Polyphenols In Wine
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Phenolic compounds— natural phenol and
polyphenol Polyphenols () are a large family of naturally occurring phenols. They are abundant in plants and structurally diverse. Polyphenols include phenolic acids, flavonoids, tannic acid, and ellagitannin, some of which have been used historically as ...
s—occur naturally in
wine Wine is an alcoholic drink made from Fermentation in winemaking, fermented fruit. Yeast in winemaking, Yeast consumes the sugar in the fruit and converts it to ethanol and carbon dioxide, releasing heat in the process. Wine is most often made f ...
. These include a large group of several hundred
chemical compound A chemical compound is a chemical substance composed of many identical molecules (or molecular entities) containing atoms from more than one chemical element held together by chemical bonds. A molecule consisting of atoms of only one element ...
s that affect the
taste The gustatory system or sense of taste is the sensory system that is partially responsible for the perception of taste. Taste is the perception stimulated when a substance in the mouth biochemistry, reacts chemically with taste receptor cells l ...
,
color Color (or colour in English in the Commonwealth of Nations, Commonwealth English; American and British English spelling differences#-our, -or, see spelling differences) is the visual perception based on the electromagnetic spectrum. Though co ...
and mouthfeel of wine. These compounds include phenolic acids,
stilbenoid Stilbenoids are hydroxylated derivatives of stilbene. They have a C6–C2–C6 structure. In biochemical terms, they belong to the family of phenylpropanoids and share most of their biosynthesis pathway with Chalconoid, chalcones. Most stilbenoids ...
s, flavonols, dihydroflavonols, anthocyanins, flavanol monomers ( catechins) and flavanol polymers (
proanthocyanidin Proanthocyanidins are a class of polyphenols found in many plants, such as cranberry, blueberry, and grape seeds. Chemically, they are oligomeric flavonoids. Many are oligomers of catechin and epicatechin and their gallic acid esters. More complex ...
s). This large group of natural phenols can be broadly separated into two categories,
flavonoid Flavonoids (or bioflavonoids; from the Latin word ''flavus'', meaning yellow, their color in nature) are a class of polyphenolic secondary metabolites found in plants, and thus commonly consumed in the diets of humans. Chemically, flavonoids ...
s and non-flavonoids. Flavonoids include the anthocyanins and
tannin Tannins (or tannoids) are a class of astringent, polyphenolic biomolecules that bind to and Precipitation (chemistry), precipitate proteins and various other organic compounds including amino acids and alkaloids. The term ''tannin'' is widel ...
s which contribute to the color and mouthfeel of the wine. The non-flavonoids include the
stilbenoid Stilbenoids are hydroxylated derivatives of stilbene. They have a C6–C2–C6 structure. In biochemical terms, they belong to the family of phenylpropanoids and share most of their biosynthesis pathway with Chalconoid, chalcones. Most stilbenoids ...
s such as
resveratrol Resveratrol (3,5,4′-trihydroxy-''trans''-stilbene) is a stilbenoid, a type of natural phenol or polyphenol and a phytoalexin produced by several plants in response to injury or when the plant is under attack by pathogens, such as bacterium, ba ...
and phenolic acids such as benzoic, caffeic and cinnamic acids.


