201, 322, 405, 159, 228, 157324, 260MS ✓
119Monomerstrans-PiceatannolC14H12O4244.246243175, 225, 149, 215, 201, 159, 181, 132, 199, 143325, 290, 306MS, NMR ✓ ✓ ✓ ✓ ✓
120Monomerscis-ResveratrolosideC20H22O8390.388389227, 371, 209280MS ✓
121Monomers cis-PiceidC20H22O8390.383389227, 269, 241, 185, 209, 371, 143284, 230MS, NMR ✓ ✓ ✓
122Monomerstrans-Isorhapontin C21H24O9420.411419257, 241, 225, 175, 242, 201, 159, 281, 132326, 303, 290MS ✓
123Monomerstrans-ResveratrolC14H12O3228.247227185, 143, 183, 159, 157, 212, 205306, 319, 228MS, NMR, DAD ✓ ✓ ✓ ✓ ✓
124Monomers2,4,6-Trihydroxyphenanthrene-2-O-glucosideC20H20O8388.372389371, 353, 335, 227, 209, 199261, 222MS ✓
126Monomerstrans-IsorhapontigeninC15H14O4258.270257242, 241, 224, 172, 213, 185325, 303, 290MS ✓ ✓ ✓
127Monomerstrans-Pinostilbene-4′-O-glucosideC21H24O8404.410403241, 226, 225NAMS ✓
128Monomerscis-ResveratrolC14H12O3228.247227185, 159, 143, 157, 212, 143285, 232MS, NMR ✓ ✓
145Monomerstrans-PterostilbeneC16H16O3256.296255239, 197, 209, 226, 165298, 305, 275MS, NMR, DAD ✓ ✓
146Monomerscis-PterostilbeneC16H16O3256.296255197, 239, 209, 226, 165279MS ✓
153Monomerscis-IsorhapontigeninC15H14O4258.270257241, 213, 185, 224318, 220MS ✓
154Monomerstrans-Rhaponticin C21H24O9420.414419257, 241, 281, 299, 323, 405, 389, 243, 169, 395324, 220MS ✓
155Monomerstrans-PinostilbeneC15H14O3242.270241181, 225, 197, 169NAMS ✓
156Monomerscis-PinostilbeneC15H14O3242.270241181, 225, 197, 169NAMS ✓
111DimersLeachianol G C28H24O7472.496471387, 377, 349, 255, 121280, 218MS, NMR ✓ ✓ ✓
112DimersLeachianol F C28H24O7472.496471349, 453, 255, 287, 153, 241, 121280, 218MS, NMR ✓ ✓ ✓
114DimersRestrytisol AC28H24O7472.486471377, 255, 349, 121, 471280, 221MS ✓ ✓ ✓
115DimersAmpelopsin AC28H22O7470.479469345, 451, 375, 363, 257, 357, 423, 317, 241283MS, NMR ✓ ✓ ✓ ✓
116DimersPallidolC28H22O6454.478453359, 265, 435, 406, 391, 346, 273284MS, NMR ✓ ✓ ✓ ✓ ✓
118DimersCaraphenol BC28H22O7470.473469451, 281, 363, 375, 227, 423 326, 291MS ✓ ✓
130DimersAmpelopsin D C28H22O6454.478453359, 361, 437, 215, 343, 199, 255, 289314, 280MS, NMR ✓ ✓ ✓ ✓
131DimersQuadrangularin A C28H22O6454.471453359, 289, 411, 435, 347, 253314MS, NMR ✓ ✓
132Dimers(+)-cis-ε-Viniferin C28H22O6454.471453435, 347, 411, 333, 359, 369, 253286, 201, 230MS, NMR ✓ ✓
134Dimers(+)-trans-ε-Viniferin C28H22O6454.471453359, 435, 347, 369, 411, 333, 253, 225327, 285, 308MS, NMR, DAD ✓ ✓ ✓ ✓ ✓
135DimersViniferifuran C28H20O6452.455451NA317, 289, 209MS, NMR ✓
136DimersDiptoindonesin AC34H32O11616.610615453, 359, 411, 347, 585326, 226MS, NMR ✓ ✓
141Dimerstrans-ω-Viniferin C28H22O6454.478453435, 359, 347, 411, 395, 333, 285324, 280MS, NMR ✓ ✓ ✓ ✓
144Dimerscis-ω-Viniferin C28H22O6454.478453435, 411, 395, 333, 285, 359, 225294MS. NMR ✓
149Dimerstrans-δ-ViniferinC28H22O6454.478453435, 369, 411, 347, 333, 359, 225, 409312, 225MS, DAD ✓ ✓ ✓ ✓
152Dimerscis-δ-ViniferinC28H22O6454.478453435, 411, 369, 359, 333, 347, 317, 307, 251, 267285, 232MS ✓
157Dimerstrans-ε-Viniferin derivative (dimethylated)C30H26O6482.523481387, 375, 226, 197, 466325MS ✓
158Dimerstrans-δ-Viniferin derivative (dimethylated)C30H26O6482.523481397, 361, 439, 387, 463313MS ✓
159Dimerstrans-Scirpusin A C28H22O7470.470469375, 451, 385, 359, 241, 427, 728, 445, 287, 514, 955320, 286, 204MS, NMR ✓
