Tag Archives: flavanols or cathechins

Polyphenols in grapes and wine: chemical composition and biological activities

Polyphenols in grapes and wine: contents in brief

Polyphenols in Grapes
Fig. 1 – Red Grapes

The consumption of grapes and grape-derived products, particularly red wine but only at meals, has been associated with numerous health benefits, which include, in addition to the antioxidant/antiradical effect, also anti-inflammatory, cardioprotective, anticancer, antimicrobial, and neuroprotective activities.
Grapes contain many nutrients such as sugars, vitamins, minerals, fiber and phytochemicals. Among the latter, polyphenols are the most important compounds in determining the health effects of the fruit and derived products.
Indeed, grapes are among the fruits with highest content in polyphenols, whose composition is strongly influenced by several factors such as:

  • cultivar;
  • climate;
  • exposure to disease;
  • processing

Nowadays, the main species of grapes cultivated worldwide are: European grapes, Vitis vinifera, North American grapes, Vitis rotundifolia and Vitis labrusca, and French hybrids.
Note: grapes are not a fruit but an infructescence, that is, an ensemble of fruits (berries): the bunch of grapes. In turn, it consists of a peduncle, a rachis, cap stems or pedicels, and berries.

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What are polyphenols in grapes and wine?

Polyphenols in red grapes and wine are significantly higher, both in quantity and variety, than in white ones. This, according to many researchers, would be the basis of the more health benefits related to the consumption of red grapes and wine than white grapes and derived products.
Polyphenols in grapes and wine are a complex mixture of flavonoid compounds, the most abundant group, and non-flavonoid compounds.
Among flavonoids, they are found:

Among non-flavonoid polyphenols:

Most of the flavonoids present in wine derive from the epidermal layer of the berry skin, while 60-70% of the total polyphenols are present in the grape seeds. It should be noted that more than 70% of grape polyphenols are not extracted and remain in the pomace.
The complex chemical interactions that occur between these compounds, and between them and the other compounds of different nature present in grapes and wine, are probably essential in determining both the quality of the grapes and wine and the broad spectrum of therapeutic effects of these foods.
In wine, the mixture of polyphenols play important functions being able to influence:

  • bitterness;
  • astringency;
  • red color, of which they are among the main responsible;
  • sensitivity to oxidation, being molecules easily oxidizable by atmospheric oxygen.

Finally, they act as preservatives and are the basis of long aging.

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Polyphenols in grapes and wine: anthocyanins

They are flavonoids widely distributed in fruits and vegetables.
They are primarily located in the berry skin (in the outer layers of the hypodermal tissue), to which they confer color, having a hue that varies from red to blue. In some varieties, called “teinturier”, they also accumulate in the flesh of the berry.
There is a close relationship between berry development and the biosynthesis of anthocyanins. The synthesis starts at veraison (when the berry stops growing and changes its color), causes a color change of the berry that turns purple, and reaches the maximum levels at complete ripening.
Among wine flavonoids, they are one of the most potent antioxidants.
Each grape species and cultivars has a unique composition of anthocyanins. Moreover, in grapes of Vitis vinifera, due to a mutation in the gene coding for 5-O-glucosyltransferase, mutation that determines the synthesis of an inactive enzyme, only 3-monoglucoside derivatives are synthesized, while in other species  the glycosylation at position 5 also occurs. Interestingly, 3-monoglucoside derivatives are more intensely colored than 3,5-diglucoside derivatives.

Polyphenols in Grapes
Fig. 2 – Malvidin-3-glucoside

In red grapes and wine, the most abundant anthocyanins are the 3-monoglucosides of malvidin (the most abundant one both in grapes and wine), petunidin, delphinidin, peonidin, and cyanidin. In turn, the hydroxyl group at position 6 of the glucose can be acylated with an acetyl, caffeic or coumaric group, acylation that further enhances the stability.
Anthocyanidins, namely the non-conjugated molecules, are not present in grapes and in wine, except as traces.
Anthocyanins are scarcely present in white grapes and wine.
The composition of anthocyanins in wine is highly influenced both by the type of cultivar and by processing techniques, since they are present in wine as a result of extraction by maceration/fermentation processes. For this reason, wines deriving from similar varieties of grapes can have very different anthocyanin compositions.
Together with proanthocyanidins, they are the most important polyphenols in contributing to some organoleptic properties of red wine, as they are primarily responsible for astringency, bitterness, chemical stability against oxidation, as well as of the color of the young wine. In this regard, it should be underscored that with time their concentration decreases, while the color is due more and more to the formation of polymeric pigments produced by condensation of anthocyanins both among themselves and with other molecules.
During wine aging, proanthocyanidins and anthocyanins react to produce more complex molecules that can  partially precipitate.

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Polyphenols in grapes and wine: flavanols or catechins

Polyphenols in Grapes
Fig. 3 – Catechin

They are, together with condensed tannins, the most abundant flavonoids, representing up to 50% of the total polyphenols in white grapes and between 13% and 30% in red ones.
Their levels in wine depend on the type of cultivar.
Typically, the most abundant flavanol in wine is catechin, but epicatechin and epicatechin-3-gallate are also present.

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Polyphenols of grapes and wine: proanthocyanidins or condensed tannins

Polyphenols in Grapes
Fig. 4 – Procyanidin C1

Composed of catechin monomers, they are present in the berry skin, seeds and rachis of the bunch of grapes as:

  • dimers: the most common are procyanidins B1-B4, but also procyanidins B5-B8 can be present;
  • trimers: procyanidin C1 is the most abundant;
  • tetramers;
  • polymers, containing up to 8 monomers.

Their levels in wine depend on the type of grape varieties and wine-making technology, and, like anthocyanins, are much more abundant in red wines, in particular in aged wines, compared to white ones.
In addition, as previously said, together with anthocyanins, condensed tannins are important in determining some organoleptic properties of the wine.