Origin of the phenolic compounds

The natural phenols are not evenly distributed within the grape. Phenolic acids are largely present in the pulp, anthocyanins and
stilbenoid Stilbenoids are hydroxylated derivatives of stilbene. They have a C6–C2–C6 structure. In biochemical terms, they belong to the family of phenylpropanoids and share most of their biosynthesis pathway with Chalconoid, chalcones. Most stilbenoids ...
s in the skin, and other phenols ( catechins,
proanthocyanidin Proanthocyanidins are a class of polyphenols found in many plants, such as cranberry, blueberry, and grape seeds. Chemically, they are oligomeric flavonoids. Many are oligomers of catechin and epicatechin and their gallic acid esters. More complex ...
s and flavonols) in the skin and the seeds. During the growth cycle of the grapevine, sunlight will increase the concentration of phenolics in the grape berries, their development being an important component of canopy management. The proportion of the different phenols in any one wine will therefore vary according to the type of vinification. Red wine will be richer in phenols abundant in the skin and seeds, such as anthocyanin,
proanthocyanidin Proanthocyanidins are a class of polyphenols found in many plants, such as cranberry, blueberry, and grape seeds. Chemically, they are oligomeric flavonoids. Many are oligomers of catechin and epicatechin and their gallic acid esters. More complex ...
s and flavonols, whereas the phenols in
white wine White wine is a wine that is Fermentation in winemaking, fermented without undergoing the process of Maceration (wine), maceration, which involves prolonged contact between the juice with the grape skins, seeds, and pulp. The wine color, colou ...
will essentially originate from the pulp, and these will be the phenolic acids together with lower amounts of catechins and stilbenes. Red wines will also have the phenols found in white wines. Wine simple phenols are further transformed during wine aging into complex molecules formed notably by the condensation of proanthocyanidins and anthocyanins, which explains the modification in the color. Anthocyanins react with catechins, proanthocyanidins and other wine components during wine aging to form new polymeric pigments resulting in a modification of the wine color and a lower astringency. Average total polyphenol content measured by the Folin method is 216 mg/100 ml for red wine and 32 mg/100 ml for white wine. The content of phenols in rosé wine (82 mg/100 ml) is intermediate between that in red and white wines. In
winemaking Winemaking, wine-making, or vinification is the production of wine, starting with the selection of the fruit, its Ethanol fermentation, fermentation into alcohol, and the bottling of the finished liquid. The history of wine-making stretches over ...
, the process of maceration or "skin contact" is used to increase the concentration of phenols in wine. Phenolic acids are found in the pulp or juice of the wine and can be commonly found in white wines which usually do not go through a maceration period. The process of oak aging can also introduce phenolic compounds into wine, most notably vanillin which adds
vanilla Vanilla is a spice derived from orchids of the genus ''Vanilla (genus), Vanilla'', primarily obtained from pods of the flat-leaved vanilla (''Vanilla planifolia, V. planifolia''). ''Vanilla'' is not Autogamy, autogamous, so pollination ...
aroma to wines.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, pp 517-518. Oxford University Press 2006 . Most wine phenols are classified as secondary metabolites and were not thought to be active in the primary
metabolism Metabolism (, from ''metabolē'', "change") is the set of life-sustaining chemical reactions in organisms. The three main functions of metabolism are: the conversion of the energy in food to energy available to run cellular processes; the co ...
and function of the grapevine. However, there is evidence that in some plants
flavonoid Flavonoids (or bioflavonoids; from the Latin word ''flavus'', meaning yellow, their color in nature) are a class of polyphenolic secondary metabolites found in plants, and thus commonly consumed in the diets of humans. Chemically, flavonoids ...
s play a role as endogenous regulators of auxin transport. They are
water-soluble In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution. The extent of the solub ...
and are usually secreted into the
vacuole A vacuole () is a membrane-bound organelle which is present in Plant cell, plant and Fungus, fungal Cell (biology), cells and some protist, animal, and bacterial cells. Vacuoles are essentially enclosed compartments which are filled with water ...
of the grapevine as
glycosides In chemistry, a glycoside is a molecule in which a sugar is bound to another functional group via a glycosidic bond. Glycosides play numerous important roles in living organisms. Many plants store chemicals in the form of inactive glycosides. ...
.


Grape polyphenols

''
Vitis vinifera ''Vitis vinifera'', the common grape vine, is a species of flowering plant, native to the Mediterranean Basin, Mediterranean region, Central Europe, and southwestern Asia, from Morocco and Portugal north to southern Germany and east to northern ...
'', the common grape vine, from which European style wines are made the world over, produces many phenolic compounds. There is a varietal effect on the relative composition.


Flavonoids

In red wine, up to 90% of the wine's phenolic content falls under the classification of
flavonoid Flavonoids (or bioflavonoids; from the Latin word ''flavus'', meaning yellow, their color in nature) are a class of polyphenolic secondary metabolites found in plants, and thus commonly consumed in the diets of humans. Chemically, flavonoids ...
s. These phenols, mainly derived from the stems, seeds and skins are often leached out of the grape during the maceration period of winemaking. The amount of phenols leached is known as extraction. These compounds contribute to the astringency, color and mouthfeel of the wine. In white wines the number of flavonoids is reduced due to the lesser contact with the skins that they receive during winemaking. There is on-going study into the health benefits of wine derived from the
antioxidant Antioxidants are Chemical compound, compounds that inhibit Redox, oxidation, a chemical reaction that can produce Radical (chemistry), free radicals. Autoxidation leads to degradation of organic compounds, including living matter. Antioxidants ...
and chemopreventive properties of flavonoids.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, pp. 273-274. Oxford University Press 2006 .


Flavonols

Within the flavonoid category is a subcategory known as flavonols, which includes the yellow
pigment A pigment is a powder used to add or alter color or change visual appearance. Pigments are completely or nearly solubility, insoluble and reactivity (chemistry), chemically unreactive in water or another medium; in contrast, dyes are colored sub ...
- quercetin. Like other flavonoids, the concentration of flavonols in the grape berries increases as they are exposed to sunlight. Wine grapes facing too much sun exposure can see an accelerated ripening period, leading to a lessened ability for the synthesis of flavonols. Some viticulturalists will use measurement of flavonols such as quercetin as an indication of a vineyard's sun exposure and the effectiveness of canopy management techniques.