162DimersMaackin AC28H22O8486.470485244, 226, 137327, 288, 204MS, NMR ✓
164Dimerstrans-ε-Viniferin derivative (γ-lactam ring)C32H26O7N936.550536NANAMS, NMR ✓
165Dimerstrans-Resveratrol derivative (γ-lactam ring)C18H16O4N310.324310NANAMS, NMR ✓
171DimersMalibatol AC28H20O7468.454467NANAMS, NMR ✓
172DimersAmpelopsin FC28H22O6454.471453NA282, 220MS, NMR ✓
176DimersViniferalC35H26O8574.579573NANAMS, NMR ✓
177DimersVitisinol CC27H24O5428.482427NA358, 279MS ✓
178DimersVitisinol EC27H24O6444.475444NA281, 230, 204MS, NMR ✓
179DimersVitisinol BC35H26O8574.579573NA282, 228, 204MS, NMR ✓
181DimersViniferether AC29H26O7486.509485NA280, 229MS, NMR ✓
182DimersViniferether BC29H26O7486.513485NA280, 231MS, NMR ✓
125TrimersAmpelopsin B C28H22O6454.478453359, 243, 211, 183, 265281, 328MS, NMR ✓ ✓ ✓
139Trimerstrans-Miyabenol C C42H32O9680.698679661, 573, 479, 451, 637, 585, 447322, 279MS, NMR ✓ ✓ ✓ ✓ ✓
140Trimerscis-Miyabenol C C42H32O9680.699679661, 573, 479, 451, 637, 585, 447285MS, NMR ✓ ✓
142TrimersDavidiol A C42H32O9680.704679585, 447, 491, 385, 479, 465, 567284, 219MS ✓ ✓
143Trimersα-ViniferinC42H30O9678.682677571, 583, 437, 449, 463, 501, 331284, 309MS, NMR ✓ ✓ ✓
161TrimersAmpelopsin CC42H32O9680.709679NA283MS, NMR ✓ ✓
169TrimersViniferol DC42H32O9680.702679NANAMS, NMR ✓ ✓
173TrimersAmpelopsin E C42H32O9680.701679NA325, 285MS, NMR ✓ ✓
129TetramersHopeaphenol C56H42O12906.925905811, 717, 451, 611, 359, 299283, 226MS, NMR ✓ ✓ ✓ ✓
133TetramersIsohopeaphenolC56H42O12906.925905451, 675, 811, 717, 358, 265284MS, NMR ✓ ✓ ✓ ✓ ✓
137TetramersAmpelopsin HC56H42O12906.925905811, 717, 705, 793281MS, NMR ✓ ✓ ✓
138TetramersVaticanol C-like isomerC56H42O12906.929905811, 717, 793, 705, 611281MS, NMR ✓
147TetramersVitisin A (r2-viniferin)C56H42O12906.920905811, 887, 717, 693, 545, 451, 359, 265328, 285MS, NMR ✓ ✓ ✓ ✓
148TetramersVitisifuran AC56H40O12904.907903NA322, 232MS, NMR ✓
150TetramersVitisin B (r-viniferin)C56H42O12906.920905799, 887, 811, 717, 545, 451, 359, 317321, 286MS, NMR ✓ ✓ ✓ ✓
151TetramersVitisifuran BC56H40O12904.907903NA324, 228MS, NMR ✓
160TetramersVitisin C C56H42O12906.926905NANAMS, NMR ✓
166TetramersViniferol AC56H42O12906.925905559, 813, 361, 453, 651, 541, 801, 783284, 227MS, NMR ✓
167TetramersViniferol BC56H42O12906.929905559, 813, 361, 453, 651, 541, 801, 783283, 225MS, NMR ✓
168TetramersViniferol CC56H42O12906.929905NA284, 228MS, NMR ✓
170TetramersViniferol EC56H44O13924.940923NA284, 231MS, NMR ✓
174TetramersWilsonol CC56H42O12906.929905NA231NMR ✓
175TetramersHeyneanol AC56H42O12906.929905320, 284322, 237NMR ✓
180TetramersStenophyllol CC56H42O12906.923905NA285, 330, 223MS, NMR ✓
163HexamersViniphenol AC84H64O181361.3911360NANAMS, NMR ✓
1 Other reported names are found in Table S2, where compounds are numbered (ID) according to their elution patterns. 2 Another stilbene is reported in the literature as vitisinol E (compound 178), but with the formula C29H26O7, MW of 486,51, [M − H] − (m/z) of 485, λmax CH3OH of 358, 279, 253. 3 NA = not available or not applicable, MW = Molecular Weight. 4 The most abundant fragments are highlighted in bold. 5 MS = mass spectrometry detection, NMR = nuclear magnetic resonance detection, DAD = diode array or ultraviolet detection. 6 In blue with √ are detected compounds; in light red are undetected compounds or unavailable information.
