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Food Research International 37 (2004) 233–245

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Catechins and procyanidins in Mediterranean diets


Cyril Auger a, Najim Al-Awwadi b, Aurelie Bornet a, Jean-Max Rouanet c,
Francis Gasc a, Gerard Cros b, Pierre-Louis Teissedre a,*
a
Oenologie Department, Faculty of Pharmacy, University Montpellier 1, 15, Avenue Charles Flahault, B.P. 14491,
Montpellier Cedex 5 34093, France
b
Pharmacology Department, Faculty of Pharmacy, University Montpellier 1, 15, Avenue Charles Flahault,
B.P. 14491, Montpellier Cedex 5 34093, France
c
Nutrition Department, University Montpellier 2, Montpellier 34095, France
Received 20 August 2003; accepted 19 November 2003

Abstract

A great many epidemiological studies indicate that a diet rich in flavonoids from vegetables and fruits intake appear to be in-
versely related to coronary heart disease (CHD) and cancers mortality. Regular moderate consumption of wine can contribute to
this phenomenon. Flavonoids in wine and food have been shown to be antioxidant and anti-aggregant in vitro and could indeed help
protect against coronary disease. Thus, flavonoids may partly explain the protective effects of the Mediterranean diet, rich in
vegetable, fruit and wine against CHD or cancers.
The first step in evaluating this hypothesis is to create a catechins–food composition table. Fruits and vegetables as: plum, apples,
strawberries, cherry and others berries, lentil, chocolate, beans, contains good amount of catechins and procyanidins with a
maximum observed until 49 mg/100 g for plum to 157 mg/100 g for broad bean. Grapes contains catechins and procyanidins in seeds
and skins. For red wine, the consumption of 180 mL for which the mean catechin and procyanidin concentration is 557.9 mg/L gives
a mean daily intake of 100.4 mg of these compounds. This reasoning applied to each type of wine (red, white and rose) for regular
(daily), moderate (180 mL) consumption gives estimations of catechin and procyanidin intake of 100.4 mg for red wines, 2.7 mg for
white wines and 3.1 mg for rose wines. Green and black tea provide also catechins, respectively, until 42 and 25 mg/100 mL.
A second step consists to determine to what extent each of these foodstuffs contribute to antioxidant flavonoids in the blood.
Which type of diet contributes most to plasma concentration of catechin and procyanidins metabolites. If catechins monomers: (+)-
catechin and ())-epicatechin are absorbed with formation of specific metabolites; the metabolism of procyanidins is actually unclear
and more research is needed concerning this class of flavonoids.
If, as reported, antioxidant flavonoids, especially catechin and procyanidins, have a significant protective effect against CHD red
wine and some fruits and vegetables, owing to their flavonoids, may provide the highest protection among all the Mediterranean
foodstuffs which have been tested.
Ó 2004 Elsevier Ltd. All rights reserved.

1. Introduction suggest that they might prevent chronic diseases in hu-


mans. One of the key elements of Mediterranean diet is
Catechins and procyanidins, two of the major groups the use of wine, usually taken with foods. Besides the
of flavonoids, are bioactive compounds present in a evidence from human experience and ancient medicine,
variety of plant foods and beverages. Experimental data modern experimental data support the notion that the
most striking effect of wine in protecting against car-
Abbreviations: C, catechin; EC, epicatechin; B1, B2, B3, B4, B5 and diovascular disease involves the reduction of oxidative
B7, procyanidins dimers; C1, procyanidins trimer; GC, gallocatechin; damage to plasma lipoproteins. This oxidative damage
GC–C, gallocatechin–catechin; EC–EC–C, epicatechin–epicatechin– is thought to be mediated by eating foods contain-
catechin; EGC, epigallocatechin; ECG, epicatechingallate and EGCG, ing oxidized lipids. In fact, eating a meal containing
epigallocatechingallate.
*
Corresponding author. Tel.: +33-04-67-54-8674; fax: +33-04-67-54-
oxidized lipids increases the plasma level of lipid
8686. hydroperoxides and increases the susceptibility to
E-mail address: teissed@univ-montp1.fr (P.-L. Teissedre). oxidation of LDL (Ursini & Sevanian, 2002).