Anthocyanins

Anthocyanins are phenolic compounds found throughout the plant kingdom, being frequently responsible for the blue to red colors found in
flower Flowers, also known as blooms and blossoms, are the reproductive structures of flowering plants ( angiosperms). Typically, they are structured in four circular levels, called whorls, around the end of a stalk. These whorls include: calyx, m ...
s,
fruit In botany, a fruit is the seed-bearing structure in flowering plants (angiosperms) that is formed from the ovary after flowering. Fruits are the means by which angiosperms disseminate their seeds. Edible fruits in particular have long propaga ...
s and
leaves A leaf (: leaves) is a principal appendage of the stem of a vascular plant, usually borne laterally above ground and specialized for photosynthesis. Leaves are collectively called foliage, as in "autumn foliage", while the leaves, stem, ...
. In wine grapes, they develop during the stage of '' veraison,'' when the skin of red wine grapes changes color from green to red to black. As the sugars in the grape increase during ripening so does the concentration of anthocyanins. An issue associated with climate change has been the accumulation of sugars within the grape accelerating rapidly and outpacing the accumulation of anthocyanins. This leaves viticulturists with the choice of harvesting grapes with too high sugar content or with too low anthocyanin content. In most grapes anthocyanins are found only in the outer cell layers of the skin, leaving the grape juice inside virtually colorless. Therefore, to get color pigmentation in the wine, the fermenting
must Must is freshly crushed Juice, fruit juice (usually grape juice) that contains the skins, seeds, and stems of the fruit. The solid portion of the must is called pomace and typically makes up 7–23% of the total weight of the must. Making must ...
needs to be in contact with the grape skins in order for the anthocyanins to be extracted. Hence, white wine can be made from red wine grapes in the same way that many white
sparkling wine Sparkling wine is a wine with significant levels of carbon dioxide in it, making it fizzy. While it is common to refer to this as champagne, European Union countries legally reserve that word for products exclusively produced in the Champagne ( ...
s are made from the red wine grapes of
Pinot noir Pinot noir (), also known as Pinot nero, is a red-wine grape variety of the species ''Vitis vinifera''. The name also refers to wines created predominantly from Pinot noir grapes. The name is derived from the French language, French words fo ...
and Pinot Meunier. The exception to this is the small class of grapes known as teinturiers, such as Alicante Bouschet, which have a small amount of anthocyanins in the pulp that produces pigmented juice.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, p. 24. Oxford University Press 2006 . There are several types of anthocyanins (as the
glycoside In chemistry, a glycoside is a molecule in which a sugar is bound to another functional group via a glycosidic bond. Glycosides play numerous important roles in living organisms. Many plants store chemicals in the form of inactive glycosides. ...
) found in wine grapes which are responsible for the vast range of coloring from ruby red through to dark black found in wine grapes. Ampelographers can use this observation to assist in the identification of different grape varieties. The European vine family ''
Vitis vinifera ''Vitis vinifera'', the common grape vine, is a species of flowering plant, native to the Mediterranean Basin, Mediterranean region, Central Europe, and southwestern Asia, from Morocco and Portugal north to southern Germany and east to northern ...
'' is characterized by anthocyanins that are composed of only one molecule of
glucose Glucose is a sugar with the Chemical formula#Molecular formula, molecular formula , which is often abbreviated as Glc. It is overall the most abundant monosaccharide, a subcategory of carbohydrates. It is mainly made by plants and most algae d ...
while non-''vinifera'' vines such as hybrids and the American '' Vitis labrusca'' will have anthocyanins with two molecules. This phenomenon is due to a double mutation in the anthocyanin 5-O-glucosyltransferase gene of ''V. vinifera''. In the mid-20th century, French ampelographers used this knowledge to test the various vine varieties throughout France to identify which vineyards still contained non-''vinifera'' plantings. Red-berried Pinot grape varieties are also known to not synthesize para-coumaroylated or acetylated anthocyanins as other varieties do. The color variation in the finished red wine is partly derived from the
ionization Ionization or ionisation is the process by which an atom or a molecule acquires a negative or positive Electric charge, charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged at ...
of anthocyanin pigments caused by the acidity of the wine. In this case, the three types of anthocyanin pigments are red, blue and colorless with the concentration of those various pigments dictating the color of the wine. A wine with low pH (and such greater acidity) will have a higher occurrence of ionized anthocyanins which will increase the amount of bright red pigments. Wines with a higher pH will have a higher concentration of blue and colorless pigments. As the wine ages, anthocyanins will react with other acids and compounds in wines such as tannins,
pyruvic acid Pyruvic acid (CH3COCOOH) is the simplest of the keto acids, alpha-keto acids, with a carboxylic acid and a ketone functional group. Pyruvate, the conjugate acid, conjugate base, CH3COCOO−, is an metabolic intermediate, intermediate in several m ...
and acetaldehyde which will change the color of the wine, causing it to develop more "brick red" hues. These molecules will link up to create
polymer A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
s that eventually exceed their
solubility In chemistry, solubility is the ability of a chemical substance, substance, the solute, to form a solution (chemistry), solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form su ...
and become sediment at the bottom of wine bottles. Pyranoanthocyanins are chemical compounds formed in red
wine Wine is an alcoholic drink made from Fermentation in winemaking, fermented fruit. Yeast in winemaking, Yeast consumes the sugar in the fruit and converts it to ethanol and carbon dioxide, releasing heat in the process. Wine is most often made f ...
s by
yeast Yeasts are eukaryotic, single-celled microorganisms classified as members of the fungus kingdom (biology), kingdom. The first yeast originated hundreds of millions of years ago, and at least 1,500 species are currently recognized. They are est ...
during
fermentation Fermentation is a type of anaerobic metabolism which harnesses the redox potential of the reactants to make adenosine triphosphate (ATP) and organic end products. Organic molecules, such as glucose or other sugars, are catabolized and reduce ...
processes or during controlled oxygenation processes during the aging of wine.