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Polyphenols of grapes and wine: flavonols

They are present in a large variety of fruit and vegetables, even if in low concentrations.
They are the third most abundant group of flavonoids in grapes, after proanthocyanidins and catechins.
They are mainly present in the outer epidermis of the berry skin, where they play a role both in providing protection against UV-A and UV-B radiations and in copigmentation together with anthocyanins.
Flavanol synthesis begins in the sprout; the highest concentration is reached a few weeks after veraison, then it decreases as the berry increases in size.
Their total amount is very variable, with the red varieties often richer than the white ones.
In grapes, they are present as 3-glucosides and their composition depends on the type of grapes and cultivar:

  • the derivatives of quercetin, kaempferol and isorhamnetin are found in white grapes;
  • the derivatives of myricetin, laricitrin and syringetin are found, together with the previous ones, only in red grapes, due to the lack of expression in white grapes of the gene coding for flavonoid-3′,5′-hydroxylase.
Polyphenols in Grapes
Fig. 5 – Quercetin-3-glucoside

In general, the 3-glucosides and 3-glucuronides of quercetin are the major flavonols in most of the grape varieties. Conversely, quercetin-3-rhamnoside and quercetin aglycone are the major flavonols in muscadine grapes.
In wine and grape juice, unlike grapes, they are also found as aglycones, as a result of the acid hydrolysis that occurs during processing and storage. They are present in wine in a variable amount, and the major molecules are the glycosides of quercetin and myricetin, which alone represent 20-50% of the total flavonols in red wine.

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Polyphenols in grapes and wine: hydroxycinnamates

Polyphenols in Grapes
Fig. 6 – Ferulic Acid

Hydroxycinnamic acids are the main class of non-flavonoid polyphenols in grapes and the major polyphenols in white wine.
The most important are p-coumaric, caffeic, sinapic, and ferulic acids, present in wine as esters with tartaric acid.
They have antioxidant activity and in some white varieties of Vitis vinifera, together with flavonols, are the polyphenols mainly responsible for absorbing UV radiation in the berry.

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Polyphenols in grapes and wine: stilbenes

Polyphenols in Grapes
Fig. 7 – trans-Resveratrol

They are phytoalexins which are produced in low concentrations only by a few edible species, including grapevine (on the contrary, flavonoids are present in all higher plants).
Together with the other polyphenols in grapes and wine, also stilbenes, particularly resveratrol, have been associated with health benefits resulting from the consumption of wine.
Their content increases from the veraison to the ripening of the berry, and is influenced by the type of cultivar, climate, wine-making technology, and fungal pressure.
The main stilbenes present in grapes and wine are:

  • cis- and trans-resveratrol (3,5,4′-trihydroxystilbene);
  • piceid or resveratrol-3-glucopyranoside and astringin or 3′-hydroxy-trans-piceid;
  • piceatannol;
  • dimers and oligomers of resveratrol, called viniferins, of which the most important are:

α-viniferin, a trimer;
β-viniferin, a cyclic tetramer;
γ-viniferin, a highly polymerized oligomer;
ε-viniferin, a cyclic dimer.

In grapes, other glycosylated and isomeric forms of resveratrol and piceatannol, such as resveratroloside, hopeaphenol, or resveratrol di- and tri-glucoside derivatives, have been found in trace amounts.
Glycosylation of stilbenes is important for the modulation of antifungal activity, protection from oxidative degradation, and storage of the wine.
The synthesis of dimers and oligomers of resveratrol, both in grapes and wine, represents a defense mechanism against exogenous attacks or, on the contrary, the result of the action of extracellular enzymes released from pathogens in an attempt to eliminate undesirable compounds.

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Polyphenols in grapes and wine: hydroxybenzoates

Polyphenols in Grapes
Fig. 8 – Gallic Acid

The hydroxybenzoic acid derivatives are a minor component in grapes and wine.
In grapes, gentisic, gallic, p-hydroxybenzoic and protocatechuic acids are the main ones.
Unlike hydroxycinnamates, which are present in wine as esters with tartaric acid, they are found in their free form.
Together with flavonols, proanthocyanidins, catechins, and hydroxycinnamates they are among the responsible of astringency of wine.

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References

Andersen Ø.M., Markham K.R. Flavonoids: chemistry, biochemistry, and applications. CRC Press Taylor & Francis Group, 2006

Basli A, Soulet S., Chaher N., Mérillon J.M., Chibane M., Monti J.P.,1 and Richard T. Wine polyphenols: potential agents in neuroprotection. Oxid Med Cell Longev 2012. doi:10.1155/2012/805762

de la Rosa L.A., Alvarez-Parrilla E., Gonzàlez-Aguilar G.A. Fruit and vegetable phytochemicals: chemistry, nutritional value, and stability. 1th Edition. Wiley J. & Sons, Inc., Publication, 2010

Flamini R., Mattivi F.,  De Rosso M., Arapitsas P. and Bavaresco L. Advanced knowledge of three important classes of grape phenolics: anthocyanins, stilbenes and flavonols. Int J Mol Sci 2013;14:19651-19669. doi:10.3390/ijms141019651

Georgiev V., Ananga A. and Tsolova V. Recent advances and uses of grape flavonoids as nutraceuticals. Nutrients 2014;6: 391-415. doi:10.3390/nu6010391

Guilford J.M. and Pezzuto J.M. Wine and health: a review. Am J Enol Vitic 2011;62(4):471-486. doi:10.5344/ajev.2011.11013

He S., Sun C. and Pan Y. Red wine polyphenols for cancer prevention. Int J Mol Sci 2008;9:842-853. doi:10.3390/ijms9050842

Xia E-Q., Deng G-F., Guo Y-J. and Li H-B. Biological activities of polyphenols from grapes. Int J Mol Sci 2010;11-622-646. doi:10.3390/ijms11020622

Waterhouse A.L. Wine phenolics. Ann N Y Acad Sci 2002;957:21-36. doi:10.1111/j.1749-6632.2002.tb02903.x

Weight loss and green tea: myth and legend

Green tea: a fat burning food for weight loss?