Table
Table 3. Levels (mg/kg) of 92 polyphenols (excluding stilbenes) identified in grapevine leaves.
Table 3. Levels (mg/kg) of 92 polyphenols (excluding stilbenes) identified in grapevine leaves.
IdCompound Name 1Minimum Value 2,3Maximum ValueMean Value 4Standard DeviationN5References
63Quercetin-3-O-glucuronide868.6346,528.5510,305.1013,363.5110[1,2,4,5,19,59,60,66,75,79,81,82,84,85,86]
58Quercetin-3-O-galactoside 21.7228,831.117436.949880.9014[2,3,5,20,22,73,75,79,81,85]
60Quercetin-3-O-glucoside 27.6522,610.137256.427628.7124[1,2,3,5,19,20,22,59,60,66,73,75,79,80,81,82,84,85,86]
24Caftaric acid 12.4614,052.624151.973984.7918[3,4,5,19,20,22,59,60,66,73,75,79,81,82,84,85,86]
69Quercetin-3-O-rhamnoside1210.534206.672708.601498.072[1,2]
79Kaempferol-3-O-glucoside 2.566203.851730.091812.1520[2,3,19,20,22,59,60,66,73,75,79,80,81,84,85,86]
73Kaempferol-3-O-glucuronide 47.921698.41662.34736.833[2,19,66,79,81,82,85,86]
27Coutaric acid 4.541491.02635.81432.7010[3,19,20,22,73,75,79,81,82,85]
53Myricetin-3-O-glucosideND850.12291.23254.658[2,3,20,22,73,85]
54Quercetin-3-O-rutinoside 1.301650.01257.51473.2612[2,4,5,32,73,75,79,81,82,85,87]
71Kaempferol-3-O-rutinoside 0.12730.01200.34307.134[2,19,75,79,81,85,86]
32Fertaric acid 85.4885.4885.480.001[81,82]
7p-Hydroxybenzoic acid15.80151.0083.4067.602[19,32]
42Gallocatechin gallate20.1078.7049.4029.302[32]
68Myricetin 1.00193.2844.7574.375[1,3,22,81,88]
3Gallocatechin4.84102.0040.2043.853[32,81,82]
5Aesculin1.6050.7025.6320.063[32,81]
15Epigallocatechin 1.6766.3023.7730.083[32,81,82]
37Epigallocatechin gallate 0.0443.8110.6916.716[32,73,81,82]
23Catechin 0.0276.5810.6221.4418[19,32,59,60,73,75,79,81,82,84,87,88]
46Ferulic acid 0.00889.809.0725.6111[32,59,60,73,79,81,84]
82Quercetin 0.1352.178.8416.5516[1,4,19,32,59,60,73,84,87,88]
6Procyanidin B10.3925.566.8010.834[73,75,79,81,82]
4Protocatechuic acid 1.2510.505.884.632[32]
8Gentisic acid 0.598.854.724.132[32]
11Phlorizin 2.952.952.950.001[81,82]
2Gallic acid0.017.802.772.959[32,79,81,82,87,88]
78Quercetin-3-(3-O-rhamnosyl)glucoside-7-O-rhamnoside1.324.212.771.442[1]
40Epicatechin 0.0115.022.464.6918[32,59,60,73,75,79,81,82,84,87,88]
94Quercetin-3-(6-O-rhamnosyl)galactoside0.024.022.022.002[1]
29Procyanidin B2 0.355.691.912.214[75,79,81,82]
47Epicatechin gallate 0.018.451.742.579[59,60,81,82,84,88]
28Chlorogenic acid 0.0111.501.743.708[32,73,79,88]
35Caffeic acid 0.00319.601.684.8415[1,32,59,73,79,81,82,84,87,88]
25Procyanidin B3 0.742.411.570.842[75,81,82]
26Procyanidin B4 0.612.381.490.892[75,81,86]
93Isorhamnetin-3-O-glucoside 1.481.481.480.001[2,80,81,85]
84Kaempferol 0.016.771.282.198[1,32,59,60,84,86,88]
34Cyanidin-3-O-glucoside 0.016.401.172.048[4,5,59,60,77,78,79,84,88]
98Isorhamnetin-3-O-rutinoside1.121.121.120.001[2,81]
43p-Coumaric acid 0.018.170.922.4210[32,59,60,79,84,88]