Tannins

Tannins refer to the diverse group of chemical compounds in wine that can affect the color, aging ability and texture of the wine. While tannins cannot be smelled or tasted, they can be perceived during wine tasting by the tactile sensation of astringency and sense of bitterness that they can leave in the mouth. This is due to the tendency of tannins to react with
protein Proteins are large biomolecules and macromolecules that comprise one or more long chains of amino acid residue (biochemistry), residues. Proteins perform a vast array of functions within organisms, including Enzyme catalysis, catalysing metab ...
s, such as the ones found in saliva. In food and wine pairing, foods that are high in proteins (such as red meat) are often paired with tannic wines to minimize the astringency of tannins. However, many wine drinkers find the perception of tannins to be a positive trait—especially as it relates to mouthfeel. The management of tannins in the winemaking process is a key component in the resulting quality.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, p. 680. Oxford University Press 2006 . Tannins are found in the skin, stems, and seeds of wine grapes but can also be introduced to the wine through the use of oak barrels and chips or with the addition of tannin powder. The natural tannins found in grapes are known as
proanthocyanidin Proanthocyanidins are a class of polyphenols found in many plants, such as cranberry, blueberry, and grape seeds. Chemically, they are oligomeric flavonoids. Many are oligomers of catechin and epicatechin and their gallic acid esters. More complex ...
s due to their ability to release red anthocyanin pigments when they are heated in an acidic solution. Grape extracts are mainly rich in monomers and small oligomers (mean degree of polymerization < 8). Grape seed extracts contain three monomers (catechin, epicatechin and epicatechin gallate) and procyanidin oligomers. Grape skin extracts contain four monomers (catechin, epicatechin, gallocatechin and epigallocatechin), as well as procyanidins and prodelphinidins oligomers. The tannins are formed by
enzymes An enzyme () is a protein that acts as a biological catalyst by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as pro ...
during metabolic processes of the grapevine. The amount of tannins found naturally in grapes varies depending on the variety with Cabernet Sauvignon, Nebbiolo, Syrah and Tannat being 4 of the most tannic grape varieties. The reaction of tannins and anthocyanins with the phenolic compound catechins creates another class of tannins known as pigmented tannins which influence the color of red wine.Compositional investigation of pigmented tannin. Kennedy James A. and Hayasaka Yoji, A.C.S. symposium series, 2004, vol. 886, pp. 247-264, Commercial preparations of tannins, known as ''enological tannins'', made from oak wood,
grape A grape is a fruit, botanically a berry, of the deciduous woody vines of the flowering plant genus ''Vitis''. Grapes are a non- climacteric type of fruit, generally occurring in clusters. The cultivation of grapes began approximately 8,0 ...
seed and skin, plant
gall Galls (from the Latin , 'oak-apple') or ''cecidia'' (from the Greek , anything gushing out) are a kind of swelling growth on the external tissues of plants. Plant galls are abnormal outgrowths of plant tissues, similar to benign tumors or war ...
, chestnut, quebracho, gambierIdentification of the origin of commercial enological tannins by the analysis of monosaccharides and polyalcohols. Luz Sanz M., Martinez-Castro Isabel and Moreno-Arribas M. Victoria, ''Food chemistry'', 2008, vol. 111, no3, pp. 778-783, and myrobalan fruits, can be added at different stages of the wine production to improve color durability. The tannins derived from oak influence are known as "hydrolysable tannins" being created from the ellagic and gallic acid found in the wood. In the vineyards, there is also a growing distinction being made between "ripe" and "unripe" tannins present in the grape. This " physiological ripeness", which is roughly determined by tasting the grapes off the vines, is being used along with sugar levels as a determination of when to
harvest Harvesting is the process of collecting plants, animals, or fish (as well as fungi) as food, especially the process of gathering mature crops, and "the harvest" also refers to the collected crops. Reaping is the cutting of grain or pulses fo ...
. The idea is that "riper" tannins will taste softer but still impart some of the texture components found favorable in wine. In winemaking, the amount of the time that the must spends in contact with the grape skins, stems and seeds will influence the amount of tannins that are present in the wine with wines subjected to longer maceration period having more tannin extract. Following harvest, stems are normally picked out and discarded prior to fermentation but some winemakers may intentionally leave in a few stems for varieties low in tannins (like Pinot noir) in order to increase the tannic extract in the wine. If there is an excess in the amount of tannins in the wine, winemakers can use various fining agents like albumin, casein and gelatin that can bind to tannins molecule and precipitate them out as sediments. As a wine ages, tannins will form long polymerized chains which come across to a taster as "softer" and less tannic. This process can be accelerated by exposing the wine to
oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...
, which oxidize tannins to quinone-like compounds that are polymerization-prone. The winemaking technique of micro-oxygenation and decanting wine use oxygen to partially mimic the effect of aging on tannins. A study in wine production and consumption has shown that tannins, in the form of
proanthocyanidin Proanthocyanidins are a class of polyphenols found in many plants, such as cranberry, blueberry, and grape seeds. Chemically, they are oligomeric flavonoids. Many are oligomers of catechin and epicatechin and their gallic acid esters. More complex ...
s, have a beneficial effect on vascular health. The study showed that tannins suppressed production of the peptide responsible for hardening arteries. To support their findings, the study also points out that wines from the regions of southwest France and Sardinia are particularly rich in proanthocyanidins, and that these regions also produce populations with longer life spans. Reactions of tannins with the phenolic compound anthocyanidins creates another class of tannins known as ''pigmented tannins'' which influences the color of red wine.