In the phase of weight loss, as during weight maintenance, it is important to maintain as constant as possible the daily energy expenditure.
Indeed, daily caloric consumption usually decreases during weight loss.
Since the 90s of last century, it has been proposed that green tea, thanks to  its content of caffeine and catechins, particularly epigallocatechin gallate (EGCG), which are also present in oolong tea and white tea, could be of help for:

  • maintaining , or even increasing, the daily energy expenditure;
  • increasing fat oxidation, thus acting as a fat-burning food.
Weight Loss and Green Tea
Fig. 1 – Waist Circumference

Therefore, it was attributed to green tea the ability to cause a fat loss, and so to be of help for overweight or obese adults in achieving the ideal weight.
In addition to these potential lipolytic and thermogenic effects, catechins and caffeine may be useful by acting on other targets, such as the intestinal absorption of fat and the energy intake, probably through their impact on the gut microbiota and gene expression.
Therefore, products for weight loss and weight maintenance based on green tea extracts have been marketed. It should be noted that these products contain catechins and caffeine in amount much greater than the classic drink.

How much truth is there in green tea “fat burning” properties?

The issue seems to have been resolved by a careful meta-analysis of 15 studies on weight loss and intake of these “fat burning” products.
Eight of the 15 analyzed studies were conducted in Japan, and the rest outside of Japan, for a total number of 1945 subjects, which were followed for a period of between 12 and 13 weeks.
The study showed that the consumption of green tea-based products induces, in overweight and obese adults, a weight loss that is:

  • not statistically significant;
  • very small;
  • probably not clinically important.

These “fat burning” products have not proved to be useful not even in weight maintenance.
Thus, on the basis of scientific evidence, green tea does not seem to be helpful in fat loss nor in weight maintenance.
There are no magic bullets: the only way to lose weight (body fat) and avoid future increases is to control your daily calorie intake and take part in physical activity on a regular basis.

References

Hursel R. and Westerterp-Plantenga M.S. Catechin- and caffeine-rich teas for control of body weight in humans. Am J Clin Nutr 2013;98:1682S-1693S [Abstract]

Hursel R., Viechtbauer W. and Westerterp-Plantenga M.S. The effects of green tea on weight loss and weight maintenance: a meta-analysis. Int J Obesity 2009;33:956-961 [Full text]

Jurgens T.M., Whelan A.M., Killian L., Doucette S., Kirk S., Foy E. Green tea for weight loss and weight maintenance in overweight or obese adults. Editorial group: Cochrane Metabolic and Endocrine Disorders Group. 2012:12 Art. No.: CD008650 [Abstract]

Black tea: definition, processing and polyphenols

What is black tea?

Black tea, like the other types of tea, is an infusion of processed leaves of Camellia sinensis, the tea plant, a shrub that belongs to the Theaceae family.
Black tea, a type of fully fermented tea, is the most consumed tea worldwide, accounting for about 78% of the consumed tea. It is preferred by Western populations, while the favorite tea in Asia, particularly in Japan and China, is green tea.

“Tea is drunk to forget the din of the world.”
T’ien Yiheng

Processing of black tea

The processing of the leaves of Camellia sinensins, that leads to the production of black tea, proceeds through three main steps:

  • withering or drying;
  • rolling;
  • oxidation

The last step, oxidation, gives black tea the specific organoleptic characteristics and composition in polyphenols, that are extremely different from those of green tea (green tea undergoes very slight oxidative processes during processing).

Withering or drying

Black Tea: Withering or Drying  of Tea Leaves
Fig. 1 – Withering or Drying of Tea Leaves

The withering or drying step is the first, and most basic process during processing of black tea. In this step, water in the leaves is removed (about 75% of the leaf’s weight is made up of water), thus determining the concentration of the sap of the leaf itself. The withering also makes the next step easier.
Withering can be achieved in three different ways:

  • exposing leaves to sunlight, that is, sun withering;
  • heating in an appropriate manner the rooms where the leaves are placed;
  • using machines that artificially ventilate the leaves.

Rolling

The rolling step follows the withering of the leaves. It breaks the leaf tissue, facilitating the outflow of lymph; thus, it promotes the subsequent enzymatic oxidation of polyphenols. This step is essential for the creation of the aroma, color and flavor of black tea.

Oxidation

The oxidation, also improperly called fermentation, is the last stage of black tea processing, and is crucial in determining the quality of the tea. In this step, the enzymatic oxidation of about 90–95 % of the polyphenols occurs, accompanied by other changes that make the green tea leaves into red color.
Temperature (typically 25°C), pH, relative humidity (95% or more), ventilation, and duration are crucial factors too.

Black tea polyphenols

During the oxidation step, the main compounds that undergo oxidation processes, both enzymatic, by polyphenol oxidase, and chemical, by the action of atmospheric oxygen, are:

  • monomeric catechins and gallate catechins;
  • to a lesser extent, the glycosides of catechins, especially myricetin;
  • but also not flavonoids compounds, such as teogallin (ester of gallic acid).

Therefore, throughout the process, a reduction in the concentration of monomeric catechins, characteristics of fresh leaves of Camellia sinensis and green tea, occurs, with the formation of complex polyphenols, such as:

  • thearubigins, red-brown or dark-brown in color;
  • theaflavins and theaflavic acids, red-orange in color.

Thearubigins, polymers of catechins not yet well characterized, are the major polyphenols in black tea, accounting for about 20% of extracted solids. In addition to the reddish color, thearubigins contribute the richness in taste, the so-called “body” to black tea.
Theaflavins, dimers of catechins much better characterized than thearubigins, account for about 3-5% of the solids in black tea infusion. Theaflavins contribute the astringent and brisk taste, as well as the red-orange color of the beverage.
The main theaflavins are:

  • theaflavin digallate;
  • theaflavin-3-gallate;
  • theaflavin-3′-gallate.

Black tea benefits and oxidized polyphenols

Although this type of tea is still able to improve health, oxidative processes suffered from the leaves during the processing attenuate health benefits of black tea, which are instead reported after intake of green tea (particularly, the benefits of green tea are ascribed to its content of catechins, such as EGCG, epicatechin and epicatechin gallate).

Black tea’s caffeine content does not vary significantly.