0963-9969/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.foodres.2003.11.008
234 C. Auger et al. / Food Research International 37 (2004) 233–245

However, the epidemiological studies in this field are moderate amounts of wine, more so than other Medi-
based on data concerning the flavonoid composition of terranean countries. Analyses of the dietary pattern of
foods, and the contribution of a regular, moderate the diet of Crete shows a number of protective sub-
consumption of foods and beverages remains difficult to stances, such as selenium, glutathione, a balanced ratio
quantify. In this study, we have tried to obtain an esti- of (n  6):(n  3) essential fatty acids (EFA), high
mation of catechins and procyanidins contents in foods amounts of fiber, antioxidants (especially resveratrol
and beverages entering in mediterranean diet. We also from wine and polyphenols from olive oil), vitamins E
discuss the metabolism of these molecules and the and C, some of which have been shown to be associated
appearance of metabolites in the plasma. with lower risk of cancer, including cancer of the breast.
Recently, it was found that the inhabitants of Greece
and Southern Italy had a very low incidence of coronary
2. Mediterranean diet artery disease and that, among other components, their
diets were very rich in oleic acid, the main constituent of
‘‘The traditional mediterranean diet is based on a the olive oil, making up about 29% of their daily caloric
daily consumption of: fruits, vegetables, beans, other intake. It was observed for in vitro models of early
legumes and nuts, breads, pasta, rice, couscous, polenta, atherogenesis based on cytokine-stimulated cultured
bulgur, other grains and potatoes, olive oil, cheese and endothelial cells, that the incorporation of oleic acid in
yogurt. A few times per week people can have fish, total cell lipids is accompanied by decreased expression
poultry, eggs and sweets. Red meat can be consumed of a number of major pro-inflammatory proteins, such
only a few time per month. Usually people drink wine as endothelial leukocyte adhesion molecules. Oleic acid
daily in moderation and maintain a regular physical was purposed for a direct vascular atheroprotective ef-
activity. fect, and it was suggested that it may be possible to
This diet is poor in saturated fat but rich in fibers. Its prevent atherosclerosis by modulating the vascular re-
high fat acids monounsaturated rate is mainly provided sponse to classical triggers (high levels of cholesterol and
by olive oil’’ (WHO, 1994). During a median of 44 the advanced glycation end-products of diabetes,
months of a follow-up population-based, prospective Massaro & De Caterina, 2002).
investigation involving 22,043 adults in Greece, there An Identification and quantitation study of major
were 275 deaths. A higher degree of adherence to the carotenoids in selected components of the Mediterra-
Mediterranean diet was associated with a reduction in nean diet (green leafy vegetables, figs and olive oil)
total mortality (adjusted hazard ratio for death associ- commonly eaten by Greek migrants to Melbourne, a
ated with a two-point increment in the Mediterranean- population group maintaining a traditional dietary
diet score, 0.75 [95% confidence interval, 0.64–0.87]). An regimen, and who exhibit relatively high circulating ca-
inverse association with greater adherence to this diet rotenoid concentrations and low cardiovascular disease
was evident for both death due to coronary heart disease mortality, was realized. Prior to analyses, foods were
(adjusted hazard ratio, 0.67 [95% confidence interval, selected on the basis that they are commonly eaten by
0.47–0.94]) and death due to cancer (adjusted hazard Greek migrants but not by Anglo-Celtic persons and the
ratio, 0.76 [95% confidence interval, 0.59–0.98]). A dietary intake was assessed for both populations. Wild
greater adherence to the traditional Mediterranean diet green vegetables contained high concentrations of lutein
is associated with a significant reduction in total mor- (sow thistle > amaranth > purslane > dandelion) and
tality (Trichopoulou, Costacou, Bamia, & Trichopou- b-carotene (sow thistle > amaranth > purslane ¼ dande-
los, 2003). lion). Sow thistle and amaranth contained lutein (15 and
For Simopoulos (2001), the term ‘‘Mediterranean 13 mg/100 g, respectively) and b-carotene (3.3 and 4.0
diet’’, implying that all Mediterranean people have the mg/100 g, respectively) at concentrations greater than
same diet, is a misnomer. The countries around the that seen in the commercially available species of chic-
Mediterranean basin have different diets, religions and ory and endive. Figs contained all major carotenoids
cultures. Their diets differ in the amount of total fat, appearing in plasma, albeit at low concentrations. Extra
olive oil, type of meat and wine intake; milk vs. cheese; virgin cold-pressed olive oil contained substantial
fruits and vegetables; and the rates of coronary heart quantities of lutein and b-carotene, but the more-refined
disease and cancer, with the lower death rates and Ôextra lightÕ olive oil did not. In these investigations,
longer life expectancy occurring in Greece. Extensive these components of the traditional Mediterranean diet
studies on the traditional diet of Greece (the diet before contribute to the higher circulating concentrations
1960) indicate that the dietary pattern of Greeks consists of carotenoids in Greek migrants compared to Anglo-
of a high intake of fruits, vegetables (particularly wild Celtic Australians (Su, Rowley, Itsiopoulos, & OÕDea,
plants), nuts and cereals mostly in the form of sour- 2002).
dough bread rather than pasta; more olive oil and olives; In another study (Tokudome et al., 2000), morbidity
less milk but more cheese; more fish; less meat; and and mortality statistics, including incidences of fat-
C. Auger et al. / Food Research International 37 (2004) 233–245 235