= Addition of enological tannins

= Commercial preparations of tannins, known as ''enological tannins'', made from oak wood,
grape A grape is a fruit, botanically a berry, of the deciduous woody vines of the flowering plant genus ''Vitis''. Grapes are a non- climacteric type of fruit, generally occurring in clusters. The cultivation of grapes began approximately 8,0 ...
seed and skin, plant
gall Galls (from the Latin , 'oak-apple') or ''cecidia'' (from the Greek , anything gushing out) are a kind of swelling growth on the external tissues of plants. Plant galls are abnormal outgrowths of plant tissues, similar to benign tumors or war ...
, chestnut, quebracho, gambier and myrobalan fruits, can be added at different stages of the wine production to improve color durability.


= Effects of tannins on the drinkability and aging potential of wine

= Tannins are a natural preservative in wine. Un-aged wines with high tannin content can be less palatable than wines with a lower level of tannins. Tannins can be described as leaving a dry and puckered feeling with a "furriness" in the mouth that can be compared to a stewed tea, which is also very tannic. This effect is particularly profound when drinking tannic wines without the benefit of food. Many wine lovers see natural tannins (found particularly in varietals such as Cabernet Sauvignon and often accentuated by heavy oak barrel aging) as a sign of potential longevity and ageability. Tannins impart a mouth-puckering astringency when the wine is young but "resolve" (through a chemical process called
polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...
) into delicious and complex elements of "bottle bouquet" when the wine is cellared under appropriate temperature conditions, preferably in the range of a constant . Such wines mellow and improve with age with the tannic "backbone" helping the wine survive for as long as 40 years or more. In many regions (such as in
Bordeaux Bordeaux ( ; ; Gascon language, Gascon ; ) is a city on the river Garonne in the Gironde Departments of France, department, southwestern France. A port city, it is the capital of the Nouvelle-Aquitaine region, as well as the Prefectures in F ...
), tannic grapes such as Cabernet Sauvignon are blended with lower-tannin grapes such as Merlot or Cabernet Franc, diluting the tannic characteristics. White wines and wines that are vinified to be drunk young (for examples, see nouveau wines) typically have lower tannin levels.


Other flavonoids

Flavan-3-ol Flavan-3-ols (sometimes referred to as flavanols) are a subgroup of flavonoids. They are derivatives of flavans that possess a 2-phenyl-3,4-dihydro-2''H''-chromen-3-ol skeleton. Flavan-3-ols are structurally diverse and include a range of compo ...
s (catechins) are flavonoids that contribute to the construction of various tannins and contribute to the perception of bitterness in wine. They are found in highest concentrations in grape seeds but are also in the skin and stems. Catechins play a role in the microbial defense of the grape berry, being produced in higher concentrations by the grape vines when it is being attacked by grape diseases such as
downy mildew Downy mildew refers to any of several types of oomycete microbes that are obligate parasites of plants. Downy mildews exclusively belong to the Peronosporaceae family. In commercial agriculture, they are a particular problem for growers of c ...
. Because of that grape vines in cool, damp climates produce catechins at high levels than vines in dry, hot climates. Together with anthocyanins and tannins they increase the stability of a wines color-meaning that a wine will be able to maintain its coloring for a longer period of time. The amount of catechins present varies among grape varieties with varietals like Pinot noir having high concentrations while Merlot and especially Syrah have very low levels. As an antioxidant, there are some studies into the health benefits of moderate consumption of wines high in catechins.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, p. 144. Oxford University Press 2006 . In red grapes, the main flavonol is on average quercetin, followed by myricetin, kaempferol, laricitrin, isorhamnetin, and syringetin. In white grapes, the main flavonol is quercetin, followed by kaempferol and isorhamnetin. The delphinidin-like flavonols myricetin, laricitrin, and syringetin are missing in all white varieties, indicating that the enzyme flavonoid 3',5'-hydroxylase is not expressed in white grape varieties. Myricetin, laricitrin and syringetin, flavonols which are present in red grape varieties only, can be found in red wine.


Non-flavonoids


Hydroxycinnamic acids

Hydroxycinnamic acids are the most important group of nonflavonoid phenols in wine. The four most abundant ones are the tartaric acid esters ''trans''-caftaric, ''cis''- and ''trans''- coutaric, and ''trans''- fertaric acids. In wine they are present also in the free form (''trans''- caffeic, ''trans''- p-coumaric, and ''trans''- ferulic acids).