References

Asil M.H., Rabiei B., Ansari R.H. Optimal fermentation time and temperature to improve biochemical composition and sensory characteristics of black tea. Aust J Crop Sci 2012;6(3):550-8 [PDF]

Kuhnert N. Unraveling the structure of the black tea thearubigins. Arch Biochem Biophys 2010;501(1):37-51 [Abstract]

Li S., Lo C-Y., Pan M-H., Lai C-S. and Ho C-T. Black tea: chemical analysis and stability. Food Funct 2013;4:10-18 [Abstract]

Menet M-C., Sang S., Yang C.S., Ho C-T., and Rosen R.T. Analysis of theaflavins and thearubigins from black tea extract by MALDI-TOF mass spectrometry. J Agric Food Chem 2004;52:2455-61 [Abstract]

Sharma V.K., Bhattacharya A., Kumar A. and Sharma H.K. Health benefits of tea consumption. Trop J Pharm Res 2007;6(3):785-792 [Abstract]

Green tea: definition, processing, properties, polyphenols

What is green tea?

Green tea is an infusion of processed leaves of tea plant, Camellia sinensis, a member of the Theaceae family.
It is the most consumed beverages in Asia, particularly in China and Japan.
Western populations consume black tea more frequently than green tea. However, in recent years, thanks to its health benefits, it has been gaining their attention.
Currently, it accounts for 20% of the tea consumed worldwide.

“You can never get a cup of tea large enough or a book long enough to suit me.”C.S. Lewis

Processing and properties of green tea

Green Tea
Fig. 1 – Camellia sinensis

As all other types of tea, it is produced from fresh leaves of Camellia sinensis.
The peculiar properties of the beverage depend on the type of processing that the leaves undergo. In fact, they are processed in such a way as to minimize both enzymatic and chemical oxidation processes of the substances contained in them, in particular catechins.
Therefore, among the different types of tea, it undergoes the lowest degree of oxidation during processing.
At the end of the processing, tea leaves retain their green color, thanks to the little chemical modifications/oxidations they have undergone. The infusion shows off a yellow-gold color.
Finally, the processing of tea leaves ensures that green tea flavor is more delicate and lighter than black tea.

The three main steps in the processing of green tea

After harvesting, tea leaves are exposed to the sun for 2-3 hours and withered/dried; then, the real processing starts.
It consists of three main steps: heat treatment, rolling and drying.

Heat treatment

Heat treatment, short and gentle, is the crucial step for the quality and properties of the beverage.
It occurs with steam (the traditional Japanese method) or by dry cooking in hot pans (a large wok, the traditional Chinese method). Heat treatment has the purpose of:

  • inactivate the enzymes present in the tissues of the leaves, thus stopping enzymatic oxidation processes, particularly of polyphenols;
  • eliminate the grassy smell in order to stand out tea flavor;
  • evaporate part of the water present in the fresh leaf (water constitutes about 75% of the weight of the leaf), making it softer, so as to make the next step easier.

Rolling

The rolling step follows the heat treatment of the leaves; this step has the purpose of:

  • facilitate the next stage of drying;
  • destroy the tissues of the leaves in order to favor, later, the release of aromas, thus improving the quality of the product.

Drying

The drying is the last step, which also leads to the production of new compounds and improves the appearance of the product.

Green tea polyphenols

Gree Tea
Fig. 2 – EGCG

All types of tea are rich in polyphenols, compounds that are also present in fruits, vegetables, extra virgin olive oil, and red wine.
Fresh tea leaves are rich in water-soluble polyphenols, especially catechins (or flavanols) and glycosylated catechins (both belonging to the class of flavonoids), molecules which are believed to be the responsibles of the benefits of green tea.
The major catechins in green tea are epigallocatechin-3-gallate (EGCG), epigallocatechin, epicatechin-3-gallate, epicatechin, epicatechin, but also catechin, gallocatechin, catechin gallate, and gallocatechin gallate are present, even if in lower amount. These polyphenols account for 30%-42% of the dry leaf weight (but only 3%–10% of the solid content of black tea).
Green tea caffeine accounts for 1,5-4,5% of the dry leaf weight.

How to maximize the absorption of green tea catechins

In vitro studies have shown the high antioxidant power of catechins, greater than that of vitamin C and vitamin E. In vitro, EGCG is generally considered the most biologically active catechin.
In vivo studies and several epidemiologic studies have shown the possible preventive effects of green tea catechins, especially EGCG, in preventing the development of:

  • cardiovascular disease, such as hypertension and stroke;
  • some cancers, such as lung cancer (but not among smokers) and oral and digestive tract cancers.

For these reasons, it is essential to maximize the intestinal absorption of catechins.
Catechins are stable in acidic environment, but not in non-acidic environment, as in the small intestine; also for this reason, after digestion, less than 20% of the total remains.
Studies with models of the digestive tract of rat and man, that simulate digestion in stomach and small intestine, have shown that the addition of citrus juice or vitamin C to green tea significantly increases the absorption of catechins.
Among tested citrus juices, lemon juice is the best, followed by orange, lime and grapefruit juices. Citrus juices seem to have a stabilizing effect on catechins that goes beyond what would be predicted solely based on their ascorbic acid content.

References

Clifford M.N., van der Hooft J.J.J., and Crozier A. Human studies on the absorption, distribution, metabolism, and excretion of tea polyphenols. Am J Clin Nutr 2013;98:1619S-1630S [Abstract]

Dwyer J.T. and Peterson J. Tea and flavonoids: where we are, where to go next. Am J Clin Nutr 2013;98:1611S-1618S [Abstract]

Green R.J., Murphy A.S., Schulz B., Watkins B.A. and Ferruzzi M.G. Common tea formulations modulate in vitro digestive recovery of green tea catechins. Mol Nutr Food Res 2007;51(9):1152-1162 [Abstract]

Huang W-Y., Lin Y-R., Ho R-F., Liu H-Y., and Lin Y-S. Effects of water solutions on extracting green tea leaves. ScientificWorldJournal 2013;Article ID 368350 [Abstract]

Sharma V.K., Bhattacharya A., Kumar A. and Sharma H.K. Health benefits of tea consumption. Trop J Pharm Res 2007;6(3):785-792 [Abstract]

Anthocyanins: foods, absorption, metabolism

Anthocyanin rich foods

Anthocyanin
Fig. 1 – Red Cherries

Together with catechins and proanthocyanidins, anthocyanins and their oxidation products are the most abundant flavonoids in the human diet.
They are found in:

  • certain varieties of grains, such as some types of pigmented rice (e.g. black rice) and maize (purple corn);
  • in certain varieties of root and leafy vegetables such as aubergine, red cabbage, red onions and radishes, beans;
  • but especially in red fruits.