related cancers (FRCs), and dietary intake and sources than in other industrialised countries, even though the
of fats and oils were compared for Japanese, Mediter- consumption of saturated fats in France is much the
ranean and American people. Incidences of FRCs, ex- same and blood cholesterol levels are generally higher
cept for steeply increasing colon cancer, have remained (World Health Organisation (1989)). Furthermore,
low in Japan. Similarly, Mediterranean people enjoy other factors associated with risk of coronary artery
relatively low risks of FRCs compared with American disease, such as arterial blood pressure, body weight and
people. The low risks of FRCs in Japanese could be smoking, are no lower in France than in the other
explained by limited intake of fats and oils as a whole, countries. This is the French Paradox.
and a low ratio of n  6 polyunsaturated fatty acids Renaud and de Lorgeril used WHO and OECD data
(PUFAs) versus n  3 PUFAs through consumption of to study which food parameters could be correlated with
the latter from marine foods. They also frequently cardiovascular disease (CVD) mortality levels. Among
consume vegetables and fruit, and dietary fiber. Medi- the numerous different foods, only the consumption of
terranean people moderately consume fats and oils from dairy fats (between 1980 and 1985) showed positive
a large amount of olive oil, containing not only oleic correlation with CVD mortality (1987 levels), but this
acid but also polyphenols (including flavonoids), a- correlation was highly significant (r ¼ 0:73, P < 0:001).
tocopherol and carotenoids (including carotene), which However, although the consumption of dairy fats is the
are antioxidants and anti-carcinogenic as in red wine, same in France as in the UK, Australia and Germany,
vegetables (including herbs) and fruit. The diet also mortality from coronary artery disease is lower in
features medium intake of fish and shellfish along with France. Using multifactor analysis, Renaud and de
cereals/pasta/bread. From the standpoint of intake of Lorgeril revealed that in 17 wine-drinking countries, the
total fat, the low risks of FRCs in Japanese seem only dietary factor correlating significantly with coro-
‘‘plausible’’, while the low risks in Mediterranean people nary artery disease mortality, apart from dairy fats, was
may be termed ‘‘paradoxical.’’ The authors suggest that wine (r ¼ 0:87, P < 0:001). Moreover, wine consump-
a limited consumption of fats and oils, moderate intakes tion had a negative coefficient indicating a protective
of marine foods, and vegetables and fruit, in line with effect. It was thus realised that the French case was not
a modest intake of energy may be advocated for paradoxical when wine consumption was taken into
promoting health, prolonging life and prevention of account. In this study, the protection afforded by wine
lifestyle-related diseases including FRCs. consumption was also detected in Switzerland and other
In their conclusion study Trichopoulou and Vasi- industrialised countries. From this, attention turned to
lopoulou (2000) indicate that a diet that adheres to the the non-alcoholic fractions of wine.
principles of the traditional Mediterranean is associated Wine, particularly red wine, is an important source of
with longer survival. The Greek version of the Medi- polyphenols which are capable of inhibiting the pro-
terranean diet is dominated by the consumption of olive cesses behind coronary artery disease. This hypothesis is
oil and by high consumption of vegetables and fruits. supported by the results of recent epidemiological
Antioxidants are a common element in these foods and studies concerning foodstuff polyphenols, particularly
an antioxidant action provides a plausible explanation flavonoids. A correlation was also noticed between in-
for the apparent benefits. These authors suggest that creasing levels of flavonoid ingestion from fruit and
wild edible greens frequently eaten in rural Greece in the vegetables and reduction in coronary artery disease. The
form of salads and pies contain very high quantities of studies carried out by Hertog, Feskens, Hollman, Ka-
flavonoids that could be considerably higher than those tan, and Kromhout (1993), Knekt, Jarvinen, Reunanen,
found in red wine or black tea. While there is no direct and Maatela (1996) and Rimm, Katan, Ascherio,
evidence that these antioxidants are central to the ben- Stampfer, and Willett (1996) reveal the benefits of a diet
efits of the Mediterranean Diet, indirect evidence from rich in flavonoids. Recently, the total dietary intakes of
epidemiological data and the increasing understanding 10,054 men and women during the year preceding the
of their mechanisms of action suggest that antioxidants baseline examination were determined with a dietary
may play a major role. history method. Flavonoid intakes were estimated,
However, in one of the best known studies, Renaud mainly on the basis of the flavonoid concentrations in
and de Lorgeril (1992) suggest an explanation of the Finnish foods. The persons with higher quercetin in-
phenomenon particularly favourable to the French takes had lower mortality from ischemic heart disease.
population with regard to cardiovascular disease, The incidence of cerebrovascular disease was lower at
known as the ‘‘French Paradox’’, which was first de- higher kaempferol, naringenin and hesperetin intakes.
scribed in 1987 by Richard (Richard (1987)). The results Men with higher quercetin intakes had a lower lung
of the Monica program (1989), a worldwide CAD sur- cancer incidence, and men with higher myricetin intakes
veillance system organised by the World Health Orga- had a lower prostate cancer risk. Asthma incidence was
nization (WHO), confirm that mortality levels provoked lower at higher quercetin, naringenin and hesperetin
by coronary artery disease are much lower in France intakes. A trend toward a reduction in risk of type 2
236 C. Auger et al. / Food Research International 37 (2004) 233–245