Stilbenoids

''V. vinifera'' also produces
stilbenoid Stilbenoids are hydroxylated derivatives of stilbene. They have a C6–C2–C6 structure. In biochemical terms, they belong to the family of phenylpropanoids and share most of their biosynthesis pathway with Chalconoid, chalcones. Most stilbenoids ...
s.
Resveratrol Resveratrol (3,5,4′-trihydroxy-''trans''-stilbene) is a stilbenoid, a type of natural phenol or polyphenol and a phytoalexin produced by several plants in response to injury or when the plant is under attack by pathogens, such as bacterium, ba ...
is found in highest concentration in the skins of wine grapes. The accumulation in ripe berries of different concentrations of both bound and free resveratrols depends on the maturity level and is highly variable according to the genotype. Both red and white wine grape varieties contain resveratrol, but more frequent skin contact and maceration leads to red wines normally having ten times more resveratrol than white wines. Resveratrol produced by grape vines provides defense against microbes, and production can be further artificially stimulated by
ultraviolet radiation Ultraviolet radiation, also known as simply UV, is electromagnetic radiation of wavelengths of 10–400 nanometers, shorter than that of visible light, but longer than X-rays. UV radiation is present in sunlight and constitutes about 10% of t ...
. Grapevines in cool, damp regions with higher risk of grape diseases, such as
Bordeaux Bordeaux ( ; ; Gascon language, Gascon ; ) is a city on the river Garonne in the Gironde Departments of France, department, southwestern France. A port city, it is the capital of the Nouvelle-Aquitaine region, as well as the Prefectures in F ...
and Burgundy, tend to produce grapes with higher levels of resveratrol than warmer, drier wine regions such as
California California () is a U.S. state, state in the Western United States that lies on the West Coast of the United States, Pacific Coast. It borders Oregon to the north, Nevada and Arizona to the east, and shares Mexico–United States border, an ...
and
Australia Australia, officially the Commonwealth of Australia, is a country comprising mainland Australia, the mainland of the Australia (continent), Australian continent, the island of Tasmania and list of islands of Australia, numerous smaller isl ...
. Different grape varieties tend to have differing levels, with
Muscadine ''Vitis rotundifolia'', or muscadine, is a grapevine species native to the southern United States, southeastern and south-central United States. The growth range extends from Florida to New Jersey coast, and west to eastern Texas and Oklahoma. I ...
s and the Pinot family having high levels while the Cabernet family has lower levels of resveratrol. In the late 20th century interest in the possible health benefits of resveratrol in wine was spurred by discussion of the French paradox involving the health of wine drinkers in France.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, p. 569. Oxford University Press 2006 . Piceatannol is also present in grape from where it can be extracted and found in red wine.


Phenolic acids

Vanillin is a phenolic aldehyde most commonly associated with the vanilla notes in wines that have been aged in oak. Trace amounts of vanillin are found naturally in grapes, but they are most prominent in the
lignin Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidit ...
structure of oak barrels. Newer barrels will impart more vanillin, with the concentration present decreasing with each subsequent usage.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, p. 727. Oxford University Press 2006 .


Phenols from oak ageing

Oak barrel will add compounds such as vanillin and hydrolysable tannins (
ellagitannin image:Castalagin.svg, 130px, Castalagin is a representative ellagitannin, characterized by coupled gallic acid substituents The ellagitannins are a diverse class of hydrolyzable tannins, a type of polyphenol formed primarily from the oxidative link ...
s). The hydrolyzable tannins present in oak are derived from
lignin Lignin is a class of complex organic polymers that form key structural materials in the support tissues of most plants. Lignins are particularly important in the formation of cell walls, especially in wood and bark, because they lend rigidit ...
structures in the wood. They help protect the wine from oxidation and reduction.J. Robinson (ed), ''"The Oxford Companion to Wine"''. Third Edition, p. 492, Oxford University Press 2006, . 4-Ethylphenol and 4-ethylguaiacol are produced during ageing of red wine in oak barrels that are infected by brettanomyces .


Natural phenols and polyphenols from cork stoppers

Low molecular weight polyphenols, as well as ellagitannins, are susceptible to be extracted from cork stoppers into the wine. The identified polyphenols are gallic, protocatechuic, vanillic, caffeic, ferulic, and ellagic acids; protocatechuic, vanillic, coniferyl, and sinapic aldehydes; the coumarins aesculetin and scopoletin; the ellagitannins are roburins A and E, grandinin,
vescalagin Castalagin is an ellagitannin, a type of hydrolyzable tannin, found in oak and chestnut wood and in the stem barks of ''Terminalia leiocarpa'' and ''Terminalia avicennoides''. Castalagin is the diastereomer of vescalagin in C-1 of the glycosidic c ...
and castalagin. Guaiacol is one of the molecules responsible for the cork taint wine fault.


Phenolic content in relation with wine making techniques


Extraction levels in relation with grape pressing techniques

Flash release is a technique used in wine pressing. The technique allows for a better extraction of phenolic compounds.


Microoxygeneation

The exposure of wine to oxygen in limited quantities affects phenolic content.