64Apigenin-7-O-glucoside 0.091.600.850.752[1]
10Procyanidin A1 0.720.720.720.001[75]
66Luteolin-7-O-glucoside 0.021.910.600.695[1,4,73,81,82]
48Sinapic acid 0.550.550.550.001[81]
50Ellagic acid0.060.770.410.362[32]
41Taxifolin0.370.370.370.001[81]
83Cinnamic acid0.170.510.340.172[79]
75Quercetin-3-(3-O-arabinosyl)glucoside 0.310.310.310.001[2,81]
89Kaempferol-3-O-xyloside 0.230.230.230.001[2,75]
45Peonidin-3-O-glucoside0.010.600.200.244[5,77,78,79,88]
30Vanillic acid 0.010.540.190.195[77,78,79,81,88]
141-O-Sinapoyl-β-D-glucose 0.150.150.150.001[75]
70Kaempferol-3-O-galactoside 0.060.060.060.001[2,75,85,86]
36Syringic acid 0.010.070.040.032[88]
52Malvidin-3-O-glucoside0.010.060.040.032[1,2,3,4,5,19,32,59,66,75,77,78,79,80,81,82,84,85,86,88]
161-O-(4-Coumaroyl)-glucose 0.030.030.030.001[75]
1Quinic acidNQNQNQNQ0[4,19]
9γ-Resorcylic acid NQNQNQNQ0[82]
12FraxinNQNQNQNQ0[82]
13Aesculetin NQNQNQNQ0[19]
17Umbelliferone NQNQNQNQ0[19]
201-Caffeoyl-β-D-glucose NQNQNQNQ0[81]
21Ferulic acid pentose NQNQNQNQ0[19]
22Caftaric acid isomer NQNQNQNQ0[85]
33Delphinidin-3-O-glucoside NQNQNQNQ0[77,78,79]
44Petunidin-3-O-glucosideNQNQNQNQ0[77,78,79]
49Myricetin-3-O-galactoside NQNQNQNQ0[2,79,85]
51Myricetin-3-O-glucuronide NQNQNQNQ0[2,79]
59Petunidin-3-(6-O-acetyl)glucosideNQNQNQNQ0[77]
61Catechin gallateNQNQNQNQ0[86]
62Peonidin-3-(6-O-acetyl)glucosideNQNQNQNQ0[79]
65Myricetin-3-O-rhamnosideNQNQNQNQ0[2]
67Malvidin-3-(6-O-acetyl)glucosideNQNQNQNQ0[77,79]
72Cyanidin-3-(6-O-coumaroyl)glucoside NQNQNQNQ0[77]
74Quercetin-3-(6-O-acetyl)glucoside NQNQNQNQ0[19]
76Quercetin-3-(7-O-glucosyl)glucuronideNQNQNQNQ0[80]
80Petunidin-3-(6-O-coumaroyl)glucosideNQNQNQNQ0[77]
81Peonidin-3-(6-O-coumaroyl)glucoside NQNQNQNQ0[2,77,79]
85Malvidin-3-(6-O-coumaroyl)glucosideNQNQNQNQ0[77,79]
88Hesperetin NQNQNQNQ0[4]
90Kaempferol-3-O-rhamnoside NQNQNQNQ0[2]
92Isorhamnetin-3-O-galactoside NQNQNQNQ0[2,85]
95Eriodictyol-7-O-glucoside NQNQNQNQ0[19]
96Isorhamnetin-3-O-arabinose NQNQNQNQ0[2]
97Isorhamnetin-3-O-glucuronide NQNQNQNQ0[2]
100Isorhamnetin-3(4-O-rhamnosyl)rutinosideNQNQNQNQ0[2,80,85]
101Kaempferol-3-(6-O-coumaroyl)glucoside NQNQNQNQ0[4]
102Kaempferol-3 (7-O-glucosyl)galactoside NQNQNQNQ0[80]
103NaringeninNQNQNQNQ0[82]
104Naringenin-7-O-glucoside NQNQNQNQ0[82]
105Diquercetin-3-(3-O-glucosyl)glucuronide NQNQNQNQ0[66]
1 Compounds 33, 43, 52, 59, 62, 67, 72, 76, 80, 83, 85, and 102 are detected using only UV. 2 ND = not detected. 3 NQ = not quantified by the authors. 4 Fresh and dry weight data were combined for the calculations, without any conversion. 5 N = number of data points used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.
Table
Table 4. Levels (mg/kg) of 40 stilbenic compounds identified in grapevine leaves.
Table 4. Levels (mg/kg) of 40 stilbenic compounds identified in grapevine leaves.