diabetes was associated with higher quercetin and my- 2.2 h, and therefore plasma concentrations reflect short-
ricetin intakes. The risk of some chronic diseases may be term intake. The relative urinary excretion varied de-
lower at higher dietary flavonoid intakes (Knekt et al., pending on the flavanone source and dose and was
2002). 30.2  25.5% and 1.1  0.8% for naringenin from
Despite emerging evidence of the role of flavonoids in grapefruit juice and orange juice, respectively, and
CVD prevention, the association remains unclear in 5.3  3.1% for hesperetin from orange juice. The con-
some studies. Recently, it was examined whether flavo- siderable difference in the relative urinary excretion of
noids and selected flavonols and flavones or their food naringenin from the two juices was most likely caused
sources are associated with CVD risk. Women (n ¼ 38 by dose-dependent renal clearance rather than differ-
445) free of CVD and cancer participated in a pro- ences in bioavailability (as indicated by the similar Cmax -
spective study with a mean follow-up of 6.9 year. On the to-dose ratios). The authors concluded that because of
basis of a food-frequency questionnaire, total flavonoids the relatively high concentrations of flavanones in
and selected flavonols and flavones were categorized plasma after ingestion of orange juice or grapefruit juice,
into quintiles, and food sources were categorized into considerable health effects could ensue in individuals
four groups. Relative risks were computed for important consuming them regularly.
vascular events (519 events; excluding revasculariza- In another work, De Vries, Hollman, Van Amer-
tions) and CVD (729 events), including myocardial in- sfoort, Olthof, and Katan (2001) studied the bioavail-
farction, stroke, revascularization and CVD death. The ability of flavonols (especially quercetin) from red wine,
mean flavonoid intake was 24.6  18.5 mg/day, primar- in comparison with that from the major dietary sources,
ily as quercetin (70.2%). For both CVD and important yellow onions and black tea. Twelve healthy men con-
vascular events, no significant linear trend was observed sumed 750 mL red wine, 50 g fried onions or 375 mL of
across quintiles of flavonoid intake (P ¼ 0:63 and 0.80, black tea, each for 4 days in random order. These sup-
respectively). No individual flavonol or flavone was as- plements provided similar amounts of quercetin (14–16
sociated with CVD. Broccoli and apple consumption mg). There was a washout period of 3 days between each
were associated with nonsignificant reductions in CVD period of supplementation. The plasma quercetin con-
risk: 25–30% and 13–22%, respectively. A small pro- centration after the consumption of wine was lower than
portion of women (n ¼ 1185) consuming P 4 cups (946 that after onions (P < 0:05) and not different from that
mL) tea/day had a reduction in the risk of important after tea. Urinary excretion of quercetin after wine did
vascular events but with a nonsignificant linear trend not differ from that after onions and was higher than
(P ¼ 0:07). In their conclusions Sesso, Gaziano, Liu, that after tea (P < 0:05). It was concluded that flavonols
and Buring (2003) indicate that flavonoid intake was not from red wine are absorbed. However, because one glass
strongly associated with a reduced risk of CVD. The of red wine provides fewer available flavonols than one
nonsignificant inverse associations for broccoli, apples portion of onions or one glass of tea, red wine appears
and tea with CVD were not mediated by flavonoids and to be a poorer source of flavonols than these other two
warrant further study. sources.
Erlund, Meririnne, Alfthan, and Aro (2001) studied In parallel to these epidemiological and bioavail-
intake of orange juice and grapefruit juice containing ability studies, biochemical data on wine flavonoids,
high amounts of flavanones naringenin and hesperetin particularly catechins and procyanidins should be con-
able to exhibitestrogenic, anti-carcinogenic and antiox- sidered. Differences in the ability of wine, and other al-
idative properties. Plasma kinetics and urinary excretion coholic beverages, to protect against cardiovascular
of flavanones (naringenin and hesperetin) were devel- disease could be explained by the specific action of
oped. Healthy volunteers ingested orange juice (five catechins and procyanidins and their metabolites from
women and three men) or grapefruit juice (two women wine, which are practically absent from other alcoholic
and three men) once (8 mL/kg). Eleven blood samples beverages.
and urine were collected between 0 and 24 h after juice
administration. Flavanones were analyzed by HPLC
with electrochemical detection. Naringenin and hes- 3. Biochemical properties of catechins and procyanidins
peretin were bioavailable from the studied juices, but
interindividual variation in bioavailability was remark- 3.1. Structure of catechins and procyanidins
able. The resulting plasma concentrations were com-
paratively high, and the peak plasma concentrations (+)-Catechin and ())-epicatechin are the basic units
(Cmax ) were 0.6  0.4 lmol/L (means  SD) for na- of this group. The procyanidins are formed from the
ringenin from orange juice and 6.0  5.4 lmol/L for association of several of these monomeric units: 2–5
naringenin from grapefruit juice. The corresponding units for catechin oligomers, over 5 units for catechin
value for hesperetin from orange juice was 2.2  1.6 polymers (Fig. 1). The procyanidins differ in the position
lmol/L. The elimination half-lives were between 1.3 and and configuration of their monomeric linkages. The
C. Auger et al. / Food Research International 37 (2004) 233–245 237