Phenolic compounds found in wine

Depending on the methods of production, wine type, grape varieties, ageing processes, the following phenolics can be found in wine. The list, sorted in alphabetical order of common names, is not exhaustive. * Acutissimin A * aesculetin * Anthocyanidin-caftaric acid adducts * Astilbin * Astringin * B type proanthocyanidin dimers * B type proanthocyanidin trimers * Caffeic acid * Caftaric acid * Castalagin * Castavinol C1 * Castavinol C2 * Castavinol C3 * Castavinol C4 * Catechin * Catechin-(4,8)-malvidin-3-O-glucoside * Compound NJ2 * Coniferyl aldehyde * Coumaric acid * Coutaric acid * Cyanidin * Cyanin (Cyanidin-3,5-O-diglucoside) * Cyanidin 3O-glucoside * Cyanidin acetyl 3O glucoside * Cyanidin coumaroyl 3O glucoside * Cyanidin-3-O-glucoside-pyruvic acid * Cyanidin-3-O-acetylglucoside-pyruvic acid * Cyanidin-coumaroylglucoside-pyruvic acid * Delphinidin * Delphinidin 3O glucoside * Delphinidin acetyl-3O glucoside * Delphinidin coumaroyl 3O glucoside * Delphinidin-3-O-glucoside-pyruvic acid * Delphinidin-3-O-acetylglucoside-pyruvic acid * Delphinidin-3-O-coumaroylglucoside-pyruvic acid * Delphinidin-3-O-glucoside-4-vinylcatechol * Delphinidin-3-O-acetylglucoside-4-vinylcatechol * Delphinidin-3-O-coumaroylglucoside-4-vinylcatechol * Delphinidin-3-O-glucoside-4-vinylphenol * Delphinidin-3-O-acetylglucoside-4-vinylphenol * Delphinidin-3-O-coumaroylglucoside-4-vinylphenol * Delphinidin-3-O-glucoside-4-vinylguaiacol * Delphinidin-3-O-glucoside-4-vinyl(epi)catechin * Delphinidin-3-O-acetylglucoside-4-vinyl(epi)catechin * Delta-viniferin * Dihydro-resveratrol * Ellagic acid * Engeletin * Epicatechin gallate * Epigallocatechin * Epsilon-viniferin * Ethyl caffeate * Ethyl gallate * Ethyl protocatechuate * 4-Ethylguaiacol * 4-Ethylphenol * Fertaric acid * Ferulic acid * Gallic acid * Gentisic acid * Grandinin * Grape reaction product (GRP) * Guaiacol * Hopeaphenol * p-Hydroxybenzoic acid * Isorhamnetol 3-glucoside * Kaempferol * Kaempferol glucoside (astragalin) * Kaempferol glucuronide * Malvidin * Malvidin 3O-glucoside (oenin) * Malvidin acetyl-3O-glucoside * Malvidin cafeoyl-3O-glucoside * Malvidin coumaroyl-3Oglucoside * Malvidin glucoside-ethyl-catechin * Malvidin-3-O-glucoside-pyruvic acid * Malvidin-3-O-acetylglucoside-pyruvic acid * Malvidin-3-O-coumaroylglucoside-pyruvic acid * Malvidin-3-O-glucoside-acetaldehyde * Malvidin-3-O-acetylglucoside-acetaldehyde * Malvidin-3-O-coumaroylglucoside-acetaldehyde * Malvidin-3-O-glucoside-4-vinylcatechol * Malvidin-3-O-acetylglucoside-4-vinylcatechol * Malvidin-3-O-coumaroylglucoside-4-vinylcatechol * Malvidin-3-O-glucoside-4-vinylphenol * Malvidin-3-O-acetylglucoside-4-vinylphenol * Malvidin-3-O-coumaroylglucoside-4-vinylphenol * Malvidin-3-O-caffeoylglucoside-4-vinylphenol * Malvidin-3-O-glucoside-4-vinylguaiacol * Malvidin-3-O-acetylglucoside-4-vinylguaiacol * Malvidin-3-O-coumaroylglucoside-vinylguaiacol * Malvidin-3-O-glucoside-4-vinyl(epi)catechin * Malvidin-3-O-acetylglucoside-4-vinyl(epi)catechin * Malvidin-3-O-coumaroylglucoside-4-vinyl(epi)catechin * Methyl gallate * Myricetol * Myricetol 3-glucoside * Myricetol 3-glucuronide * Oxovitisin A * Pallidol * Pelargonin (Pelargonidin 3,5-O-diglucoside) * Peonidin 3O-glucoside * Peonidin acetyl-3O-glucoside * Peonidin-3-(6-p-caffeoyl)-glucoside * Peonidin coumaroyl 3O-glucoside * Peonidin-3-O-glucoside-pyruvic acid * Peonidin-3-O-acetylglucoside-pyruvic acid * Peonidin-3-O-coumaroylglucoside-pyruvic acid * Peonidin-3-O-glucoside-4-vinylcatechol * Peonidin-3-O-acetylglucoside-4-vinylcatechol * Peonidin-3-O-coumaroylglucoside-4-vinylcatechol * Peonidin-3-O-glucoside-4-vinylphenol * Peonidin-3-O-acetylglucoside-4-vinylphenol * Peonidin-3-O-coumaroylglucoside-4-vinylphenol * Peonidin-3-O-glucoside-4-vinylguaiacol * Peonidin-3-O-glucoside-4-vinyl(epi)catechin * Peonidin-3-O-acetylglucoside-4-vinyl(epi)catechin * Petunidin * Petunidin 3O glucoside * Petunidin acetyl-3O-glucoside * Petunidin coumaroyl-3O glucoside * Petunidin-3-O-glucoside-pyruvic acid * Petunidin-3-O-acetylglucoside-pyruvic acid * Petunidin-3-O-coumaroylglucoside-pyruvic acid * Petunidin-3-O-glucoside-4-vinylcatechol * Petunidin-3-O-acetylglucoside-4-vinylcatechol * Petunidin-3-O-coumaroylglucoside-4-vinylcatechol * Petunidin-3-O-glucoside-4-vinylphenol * Petunidin-3-O-acetylglucoside-4-vinylphenol * Petunidin-3-O-coumaroylglucoside-4-vinylphenol * Petunidin-3-O-glucoside-4-vinylguaiacol * Petunidin-3-O-glucoside-4-vinyl(epi)catechin * Petunidin-3-O-acetylglucoside-4-vinyl(epi)catechin * Phloroglucinol carboxylic acid * Piceatannol * Piceids * Pinotin A * Oligomeric procyanidins : ** Procyanidin B1 ** Procyanidin B2 ** Procyanidin B3 ** Procyanidin B4 ** B1-3-O-gallate ** B2-3-O-gallate **
B2-3'-O-gallate B, or b, is the second letter of the Latin alphabet, used in the modern English alphabet, the alphabets of other western European languages and others worldwide. Its name in English is '' bee'' (pronounced ), plural ''bees''. It represe ...
** procyanidin C1 (epicatechin-(4β→8)-epicatechin-(4β→8)-epicatechin) ** Procyanidin C2 (catechin-(4α→8)-catechin-(4α→8)-catechin) ** procyanidin T2 (trimer) * Protocatechuic acid * protocatechuic aldehyde * Quercetin * Quercetol glucoside * Quercetol glucuronide *
Resveratrol Resveratrol (3,5,4′-trihydroxy-''trans''-stilbene) is a stilbenoid, a type of natural phenol or polyphenol and a phytoalexin produced by several plants in response to injury or when the plant is under attack by pathogens, such as bacterium, ba ...
* Roburin A * Roburin E * Scopoletin * Sinapic aldehyde * Sinapinic acid * Syringic acid * Tyrosol * Vanillic acid * vanillin *
Vescalagin Castalagin is an ellagitannin, a type of hydrolyzable tannin, found in oak and chestnut wood and in the stem barks of ''Terminalia leiocarpa'' and ''Terminalia avicennoides''. Castalagin is the diastereomer of vescalagin in C-1 of the glycosidic c ...
* 4-Vinylphenol * Vitisin A * Vitisin B * Vinylpyranomalvidin-3O-glucoside-procyanidin dimer * VinylpyranoMv-3-coumaroylglucoside-procyanidin dimer * Vinylpyranomalvidin-3O-glucoside-catechin * Vinylpyranomalvidin-3O-coumaroylglucoside-catechin * Vinylpyranomalvidin-3O-phenol * Vinylpyranopetunidin-3O-glucoside-catechin * Vinylpyranopeonidin-3O-glucoside-catechin * Vinylpyranomalvidin-3O-acetylglucoside-catechin