They are also present in red wine; as the wine ages, they are transformed into various complex molecules.
Anthocyanin content in vegetables and fruits is generally proportional to their color: it increases during maturation, and it reaches values up to 4 g/kg fresh weight (FW) in cranberries and black currants.
These polyphenols are found primarily in the skin, except for some red fruits, such as cherries and red berries (e.g. strawberries), in which they are present both in the skin and flesh.
Glycosides of cyanidin are the most common anthocyanins in foods.

Anthocyanins in fruits

  • Berries are the main source of anthocyanins, with values ranging between 67 and 950 mg/100 g FW.
  • Other fruits, such as red grapes, cherries and plums, have content ranging between 2 and 150 mg/100 g FW.
  • Finally, in fruits such as nectarines, peaches, and some types of apples and pears, anthocyanins are poorly present, with a content of less than 10 mg/100 g FW.

Cranberries, besides their very high content of anthocyanins, are one of the rare food that contain glycosides of the six most commonly anthocyanidins present in foods: pelargonidin, delphinidin, cyanidin, petunidin, peonidin, and malvidin. The main anthocyanins are the 3-O-arabinosides and 3-O-galactosides of peonidin and cyanidin. A total of 13 anthocyanins have been detected, mainly 3-O-monoglycosides.

Intestinal absorption of anthocyanins

Until recently, it was believed that anthocyanins, together with proanthocyanidins and gallic acid ester derivatives of catechins, were the least well-absorbed polyphenols, with a time of appearance in the plasma consistent with the absorption in the stomach and small intestine. Indeed, some studies have shown that their bioavailability has been underestimated since, probably, all of their metabolites have not been yet identified.
In this regard, it should be underlined that only a small part of the food anthocyanins is absorbed in their glycated forms or as hydrolysis products in which the sugar moiety has been removed. Therefore, a large amount of these ingested polyphenols enters the colon, where they can also suffer methylation, sulphatation, glucuronidation and oxidation reactions.

Anthocyanins and colonic microbiota

Few studies have examined the metabolism of anthocyanins by the colonic microbiota.
Within two hours, it seems that all the anthocyanins lose their sugar moieties, thus producing anthocyanidins.
Anthocyanidins are chemically unstable in the neutral pH of the colon. They can be metabolized by colonic microbiota or chemically degraded producing a set of new molecules that have not yet fully identified, but which include phenolic acids such as gallic acid, syringic acid, protocatechuic acid, vanillic acid and phloroglucinol (1,3,5-trihydroxybenzene). These molecules, thanks to their higher microbial and chemical stability, might be the main responsible for the antioxidant activities and the other physiological effects that have been observed in vivo and attributed to anthocyanins.

References

de la Rosa L.A., Alvarez-Parrilla E., Gonzàlez-Aguilar G.A. Fruit and vegetable phytochemicals: chemistry, nutritional value, and stability. 1th Edition. Wiley J. & Sons, Inc., Publication, 2010

de Pascual-Teresa S., Moreno D.A. and García-Viguera C. Flavanols and anthocyanins in cardiovascular health: a review of current evidence. Int J Mol Sci 2010;11:1679-1703 [Abstract]

Escribano-Bailòn M.T., Santos-Buelga C., Rivas-Gonzalo J.C. Anthocyanins in cereals. J Chromatogr A 2004:1054;129-141 [Abstract]

Han X., Shen T. and Lou H. Dietary polyphenols and their biological significance. Int J Mol Sci 2007;9:950-988 [Abstract]

Manach C., Scalbert A., Morand C., Rémésy C., and Jime´nez L. Polyphenols: food sources and bioavailability. Am J Clin Nutr 2004;79(5):727-47 [Abstract]

Tsao R. Chemistry and biochemistry of dietary polyphenols. Nutrients 2010;2:1231-1246 [Abstract]

Tea polyphenols: bioactive compounds from leaves of tea plant

Tea polyphenols: from the leaf to the cup

Tea Polyphenols
Fig. 1 – Camellia sinensis

The leaves of the tea plant, Camellia sinensis, and tea are rich in bioactive compounds.
More than 4000 molecules have been found in the beverage.
Approximately one third of these compounds are polyphenols, the most important molecules in determining nutritional value and health benefits of the beverage.

Tea is a cup of life.” Anonymus author

Tea polyphenols are mostly flavonoids, such as catechins in green tea (e.g. EGCG), and thearubigins and theaflavins in black tea.
Other bioactive compounds present in tea are:

  • alkaloids, such as caffeine, theophylline and theobromine;
  • amino acids, and among them, theanine (r-glutamylethylamide), that is also a brain neurotransmitter and one of the most important amino acids in green tea;
  • proteins;
  • carbohydrates;
  • chlorophyll;
  • volatile organic molecules, that is, compounds that easily produce vapors and contribute to the odor of the beverage;
  • fluoride, aluminum and trace elements.

These molecules provide the nutritional value of the tea, affecting human health in many ways. Their composition is highly influenced by processing of tea leaves.

Biological activities of polyphenols

Polyphenols, both in vivo and in vitro, have a broad spectrum of biological activities such as:

  • antioxidant properties;
  • reduction of various types of tumors;
  • inhibition of inflammation;
  • protective effects against hyperlipidemia and diabetes.

Therefore, they have a protective role against the development of many diseases.
Thanks to the abundance of tea polyphenols, there has been a growing interest in recent years about the possible preventive effects of beverage against several diseases, particularly cardiovascular disease, for example in the development and progression of atherosclerosis.