(8)

(4)

(+)-Catechin (-)-Epicatechin

NAME STRUCTURE

Procyanidin B1 ( -)-epicatechin-(4-8)-(+)-catechin

Procyanidin B2 ( -)-epicatechin-(4-8)-(-)-epicatechin

Procyanidin B3 (+)-catechin-(4-8)-(+)-catechin

Procyanidin B4 (+)-catechin-(4-8)-(-)-epicatechin

Procyanidin C1 ( -)-epicatechin-(4-8)-(-)-epicatechin-(4-8)-(-)-epicatechin
Procyanidin C2 ( - )-epicatechin-(4-8)-(-)-epicatechin-(4-8)-(+)-catechin

Fig. 1. Catechins and Procyanidins structures.

structures of procyanidin dimers B1, B2, B3 and B4, and Catechins and procyanidins have been shown in vitro
trimers C1 and C2 are the best known. to be powerful inhibitors of LDL oxidation, more so
than a-tocopherol (Teissedre, Frankel, Waterhouse,
3.2. Antioxidant and anti-aggregant properties Peleg, & German, 1996). It was also demonstrated that
vitamins and especially flavonoids in common beverages
These molecules possess a structure that confers them are powerful in vitro antioxidants which enrich lower
with an antioxidant property which can inhibit the density lipoproteins and increase their oxidative resis-
processes leading in the long term to atherosclerosis and tance after ex vivo spiking in human plasma (Vinson
arterial thrombosis. et al., 1999). Catechins have been also shown to be in-
The flavonoids are the most lipophilic of the natural hibitors of platelet aggregation (Ruf et al., 1995) and in
antioxidants; but less so than a-tocopherol. The a- Russo, Tedesco, Russo, Russo, Venezia, and Cicala
tocopherol seems to be located in the lipid membrane (2001) red wine polyphenols may reduce platelet aggre-
within the phospholipid bilayer while the flavonoids are gability, and the effect of de-alcoholated red wine
probably mainly located at the polar surface of the bi- (DRW) and its phenolic fractions on rat platelet ag-
layer. The aqueous, i.e., transported in the plasma, free gregation and cyclic AMP (c-AMP) content was evalu-
radicals would therefore be captured more easily by the ates. DRW was fractionated into four classes of
flavonoids than by the less accessible a-tocopherol. phenolic compounds: phenolic acids (fraction 1),
Thus, the flavonoids could be concentrated near to procyanidins, catechins and monomeric anthocyanidins
the membranous surface of the low density lipoprotein (fraction 2), flavonols and resveratrol (fraction 3) and
(LDL) particles, ready to capture the oxygenated polymeric anthocyanidins (fraction 4). The effect of each
aqueous free radicals. They would in this way prevent fraction on ADP-induced rat platelet aggregation and c-
the consumption of lipophilic a-tocopherol and thus AMP content was compared with that of DRW and
delay oxidation of the lipids contained in the LDL. pure phenolic compounds (quercetin, catechin, resvera-
Moreover, if, as research suggests, the initiation phase trol and caffeic acid). DRW completely inhibited ADP-
and the propagation phase of lipid peroxidation take induced platelet aggregation. Fraction 2 also showed a
place, respectively, at the surface and the interior of the significant anti-aggregating activity, whereas the effects
membranes, then the flavonoids could well hinder the of fractions 3 and 4 and the pure phenolics were not
correct course of the reaction by limiting the initiation significant. A significant increase in platelet c-AMP
phase. content was observed after the addition of DRW and
238 C. Auger et al. / Food Research International 37 (2004) 233–245