IdCompound NameMinimum Value 1,2Maximum ValueMean Value 3Standard DeviationN4References
123trans-ResveratrolND1886.80137.88444.1524[6,10,11,19,23,32,59,60,61,62,63,64,68,70,73,81,82,84,87,88,89]
138Vaticanol C-like isomerND226.8096.85102.356[61,81,82,89]
121cis-PiceidND368.4078.38132.576[10,62,63,64,68,81,82]
119trans-PiceatannolND232.1078.04108.945[23,63,82,88]
137Ampelopsin HND226.8076.08106.586[61,81,82,89]
143α-ViniferinND189.0671.6175.196[10,61,81,89]
140cis-Miyabenol C ND148.6050.6769.296[61,81,82,89]
110cis-Resveratrol-3-O-glucoside ND232.6347.4183.306[59,60,84]
113trans-PiceidND170.2344.7164.6917[6,10,11,23,61,62,63,64,68,70,73,81,82,89]
139trans-Miyabenol C ND121.3041.5756.436[61,81,82,89]
149trans-δ-Viniferin1.09165.7135.5553.318[6,10,11,62,68,70,82]
120cis-Resveratroloside15.2037.5026.3511.152[63]
134(+)-trans-ε-Viniferin ND98.2025.1135.7915[6,10,11,23,61,62,68,70,73,81,82,89]
130Ampelopsin D ND67.6022.7831.706[10,61,81,82,89]
141trans-ω-Viniferin ND63.5521.3529.846[10,61,81,82,89]
144cis-ω-Viniferin ND63.5521.2429.926[10,61,81,82,89]
128cis-ResveratrolND53.1019.4620.504[62,63,64,73,82]
107trans-Resveratroloside 7.5021.8014.657.152[63]
116PallidolND26.7111.5212.096[61,81,82,89]
131Quadrangularin A ND33.8011.2915.926[10,61,81,82,89]
133IsohopeaphenolND131.177.1212.336[61,81,82,89]
153cis-Isorhapontigenin0.1013.006.556.452[63]
122trans-Isorhapontin 0.0721.306.448.694[63,81,82]
126trans-Isorhapontigenin0.109.604.854.752[63]
145trans-PterostilbeneND10.833.924.2410[6,10,61,62,64,68,70,82,89]
132(+)-cis-ε-Viniferin ND7.311.833.174[10,62,68,82,89]
106trans-Astringin 0.047.603.023.094[63,81,82]
152cis-δ-ViniferinND3.421.711.712[62,68]
127trans-Pinostilbene-4′-O-glucoside0.103.301.701.602[63]
117cis-Astringin0.202.101.150.952[63]
155trans-Pinostilbene0.102.001.050.952[63]
154trans-Rhaponticin 0.101.800.950.852[63]
156cis-Pinostilbene0.100.300.200.102[63]
114Restrytisol ANQNQNQNQ0[10]
1242,4,6-Trihydroxyphenanthrene-2-O-glucosideNQNQNQNQ0[64]
125Ampelopsin B NQNQNQNQ0[10]
142Davidiol A NQNQNQNQ0[10]
146cis-PterostilbeneNQNQNQNQ0[10]
157trans-ε-Viniferin derivative (dimethylated)NQNQNQNQ0[10]
158trans-δ-Viniferin derivative (dimethylated)NQNQNQNQ0[10]
1 ND = not detected. 2 NQ = not quantified by the authors. 3 Fresh and dry weight data were combined for the calculations, without any conversion. 4 N = number of data points used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.
Table
Table 5. Levels (mg/kg) of 41 polyphenols (excluding stilbenes) identified in grapevine stems.
Table 5. Levels (mg/kg) of 41 polyphenols (excluding stilbenes) identified in grapevine stems.
IdCompound Name 1Minimum Value 2Maximum ValueMean Value 3Standard DeviationN4References
58Quercetin-3-O-galactoside 1920.3441,831.7017,403.6115,457.564[21,50]
23Catechin 283.7298,290.9514,900.4527,191.1012[9,21,37,50,53,55,69,74,90]
2Gallic acid386.5432,960.4110,307.3613,374.204[9,21,34,37,55]
40Epicatechin 193.6133,154.039251.6412,435.1214[9,21,33,50,53,54,55,69,90]
6Procyanidin B1215.3650,709.009216.1814,385.6110[9,33,37,50,53,54,55,69]
19Procyanidin T2 1388.9035,015.049100.998406.542[9,34,50,55,69]
25Procyanidin B3 186.0423,108.658724.235791.294[9,21,55,69]
47Epicatechin gallate 2371.559862.086362.962950.306 [9,21,33,54,55]
18Procyanidin C1 305.519710.005007.764702.252[9,50,55,69]
82Quercetin 321.888210.204266.043944.162[21]
24Caftaric acid 110.3516,110.623373.185723.496[33,54,74,87]
26Procyanidin B4 131.004355.202243.102112.102[69]
39Procyanidin dimer gallate 110.044358.122234.082124.042[9,33,34,50,54,69]
29Procyanidin B2 10.496670.762056.932735.524[9,21,50,53,55,69,74]
60Quercetin-3-O-glucoside 29.887270.121785.382544.066 [9,21,37,53,55,90]
69Quercetin-3-O-rhamnoside320.202820.001570.101249.902[21]
10Procyanidin A1 674.911833.851254.38579.474[33,50,54]
84Kaempferol 70.121830.57950.35880.232[21]
63Quercetin-3-O-glucuronide391.521424.35908.82469.546[33,34,37,54,74]
87Malvidin-3-O-rutinoside451.00628.77539.8988.884 [33,54]
52Malvidin-3-O-glucoside224.88801.37513.13288.254[33,54]
43p-Coumaric acid 12.00934.08473.04461.042[9,21,55]
35Caffeic acid 10.18647.32328.75318.572[9,21,55]
38Prodelphinidin A-type 27.46292.88160.17132.712[33,50,54]
99Isorhamnetin-3-(6-O-feruloyl)glucoside81.10115.0798.0916.994[33,54]
86Malvidin-3-(6-O-caffeoyl)glucoside47.33119.2083.2735.944[33,54]
71Kaempferol-3-O-rutinoside 21.99127.3974.6952.704[33,54]
54Quercetin-3-O-rutinoside 10.55126.7365.8446.336[21,33,34,54,74,90]
79Kaempferol-3-O-glucoside 20.1479.0849.6129.474[33,54]
36Syringic acid 6.4832.2319.3612.882[21]
46Ferulic acid 8.0125.5516.788.772[9,21,55]
161-O-(4-Coumaroyl)-glucose NQNQNQNQ0[53]
201-Caffeoyl-β-D-glucose NQNQNQNQ0[53]
21Ferulic acid pentose NQNQNQNQ0[9,55]
31Chicoric acid NQNQNQNQ0[9,55]
55Taxifolin-O-pentosideNQNQNQNQ0[9,55]
56Taxifolin-3-O-glucosideNQNQNQNQ0[53]
57Taxifolin-3-O-rhamnoside NQNQNQNQ0[9,34,55,74]
61Catechin gallateNQNQNQNQ0[53]
77Quercetin-3-O-arabinose NQNQNQNQ0[50]
91Dihydrokaempferol-3-O-rhamnoside NQNQNQNQ0[9,55]
1 Compound 52 is detected using only UV. 2 NQ = not quantified by the authors. 3 Fresh and dry weight data were combined for the calculations, without any conversion. 4 N = number of data point used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.