Mechanisms of action of tea polyphenols

Currently, there is limited information on how tea polyphenols exert their effects at cellular level.
It seems, at least in vitro, that catechins in green tea, and theaflavins and thearubigins in black tea are the bioactive compounds responsible for the physiological effects and health benefits of tea.
And among the observed mechanisms by which tea polyphenols act at the cellular level, in addition to the antioxidant effect, it has been observed, as a consequence of polyphenol binding to specific receptors on the cell membrane, changes in the activity of various protein kinases, and growth and transcriptional factors.
Moreover, it seems that these molecules, or at least EGCG, may enter the cell and directly interact with their intracellular specific targets.

References

Dwyer J.T. and Peterson J. Tea and flavonoids: where we are, where to go next. Am J Clin Nutr 2013;98:1611S-1618S [Abstract]

Grassi D., Desideri G., Di Giosia P., De Feo M., Fellini E., Cheli P., Ferri L., and Ferri C. Tea, flavonoids, and cardiovascular health: endothelial protection. Am J Clin Nutr 2013;98:1660S-1666S [Abstract]

Lambert J.D. Does tea prevent cancer? Evidence from laboratory and human intervention studies. Am J Clin Nutr 2013;98:1667S-1675S [Abstract]

Lenore Arab L., Khan F., and Lam H. Tea consumption and cardiovascular disease risk. Am J Clin Nutr 2013;98:1651S-1659S [Abstract]

Lorenz M. Cellular targets for the beneficial actions of tea polyphenols. Am J Clin Nutr 2013;98:1642S-1650S [Abstract]

Sharma V.K., Bhattacharya A., Kumar A. and Sharma H.K. Health benefits of tea consumption. Trop J Pharm Res 2007;6(3):785-792 [Abstract]

Yuan J-M. Cancer prevention by green tea: evidence from epidemiologic studies. Am J Clin Nutr 2013;98:1676S-1681S [Abstract]

Isoflavones: definition, structure and soy

What are isoflavones?

Isoflavones are colorless polyphenols belonging to the class of flavonoids.
Unlike the majority of the other flavonoids, they have a restricted taxonomic distribution, being present almost exclusively in the Leguminosae or Fabaceae plant family, mainly in soy.
Since legumes, soy in primis, are a major part of the diet in many cultures, these flavonoids may have a great impact on human health.
They are also present in beans and broad beans, but in much lower concentrations than those found in soy and soy products.
Also red clover or meadow clover (Trifolium pratense), another member of Leguminosae family, is a good source.
Currently, they are not found in fruits and vegetables.

Together with phenolic acids, such as caffeic acid and gallic acid, and quercetin glycosides, they are the most well-absorbed polyphenols, followed by flavanones and catechins (but not gallocatechins).

In plants, some isoflavones have antimicrobial activity and are synthesized in response to attacks by bacteria or fungi; thus they act as phytoalexins.

Chemical structure of isoflavones

Isoflavones
Fig. 1 – Isoflavone Skeleton

While most flavonoids have B ring attached to position 2 of C ring, isoflavones have B ring attached to position 3 of C ring.
Even if they are not steroids, they have structural similarities to estrogens, particularly estradiol. This confers them pseudohormonal properties, such as the ability to bind estrogen receptors; therefore, they are classified as phytoestrogens or plant estrogens. The benefits often ascribed to soy and soy products (e.g. tofu) are believed to result from the ability of isoflavones to act as estrogen mimics .
It should be underlined that the binding to estrogen receptors seems to lose strength with time, therefore their potential efficacy should not be overestimated.
In foods, they are present in four forms:

  • aglycone;
  • 7-O-glucoside;
  • 6′-O-acetyl-7-O-glucoside;
  • 6′-O-malonyl-7-O-glucoside.

Soy isoflavones: genistein, daidzein and glycitein

Isoflavones
Fig. 2 – Isoflavones

Soy and soy products, such as soy milk, tofu, tempeh and miso, are the main source of isoflavones in the human diet.
The isoflavone content of soy and soy products varies greatly as a function of growing conditions, geographic zone, and processing; for example, in soy it ranges between 580 and 3800mg/kg fresh weight, while in soy milk it range between 30 and 175 mg/L. The most abundant isoflavones in soy and soy products are genistein, daidzein and glycitein, generally present in a concentration ratio of 1:1:0,2.; biochanin A and formononetin are other isoflavones present in less concentrations.
The 6′-O-malonyl derivatives have a bitter, unpleasant, and astringent taste; therefore they give a bad flavor to the food in which they are contained. However, being sensitive to temperature, they are often hydrolyzed to glycosides during processing, such as the production of soy milk.
The fermentation processes needed for the preparation of certain foods, such as tempeh and miso, determines in turn the hydrolysis of glycosides to aglycones, i.e. the sugar-free molecule.
Isoflavone glycosides present in soy and soy products can also be deglycosylated by β-glucosidases in the small intestine.
The aglycones are very resistant to heat.
Although many compounds present in the diet are converted by intestinal bacteria to less active molecules, other compounds are converted to molecules with increased biological activity. This is the case of isoflavones, but also of prenylflavonoids from hops (Humulus lupulus), and lignans, that are other phytoestrogens.

Soy isoflavones and menopause

Vasomotor symptoms, such as night sweats and hot flashes, and bone loss are very common in perimenopause, also called menopausal transition, and menopause. Hormone replacement therapy (HRT) has proved to be a highly effective treatment for the prevention of menopausal bone loss and vasomotor symptoms.
The use of alternative therapies based on phytoestrogens is increased as a result of the publication of the “Women’s Health Initiative” study, that suggests that hormone replacement therapy could lead to more risks than benefits, in particular an increased risk of developing some chronic diseases.
Soy isoflavones are among the most used phytoestrogens by menopausal women, often taken in the form of isoflavone fortified foods or isoflavone supplements.
However, many studies have highlighted the lack of efficacy of soy isoflavones, and red clover isoflavones, even in large doses, in the prevention of vasomotor symptoms (hot flushes and night sweats) and bone loss during menopause.