fraction 2. These data indicate that DRW and its cate- (2002) study. Fasting venous blood samples were taken
chin–anthocyanidin fraction exert a significant effect on before and at the end of the supplementation period and
platelet aggregation in vitro, perhaps by enhancing after 7 days of wash-out. The total antioxidant activity
platelet c-AMP levels. and the plasma concentrations of a-tocopherol were not
Moreover, it has been shown that the consumption of modified. Conversely, the levels of a-tocopherol in red
wine by humans leads to an increase in the antioxidant blood cell membranes increased significantly from
capacity of plasma (Fuhrman, Lavy, & Aviram, 1995). 1.8  0.1 to 2.8  0.2 mg/g. Similarly, the lymphocyte
Other studies have been carried out on the antioxidant oxidized DNA [8-oxo-7,8-dihydro-20 -deoxyguanosine/
activity – through inhibition of copper-catalysed oxi- 20 -deoxyguanosine ratio] was reduced from 7.23  2.47
dation of human LDL – of a selection of Californian to 2.34  0.51, and the red blood cell membrane fatty
wines, made from cabernet-sauvignon, merlot, zinfan- acid composition shifted to a higher level of polyun-
del, petite syrah, pinot-noir, sauvignon blanc and char- saturated fatty acids. On the basis of these results, it may
donnay. The relative inhibition of LDL oxidation be suggested that dietary procyanidins exert their anti-
(calculated with respect to the total phenol concentra- oxidant protection in vivo by sparing liposoluble vita-
tion of each sample) varied from 46% to 100% for red min E and reducing DNA oxidative damage.
wines and from 3% to 6% for white wines (Frankel, Moreover, Giovannelli, Testa, De Filippo, Cheynier,
Waterhouse, & Teissedre, 1995). The antioxidant activ- Clifford, and Dolara (2000) reported in their study the
ity of wines made with long maceration times exclusively effect of an oral treatment with complex polyphenols
from Rh^ one valley syrah and grenache varieties was and tannins from red wine and tea on DNA oxidative
60% relative inhibition of LDL oxidation (Teissedre, damage in the rat colon mucosa. Isolated colonocytes
Waterhouse, & Frankel, 1995). were prepared from the colon mucosa of rats treated for
Comparison of these results with the different Cali- 10 days with either wine complex polyphenols (57.2 mg/
fornian red wines showed that the Rhodanian wines kg/day) or thearubigin (40 mg/kg/day) by oral gavage.
made from syrah and grenache gave values of relative Colonocyte oxidative DNA damage was analysed at the
inhibition of human LDL oxidation identical to those of single cell level using a modification of the comet assay
cabernet–sauvignon but less than those of petite syrah technique. The results show that wine complex po-
(80%) or merlot (74%). In contrast, the syrah wines lyphenols and tannins induce a significant decrease
produced with short extractions gave a low mean value ()62% for pyrimidine and )57% for purine oxidation) in
of relative inhibition (16%) which is nevertheless 4 times basal DNA oxidative damage in colon mucosal cells
higher than that obtained for Californian white wines without affecting the basal level of single-strand breaks.
(4.4%). It was deduced from this that each phenolic On the other hand, tea polyphenols, namely a crude
compound of wine could play a role in the protection extract of thearubigin, did not affect either strand breaks
against LDL oxidation. or pyrimidine oxidation in colon mucosal cells. These
In Brunet, Blade, Salvado, and Arola (2002) it was experiments are the first demonstration that dietary
also investigate that blood transport and identification polyphenols can modulate in vivo oxidative damage in
of principal plasma proteins in humans and rats bind to the gastrointestinal tract of rodents. These data support
monomeric catechin and procyanidins in red wine ex the hypothesis that dietary polyphenols might have both
vivo. After human and rat plasma and serum incubated a protective and a therapeutic potential in oxidative
with (+)-catechin and procyanidins from grape seed, the damage-related pathologies.
origin of red wine catechins, proteins were separated by All the properties and studies reported support the
SDS–PAGE and native–PAGE to determine which present hypotheses for explaining the reduced risk of
proteins bound to these compounds. The principal mortality from coronary artery disease in moderate and
protein that bound to (+)-catechin in each species was regular consumers of wine (in particular red wine).
sequenced. SDS–PAGE showed that (+)-catechin and Although metabolism of polyphenols compounds
procyanidins mainly bound to a protein of about remains elusive, enteric absorption occurs sufficiently to
80 kDa in rats and 35 kDa in humans. Their sequencing reduce plasma indices of oxidant status. The propensity
indicated that these proteins were apo A-I in humans of a flavonoid to inhibit free-radical-mediated events is
and transferrin in rats. The fact that red wine procy- governed by its chemical structure. Since these com-
anidins bind to both proteins suggests that they may pounds are based on the flavan nucleus, the number,
have a role in reverse cholesterol transport and in the positions and types of substitutions influence radical
oxidizing action of iron. scavenging and chelating activity. The diversity and
An evaluation of the effect of supplementation with multiple mechanisms of flavonoid action, together with
procyanidins from Vitis vinifera on markers of oxidative the numerous methods of initiation, detection and
stress was realizes for 10 healthy volunteers received a measurement of oxidative processes in vitro and in vivo
daily dose of 110 mg of procyanidins for 30 days in offer plausible explanations for existing discrepancies in
Simonetti, Ciappellano, Gardana, Bramati, and Pietta structure–activity relationships. Despite some inconsis-
C. Auger et al. / Food Research International 37 (2004) 233–245 239