Table
Table 6. Levels (mg/kg) of 47 stilbenic compounds identified in grapevine stems.
Table 6. Levels (mg/kg) of 47 stilbenic compounds identified in grapevine stems.
IdCompound NameMinimum Value 1,2Maximum ValueMean Value 3Standard DeviationN4References
123trans-ResveratrolND2130.00506.41570.046[9,23,26,27,53,55,58,91]
134(+)-trans-ε-Viniferin 14.301400.67433.49765.236[9,23,26,27,28,53,55,56,58,67,91]
130Ampelopsin D ND130.0065.0065.002[53]
150Vitisin B (r-Viniferin)6.8061.1033.9527.152[26,27,28,53,58,67,91]
113trans-Piceid14.5214.5214.520.001[9,23,26,27,53,55]
126trans-IsorhapontigeninND19.809.909.902[91]
119trans-PiceatannolND21.107.429.683[9,23,26,27,53,55,58,91]
149trans-δ-Viniferin4.864.864.860.001[23]
106trans-Astringin NQNQNQNQ0[9,53,55]
107trans-Resveratroloside NQNQNQNQ0[53]
108trans-Resveratrol-2-C-glucoside NQNQNQNQ0[53]
109trans-Resveratrol-10-C-glucosideNQNQNQNQ0[56]
110trans-Resveratrol-O-glucosideNQNQNQNQ0[56]
111Leachianol G NQNQNQNQ0[26,27]
112Leachianol F NQNQNQNQ0[26,27]
114Restrytisol ANQNQNQNQ0[58]
115Ampelopsin ANQNQNQNQ0[26,27,28,53,56,58]
116PallidolNQNQNQNQ0[9,26,27,55]
118Caraphenol BNQNQNQNQ0[53]
129Hopeaphenol NQNQNQNQ0[9,26,53,55,56,58]
131Quadrangularin A NQNQNQNQ0[26,27,53]
133IsohopeaphenolNQNQNQNQ0[26,27,53,56,67]
135Viniferifuran NQNQNQNQ0[67]
136Diptoindonesin ANQNQNQNQ0[26,27,53]
137Ampelopsin HNQNQNQNQ0[26,27]
139trans-Miyabenol C NQNQNQNQ0[26,27,53,58]
140cis-Miyabenol C NQNQNQNQ0[53]
142Davidiol A NQNQNQNQ0[26,27,53]
143α-ViniferinNQNQNQNQ0[9,55]
145trans-PterostilbeneNQNQNQNQ0[9,26,27,55]
147Vitisin A (r2-Viniferin)NQNQNQNQ0[28,56,58,67]
148Vitisifuran ANQNQNQNQ0[67]
151Vitisifuran BNQNQNQNQ0[67]
159trans-Scirpusin A NQNQNQNQ0[26,27,53]
160Vitisin C NQNQNQNQ0[26,27,67]
161Ampelopsin CNQNQNQNQ0[26,27]
162Maackin ANQNQNQNQ0[26,27]
163Viniphenol ANQNQNQNQ0[26,27]
166Viniferol ANQNQNQNQ0[56]
167Viniferol BNQNQNQNQ0[56]
168Viniferol CNQNQNQNQ0[56]
169Viniferol DNQNQNQNQ0[67]
171Malibatol ANQNQNQNQ0[56]
172Ampelopsin FNQNQNQNQ0[56]
173Ampelopsin E NQNQNQNQ0[56]
176ViniferalNQNQNQNQ0[67]
178Vitisinol ENQNQNQNQ0[28]
1 ND = not detected. 2 NQ = not quantified by the authors. 3 Fresh and dry weight data were combined for the calculations, without any conversion. 4 N = number of data points used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.
Table
Table 7. Levels (mg/kg) of 26 stilbenic compounds identified in grapevine canes.