References

de la Rosa L.A., Alvarez-Parrilla E., Gonzàlez-Aguilar G.A. Fruit and vegetable phytochemicals: chemistry, nutritional value, and stability. 1th Edition. Wiley J. & Sons, Inc., Publication, 2010

Han X., Shen T. and Lou H. Dietary polyphenols and their biological significance. Int J Mol Sci 2007;9:950-988 [Abstract]

Lethaby A., Marjoribanks J., Kronenberg F., Roberts H., Eden J., Brown J. Phytoestrogens for menopausal vasomotor symptom. Cochrane Database of Systematic Reviews 2013, Issue 12. Art. No.: CD001395 [Abstract]

Manach C., Scalbert A., Morand C., Rémésy C., and Jime´nez L. Polyphenols: food sources and bioavailability. Am J Clin Nutr 2004;79(5):727-47 [Abstract]

Tsao R. Chemistry and biochemistry of dietary polyphenols. Nutrients 2010;2:1231-1246 [Abstract]

Green tea benefits for health

Benefits of green tea: science and myths

Green Tea Benefits
Fig. 1 – Green Tea Benefits

Tea drinking, particularly green tea, has always been associated, at least in East Asia cultures (mainly in China and Japan) with health benefits. Only recently, the scientific community has begun to study the health benefits of tea consumption, recognizing its preventive value in many diseases.

Green tea benefits in preventing cancer

Several epidemiological and laboratory studies have shown encouraging results with respect to possible preventive role of tea, particularly green tea and its catechins, a subgroup of flavonoids (the most abundant polyphenols in human diet) against the development of some cancers like:

  • oral and digestive tract cancers;
  • lung cancer among those who have never smoked, not among smokers.

Tea polyphenols, the most active of which is epigallocatechin-3-gallate (EGCG), seem to act not only as antioxidants, but also as molecules that, directly, may influence gene expression and diverse metabolic pathways.

Green tea benefits in cardiovascular disease

Cardiovascular disease is the main cause of deaths worldwide, particularly in low- and middle-income countries, with an estimate of about 17 million deaths in 2008 that will increase up to 23.3 million by 2030.
Daily tea consumption, especially green tea, seems to be associated with a reduced risk of developing cardiovascular disease, such as hypertension and stroke.
Among the proposed mechanisms, the improved bioactivity of the endothelium-derived vasodilator nitric oxide (NO), due to the action of tea polyphenols that enhance nitric oxide synthesis, and/or decrease superoxide-mediated nitric oxide breakdown seem to be important.

Drinking a daily cup of tea will surely starve the apothecary.” Chinese proverb

Green tea benefits and antioxidant properties

Tea polyphenols may act, in vitro, as free radical scavengers.
Since radical damage plays a pivotal role in the development of many diseases such as atherosclerosis, rheumatoid arthritis, cancer, or in ischemia-reoxygenation injury, tea polyphenols, particularly green tea catechins, may have a preventive role.

Green tea benefits in weight loss and weight maintenance

Green tea, but also oolong tea, that is, catechins and caffeine rich teas, has a potential thermogenic effect. This has made them a potential tool for:

  • weight loss, by increasing energy expenditure and fat oxidation;
  • weight maintenance, ensuring a high energy expenditure during the maintenance of weight loss.

Indeed, it has been shown that green tea and green tea extracts are not an aid in weight loss and weight maintenance, since:

  • they are not able to induce a significant weight loss in overweight and obese adults;
  • they are not helpful in the maintenance of weight loss.

Green tea benefits in preventing dental decay

Animal and in vitro studies have shown that tea, and in particular its polyphenols, seems to possess:

  • antibacterial properties against pathogenic action of cariogenic bacteria, as Streptococcus mutans, particularly green tea EGCG;
  • inhibitory action on salivary and bacterial amylase (it seems that black tea thearubigins and theaflavins are more effective than green tea catechins);
  • it is able to inhibit acid production in the oral cavity.

All these properties make green tea and black tea, beverages with potential anticariogenic activity.

References

Tea: cultivation, processing and preparation

Tea: form bush to cup for your health

Tea is an aromatic infusion extracted from the dried leaves of Camellia sinensis, a member of the Theaceae family.
Tea is a beverage with very ancient origins, dating back to almost 4000 years ago, and it is one of the most consumed beverage worldwide, particularly in Asia, with an estimated per capita consumption of approximately 0.12 L/d.
Owing to its high consumption, even small effects on person’s health could have large effects on public health.

Cultivation of Camellia sinensis, the tea plant

Tea Fields
Fig. 1 – Tea Fields

Camellia sinensis is an evergreen plant, native to South, East, and Southeast Asia, which is currently cultivated in at least 30 countries, mainly in tropical or sub-tropical climates, even if some varieties grow in Cornwall, in Europe, and Washington State, in the USA.
In nature, if left undisturbed, Camellia sinensis can grow up to 15-20 meters (49-65 ft), while in plantations it is generally pruned to height less than a meter and a half, that is, like a small tree or bush, to facilitate cultivation and harvesting of the leaves.
It can also be cultivated in mountain, up to 1500-2000 meters (4900-6550 ft) above sea level. Many of the high-quality teas are produced from mountain crops, as the plant grows more slowly acquiring a better flavor.
Currently, the two most used varieties, of the four ones recognized, are:

  • Camellia sinensis var. sinensis, native to China;
  • Camellia sinensis var. assamica, native to India.

Tea is liquid wisdom.” Anonymus author

Processing of tea leaves

All the types of teas commercially available are produced from fresh leaves of the plant. During harvesting, young leaves are generally picked, as the older ones are considered to be inferior in quality.
The differences between the types of teas, e.g. green tea, oolong tea and black tea, depend on how Camellia sinensis leaves are processed after harvesting, since processing may cause a different degrees of oxidation of the substances present, in particular of catechins, a flavonoid subgroup, and the main responsibles of the benefits of green tea.
The organoleptic characteristics of the different types of tea are influenced, in addition to the processing of the leaves, even from the cultivar, the characteristics of the soil where the plant grown up, the methods of cultivation, the altitude, the climate, and the time of year in which the harvest of the leaves occurs.