tent lines of evidence, several structure–activity rela- Quince

tionships are well established in vitro. Multiple hydroxyl Pomegranate

groups confer upon the molecule substantial antioxi- Plum

dant, chelating and prooxidant activity. Methoxy Pineapple

Pear Conferencia
groups introduce unfavorable steric effects and increase Pear Blanquilla
lipophilicity and membrane partitioning. A double bond Peach

and carbonyl function in the heterocycle or polymeri- Medlar

zation of the nuclear structure increases activity by Kiwi

Table Grape white


affording a more stable flavonoid radical through con-
Table Grape red
jugation and electron delocalization (Heim, Tagliaferro, Custard apple
& Bobilya, 2002). For Miller and Ruiz Larrea (2002), Early fig

flavonoids as a group have been referred to as ‘‘semi- Chestnut

essential’’ dietary component due to their ability to Strawberry tree fruit

Strawberry
protect vitamins C and E from oxidation in the growing
Redcurrant
plant, during food storage, cooking, digestion and ab- Raspberry
sorption, and in the circulation and body tissues. Cherry

However, Flavonoids also show non antioxidant bio- Blueberry

logical effects such as enzyme inhibition and electron/ Blackberry

Banana
proton exchange. These authors indicated that high
Apricot
potency flavonoid supplementation could be potentially Apple Red Delicious

toxic, pro-oxidant or mutagenic. Also, the evidence Apple Reinette

suggests that individuals should rely on dietary sources Apple Granny Smith

of these substances trough a plant-based diet rather than Apple Golden

0 5 10 15 20 25 30 35 40 45 50
supplementation. Further investigation of the metabo-
lism of these phytochemicals is justified to extend Fig. 2. Catechins in fruits (content mg/100 g fresh weight).
structure–activity relationships to preventive and ther-
apeutic nutritional strategies.
Chikpea

Wheat Flour

Chocolate
4. Catechin and procyanidin levels in foods and beverages Bee polen

Broad bean

Detailed quantitative information on the procyanidin White bean

profiles present in many food products is lacking. The Pinto bean

Lentil
compositional data are important for the initial under- French bean

standing of which foods contribute most to the dietary Tomato

intake of procyanidins and may be used to compile a Pepper green

Pepper red
database necessary to infer epidemiological relation- 0 20 40 60 80 100 120 140 160
ships to health and disease. In an analytical study by
Hammerstone, Lazarus, and Schmitz (2000), the Fig. 3. Catechins levels in vegetables and other products (content
procyanidin content of red wine, chocolate, cranberry mg/100 g fresh weight).
juice and four varieties of apples has been determined.
On average, chocolate and apples contained the largest developed for the quantitative analysis of individual
procyanidin content per serving (164.7 and 147.1 mg, flavanols in food. This method was applied to flavanol
respectively) compared with red wine and cranberry determination in 56 different kinds of Spanish food
juice (22.0 and 31.9 mg, respectively). However, the products, including fruit, vegetables, legumes, beverages
procyanidin content varied greatly between apple sam- (cider, coffee, beer, tea and wine) and chocolate. The
ples (12.3–252.4 mg/serving) with the highest amounts determined compounds corresponded to the catechins
on average observed for the Red Delicious (207.7 mg/ and proanthocyanidin dimers and trimers usually pres-
serving) and Granny Smith (183.3 mg/serving) varieties ent in food and, therefore, they were representative of the
and the lowest amounts in the Golden Delicious (92.5 flavanols of low degree of polymerization consumed with
mg/serving) and McIntosh (105.0 mg/serving) varieties. the diet. Similar flavanol profiles were found in the dif-
In an important study by De Pascual-Teresa, Santos- ferent samples of a similar type of product, even though
Buelga, and Rivas-Gonzalo (2000) (Fig. 2 for fruits and important variations could exist in the concentrations of
Fig. 3 for vegetables and other products), an HPLC total and individual flavanols among them. This was
method, using detection after postcolumn derivatization attributed to factors such as sample origin, stage of
with p-dimethylaminocynnamaldehyde (DMACA), was ripeness, post-harvesting conservation and processing.
240 C. Auger et al. / Food Research International 37 (2004) 233–245