Table 7. Levels (mg/kg) of 26 stilbenic compounds identified in grapevine canes.
IdCompound NameMinimum Value 1,2Maximum ValueMean Value 3Standard DeviationN4References
123trans-ResveratrolND6526.292797.172559.7217[7,12,24,25,40,48,49,50,51,52,58,72]
134(+)-trans-ε-Viniferin 21.0012,612.222449.253197.2613[7,12,24,25,40,50,51,52,58]
133IsohopeaphenolND3521.52851.431133.467[12,24,51,52]
150Vitisin B (r-Viniferin)0.012159.00668.08818.4610[7,12,24,40,50,51,52,58]
119trans-Piceatannol0.501710.24583.88799.7111[7,12,24,25,40,50,51,52,58]
141trans-ω-Viniferin ND1714.63556.41628.603[7,12,24,25,50]
129Hopeaphenol ND1439.21511.39585.409[12,24,25,40,50,51,52,58]
116Pallidol4.001276.43440.81591.083[12,24,40,50]
139trans-Miyabenol C 0.012108.47412.53702.077[7,12,24,25,40,51,52,58]
115Ampelopsin A0.011684.16370.88534.328[12,24,25,40,50,51,52,58]
147Vitisin A (r2-Viniferin)43.00717.55293.18301.673[12,24,25,50,51,58]
149trans-δ-Viniferin9.0043.0026.0017.002[24,50]
113trans-Piceid0.5036.2113.5016.115[7,40,48,49,50]
177Vitisinol C1.0029.0015.0014.002[24]
108trans-Resveratrol-2-C-glucoside NQNQNQNQ0[7]
110trans-Resveratrol-O-glucosideNQNQNQNQ0[72]
111Leachianol G NQNQNQNQ0[50]
112Leachianol F NQNQNQNQ0[50]
114Restrytisol ANQNQNQNQ0[50,58]
118Caraphenol BNQNQNQNQ0[72]
121cis-PiceidNQNQNQNQ0[50]
125Ampelopsin B NQNQNQNQ0[40]
126trans-IsorhapontigeninNQNQNQNQ0[50]
130Ampelopsin D NQNQNQNQ0[50]
164trans-ε-Viniferin derivative (γ-lactam ring)NQNQNQNQ0[25]
165trans-Resveratrol derivative (γ-lactam ring)NQNQNQNQ0[25]
1 ND = not detected. 2 NQ = not quantified by the authors. 3 Fresh and dry weight data were combined for the calculations, without any conversion. 4 N = number of data points used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.
Table
Table 8. Levels (mg/kg) of 23 polyphenols (excluding stilbenes) identified in grapevine canes.
Table 8. Levels (mg/kg) of 23 polyphenols (excluding stilbenes) identified in grapevine canes.
IdCompound NameMinimum
Value 1		Maximum
Value		Mean
Value 2		Standard
Deviation		N3References
23Catechin 65.166735.241747.012525.8810[46,48,49,50,83]
48Sinapic acid 26.412283.201154.811128.404[46,47,83]
6Procyanidin B1215.36806.87511.12295.762[50]
40Epicatechin 45.53896.17269.40289.876[48,49,50]
46Ferulic acid 0.92650.13165.63279.748[46,47,48,49,83]
2Gallic acid7.21570.13165.06234.378[46,47,48,49,83]
38Prodelphinidin A-type 27.46292.88160.17132.712[50]
4Protocatechuic acid 3.25379.85103.31159.848[46,47,48,49,83]
24Caftaric acid 18.6477.6048.1229.484[48,49]
7p-Hydroxybenzoic acid0.0195.2247.6247.614 [46,47,83]
30Vanillic acid 0.01152.1040.1364.748[46,47,48,49,83]
36Syringic acid 0.01113.0931.0547.438[46,47,48,49,83]
50Ellagic acid0.0153.2518.7820.998[46,48,49,83]
27Coutaric acid 5.2019.3912.307.104[48,49]
43p-Coumaric acid 0.0131.2011.1311.978[46,47,48,49,83]
35Caffeic acid 1.153.432.291.144[47,48,49]
10Procyanidin A1 NQNQNQNQ0[50]
18Procyanidin C1 NQNQNQNQ0[50]
19Procyanidin T2 NQNQNQNQ0[50]
29Procyanidin B2 NQNQNQNQ0[50]
39Procyanidin dimer gallate NQNQNQNQ0[50]
58Quercetin-3-O-galactoside NQNQNQNQ0[50]
77Quercetin-3-O-arabinose NQNQNQNQ0[50]
1 NQ = not quantified by the authors. 2 Fresh and dry weight data were combined for the calculations, without any conversion. 3 N = number of data points used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.
Table
Table 9. Levels (mg/kg) of 23 stilbenic compounds identified in grapevine woods.
Table 9. Levels (mg/kg) of 23 stilbenic compounds identified in grapevine woods.