Effects

Polyphenol compounds may interact with volatiles and contribute to the aromas in wine. Although wine polyphenols are speculated to provide
antioxidant Antioxidants are Chemical compound, compounds that inhibit Redox, oxidation, a chemical reaction that can produce Radical (chemistry), free radicals. Autoxidation leads to degradation of organic compounds, including living matter. Antioxidants ...
or other benefits, there is little evidence that wine polyphenols actually have any effect in humans. Limited preliminary research indicates that wine polyphenols may decrease platelet aggregation, enhance fibrinolysis, and increase HDL cholesterol, but high-quality
clinical trial Clinical trials are prospective biomedical or behavioral research studies on human subject research, human participants designed to answer specific questions about biomedical or behavioral interventions, including new treatments (such as novel v ...
s have not confirmed such effects, as of 2017.


See also

* Aging of wine *
Clarification and stabilization of wine In winemaking, clarification and stabilization are the processes by which insoluble matter Suspension (chemistry), suspended in the wine is removed before bottling. This matter may include dead yeast (wine), yeast cells (lees (wine), lees), bacter ...
* Grape seed extract * Phenolic content in tea * Wine chemistry * Wine preservatives


References


External links


Wine polyphenols vary with age and variety (Polyphenols on www.guideduvin.com)
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Polyphenol concentrations in red, white and rosé wines at www.phenol-explorer.eu
Natural phenols Polyphenols Wine chemistry