How to prepare a perfect cup of tea

  • Due to the sensitiveness of dried leaves, it is good to store the packaging in cool dry place, free of fragrances that may alter its aroma.
  • Use fresh water and warm it to a temperature of 95-100°C for black tea, and about 90°C for green tea.
  • In order not to alter tea flavor, it is advisable to use a ceramic or porcelain teapot, avoiding those of steel. For teapot washing, avoid detergents, preferring water plus baking soda.
  • To prevent sudden changes in water temperature during the infusion, it is advisable to preheat the teapot pouring a bit of boiling water. Then, emptied the pot, add hot water (about 200-250 mL/filter).
  • How many filters/g of leaves to use? Typically, a filter (about 1.5-2 g) per person, or a teaspoon of loose tea leaves per person.
    If you prepare the beverage for some people, you add a filter/teaspoon more than the number of persons.
  • The infusion time should not exceed 10 minutes in order to avoid the development of bitter flavors; it should be 3-4 minutes for black tea, and 2-3 minutes for green tea.
    If you are using filters, you should remove them at the end of the infusion time.
    Approximately 30% of the material present in the leaves is extracted in the water.

Now, it’s time to enjoy your tea.

References

Flavonols: definition, structure, food sources

What are flavonols?

Flavonols are polyphenols belonging to the class of flavonoids.
They are colorless molecules that accumulate mainly in the outer and aerial tissues, therefore skin and leaves, of fruit and vegetables, since their biosynthesis is stimulated by light. They are virtually absent in the flesh.

They are the most common flavonoids in fruit and vegetables, where they are generally present in relatively low concentrations.
Due to their widespread in nature and human diet, they should be taken into consideration when the positive effect on health associated with fruit and vegetable consumption is examined. Their effect is probably related to their ability to:

  • act as antioxidants;
  • act as anti-inflammatory agents;
  • act as anticancer factors;
  • regulate different cellular signaling pathways; an example is the action of quercetin, the most widespread flavonols, on the oxidative stress-induced MAPK activities.

Chemical structure of flavonols

Basic Skeleton of Flavanols
Fig. 1 – 3-hydroxyflavone

Chemically, these molecules differ from many other flavonoids since 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 from which, however, they differ in the presence of a hydroxyl group at the position 3. Therefore, flavonol skeleton is a 3-hydroxyflavone.
The 3-hydroxyl group can link a sugar, that is, it can be glycosylated.
Like many other flavonoids, most of them is found in fruit and vegetables, and in plant-derived foods, in glycosylated form. The sugar associated with flavonols is often glucose or rhamnose, but other sugars may also be involved, such as:

  • galactose;
  • arabinose;
  • xylose;
  • glucuronic acid.
Flavonols
Fig. 2 – Flavonols

Flavonol are mainly represented by glycosides of:

  • quercetin;
  • kaempferol;
  • myricetin;
  • isorhamnetin.

The most ubiquitous compounds are glycosylated derivatives of quercetin and kaempferol; in nature, these two molecules have respectively about 280 and 350 different glycosidic combinations.
Finally, it should be underlined that sugar moiety influences flavonol bioavailability.

Foods rich in flavonols

The major sources in human diet are:

  • fruit;
  • vegetables;
  • beverages such as red wine and tea.

In human diet, the richest source are capers, which contain up to 490 mg/100 g fresh weight (FW), but they are also abundant in onions, leeks, broccoli, curly kale, berries (e.g. blueberries), grapes and some herbs and spices, for example dill weed (Anethum graveolens). In these sources, their content ranges between 10 and 100 mg/100 g FW.
Even cocoa, tea, both green and black ones, and red wine are good sources of flavonols. In wine, together with other polyphenols such as catechins, proanthocyanidins and low molecular weight polyphenols, they contribute to the astringency of the beverage.

The main flavonols in foods

The main flavonols in foods, listed in decreasing order of abundance, are quercetin, kaempferol, myricetin and ishoramnetin.

Quercetin

The richest sources of quercetin are capers, followed by onions, asparagus, lettuce and berries; in many other fruit and vegetables, it is present in smaller amounts, between 0.1 and 5 mg/100 g FW.
This flavonol is also present in cocoa and it could be one of its main protective agents against LDL oxidation.
Together with isoflavones, quercetin glycosides are the most well-absorbed polyphenols, followed by flavanones and catechins (on the contrary, gallic acid derivatives of catechins are among the least well absorbed polyphenols, together with anthocyanins and proanthocyanidins).

Kaempferol

Typical dietary sources of kaempferol include vegetables, such as spinach, kale and endive, with concentrations between 0.1 and 27 mg/100 g FW, and some spices such as chives, fennel and tarragon, with concentrations between 6.5 and 19 mg/100 g FW.
Fruit is a poor source of the molecule, with content down to 0.1 mg/100 g FW.

Myricetin

Myricetin is the third most abundant flavonol. It is found in some spices, such as oregano, parsley, and fennel, with concentrations between 2 and 20 mg/100 g FW, but also in tea, 0.5-1.6 mg/100 ml, and red wine, 0-9.7 mg/100 ml.
In fruit, it is only found in high concentrations in berries, while in most other fruit and vegetables it is present in a content of less than 0.2 mg/100 g FW.

Isorhamnetin

A fourth flavonol, less abundant than the previous ones, is isorhamnetin. It is only present in some foods such as some spices: chives, 5.0-8.5 mg/100 g FW, fennel, 9.3 mg/100 g FW, tarragon, 5 mg/100 g FW.
In fruit and vegetables it is only present in almonds, with a concentration between 1.2 and 10.3 mg/100 g FW, pears and onions.

References

de la Rosa L.A., Alvarez-Parrilla E., Gonzàlez-Aguilar G.A. Fruit and vegetable phytochemicals: chemistry, nutritional value, and stability. 1th Edition. Wiley J. & Sons, Inc., Publication, 2010

Han X., Shen T. and Lou H. Dietary polyphenols and their biological significance. Int J Mol Sci 2007;9:950-988 [Abstract]

Manach C., Scalbert A., Morand C., Rémésy C., and Jime´nez L. Polyphenols: food sources and bioavailability. Am J Clin Nutr 2004;79(5):727-47 [Abstract]

Tsao R. Chemistry and biochemistry of dietary polyphenols. Nutrients 2010;2:1231-1246 [Abstract]