IdCompound NameMinimum
Value 1,2		Maximum
Value		Mean
Value 3		Standard
Deviation		N4References
134(+)-trans-ε-Viniferin 122.5714,080.888263.874866.897[12,13,43,45]
132(+)-cis-ε-Viniferin 2504.0814,023.653851.975759.792[13]
133Isohopeaphenol11.687913.002429.692544.597[12,13,43,45]
143α-ViniferinND4732.062366.032366.032[13]
123trans-Resveratrol15.113604.042195.121414.547[12,13,43,45]
137Ampelopsin H1144.772518.081831.43686.662[13]
116Pallidol410.602602.151647.36916.643[12,13]
111Leachianol G 350.322800.341575.331225.012[13]
129Hopeaphenol 20.095006.771570.131683.097[12,13,43,45]
141trans-ω-Viniferin 1554.161554.161554.160.001[12]
112Leachianol F 35.572805.131420.351384.782[13]
115Ampelopsin A151.003684.011345.171541.975[12,13,45]
147Vitisin A (r2-Viniferin)1298.671298.671298.670.001[12]
128cis-Resveratrol780.583609.66774.641192.862[13]
110trans-Resveratrol-O-glucoside131.001090.00610.50479.502[44]
150Vitisin B (r-Viniferin)569.18569.18569.180.001[12]
139trans-Miyabenol C ND1339.51430.02482.175[12,13,45]
125Ampelopsin B ND493.44246.72246.722[13]
119trans-Piceatannol38.00378.07160.69154.143[12,45]
130Ampelopsin D 10.51310.22160.37149.862[43]
113trans-Piceid35.0050.0042.507.502[45]
136Diptoindonesin A9.7857.7033.7423.962[44]
106trans-Astringin 2.5624.0013.2810.722[44]
1 ND = not detected. 2 NQ = not quantified by the authors. 3 Fresh and dry weight data were combined for the calculations, without any conversion. 4 N = number of data points used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.
Table
Table 10. Levels (mg/kg) of 24 stilbenic compounds identified in grapevine roots.
Table 10. Levels (mg/kg) of 24 stilbenic compounds identified in grapevine roots.
IdCompound NameMinimum
Value 1		Maximum
Value		Mean
Value 2		Standard
Deviation		N3References
134(+)-trans-ε-Viniferin 125.1018,000.986475.958163.573[12,23,30,43]
150Vitisin B (r-Viniferin)11.1012,829.856420.486409.382[12,30,41,42]
129Hopeaphenol 1814.901814.901814.900.001[12,41,42]
115Ampelopsin A15.602178.231096.921081.322[12,29,30,41,42]
147Vitisin A (r2-viniferin)87.102093.131090.121003.022[12,30]
133Isohopeaphenol529.54529.54529.540.001[12]
123trans-Resveratrol46.301095.24503.25438.743[12,23,29,30]
141trans-ω-Viniferin 127.70127.70127.700.001[12]
139trans-Miyabenol C 12.70212.34112.5299.822[12,30]
113trans-Piceid112.07112.07112.070.001[23,29]
116Pallidol73.0673.0673.060.001[12,29]
119trans-Piceatannol4.20121.3347.1852.663[12,23,30]
149trans-δ-viniferin32.7732.7732.770.001[23]
121cis-PiceidNQNQNQNQ0[29]
161Ampelopsin CNQNQNQNQ0[41,42]
169Viniferol DNQNQNQNQ0[41,42]
170Viniferol ENQNQNQNQ0[41,42]
173Ampelopsin E NQNQNQNQ0[41,42]
174Wilsonol CNQNQNQNQ0[29]
175Heyneanol ANQNQNQNQ0[29]
179Vitisinol BNQNQNQNQ0[41,42]
180Stenophyllol CNQNQNQNQ0[41,42]
181Viniferether ANQNQNQNQ0[41,42]
182Viniferether BNQNQNQNQ0[41,42]
1 NQ = not quantified by the authors. 2 Fresh and dry weight data were combined for the calculations, without any conversion. 3 N = number of data points used in the calculation of the mean value, and made of minimum, maximum, and average values extracted from each reference.

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MDPI and ACS Style

Goufo, P.; Singh, R.K.; Cortez, I. A Reference List of Phenolic Compounds (Including Stilbenes) in Grapevine (Vitis vinifera L.) Roots, Woods, Canes, Stems, and Leaves. Antioxidants 2020, 9, 398. https://doi.org/10.3390/antiox9050398

AMA Style

Goufo P, Singh RK, Cortez I. A Reference List of Phenolic Compounds (Including Stilbenes) in Grapevine (Vitis vinifera L.) Roots, Woods, Canes, Stems, and Leaves. Antioxidants. 2020; 9(5):398. https://doi.org/10.3390/antiox9050398

Chicago/Turabian Style

Goufo, Piebiep, Rupesh Kumar Singh, and Isabel Cortez. 2020. "A Reference List of Phenolic Compounds (Including Stilbenes) in Grapevine (Vitis vinifera L.) Roots, Woods, Canes, Stems, and Leaves" Antioxidants 9, no. 5: 398. https://doi.org/10.3390/antiox9050398

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