Total flavanol contents varied from nondetectable in revealed that this beverage contains high levels and that
most of the vegetables to 184 mg/100 g found in a sample the different wine-making techniques varieties and area
of broad bean. Other products contain: 7 mg/100 g of production are important factors (Archier, Cohen, &
chocolate and pinto bean, 3 mg/100 g for lentil. Sub- Roggero, 1992; Bourzeix, Weyland, & Heredia, 1986;
stantial amounts were also found in some fruits, such as Waterhouse & Teissedre, 1997). In a more recent study
plum 49 mg/100 g and apples from 10 to 43 mg/100 g, as of Carando and Teissedre (1999), the catechins and
well as in tea 25–43 mg/100 mL and red wine. Strawberry procyanidins content of wines (n ¼ 160) from all French
and others berries contains between 5 and 20 mg/100 g, regions made from diverse varieties and using varied
peach 8 mg/100 g and cherry 13 mg/100 g. Epicatechin vinification techniques – i.e., an analysis reflecting the
was the most abundant flavanol, followed by catechin great diversity of French wines was achieved with au-
and procyanidin B2. In general, catechins were found thentic standards extracted and certified by Teissedre
in all the flavanol-containing products, but the presence et al. (1996) with HPLC analytical conditions used by
of gallocatechins was only relevant in pomegranate, Lamuela-Raventos and Waterhouse (1994). The results
broad bean, lentil, grape, wine, beer and tea, and most of obtained (Table 2) were used to evaluate the catechin
the berries. Galloyled flavanols were only detected in and procyanidin intake from regular, moderate wine
strawberry, medlar, grape and tea. consumption.
Grapes used for winemaking contains levels of cate- Red wines had generally much higher levels of
chins reported by Bourzeix et al. in 1986 (Table 1). The phenolics than white wines. This difference is the result
average of total catechins was found of 377 mg/kg Fresh of different wine-making techniques. The catechins in
weight with a variability between 94 (carignane) to 1165 grapes, present mainly in the pips, diffuse into the must
mg/kg F.W (pinot-noir). The catechins average reparti- during the course of maceration. The maceration phase
tion in grapes was 65% in the seeds, 20% in stems and constitutes a fundamental difference in the vinification
14% in skins. Analytical studies on flavonoids in wine of red and white wine. It is essential for the production

Table 1
Catechins levels in grapes
Varieties Catechins (mg/kg) % in Stems % in Seeds % in Skins % in Pulp
Alicante-bouschet 551 15 64 10 11
Cabernet-sauvignon 344 10 83 7 T
Carignane 94 27 54 19 T
Cinsault 154 47 37 9 T
White grenache 144 17 51 32 T
Grenache-noir 173 25 64 11 T
Merlot 601 9 81 11 T
Mourvedre 171 25 58 17 T
Pinot-noir 1165 4 94 2 T
Colobel (hybride) 862 8 79 7 6
Average 377 20 65 14 1
T, traces.

Table 2
Mean concentrations of catechins in french wines
Compound Mean concentration (mg/L)
Red wines, n ¼ 95a White wines, n ¼ 57a Rose wines, n ¼ 8a
(+)-Catechin 114.5 (32.8–209.8)b 9.8 (4.4–13.6) 10.6 (4.7 –13.3)
())-Epicatechin 75.5 (22.1–130.4) 5.3 (2.7–8.5) 6.5 (2.7–9.5)
Procyanidin dimer B1 119.6 (21.4–215.6) NF NF
Procyanidin dimer B2 47.4 (18.3–93) NF NF
Procyanidin dimer B3 25.4 (7.8–39.1) NF NF
Procyanidin dimer B4 81.9 (20.2–107.2) NF NF
Procyanidin trimer C1 26.3 (8.6–38.5) NF NF
Procyanidin trimer C2 67.1 (26.7–79.3) NF NF
Total catechins 557.7 15.1 17.1
NF, not found.
a
Number of wines.
b
Minimum to maximum level.
C. Auger et al. / Food Research International 37 (2004) 233–245 241

60
sumption was 305 mL/person/day (Darret, Couzy,
Antoine, Magliola, & Mareschi, 1986). This level fell
50
sharply to 180 mL/person/day in 1995 (Boulet, Laporte,
Aigrin, & Lalanne, 1995). An estimation of the intake of
40
catechins and procyanidins was calculated from these
latest consumption figures and our own analytical results
30
on the catechin (monomers, dimers, trimers) content of
160 wines. Although the levels of these compounds vary
20
considerably from one wine to another, the regular
consumption of the different products available to the
10
consumer tends toward a mean value which we consid-
ered to be close to that calculated for the 160 wines.
0
For this reason, this estimation can only be consid-
Coffee Soluble Tea Black Tea Wine red Wine rosé Wine Beer ered for regular consumption of different wines over a
Cacao Green white
sufficiently long period of time (which remains to be
Fig. 4. Catechins levels in beverages (content mg/100 mL). determined statistically). The consumption of 180 mL of
red wine for which the mean catechin and procyanidin
concentration is 557.9 mg/L gives a mean daily intake of
of red wine and is deliberately avoided for the produc- 100.4 mg of these compounds. This reasoning applied to
tion of white, where rapid pressing separates the liquid each type of wine (red, white and rose) for regular
phase from the solid matter. (daily), moderate (180 mL) consumption gives estima-
Thus, the red wines studied had high overall levels of tions of catechin and procyanidin intake of 100.4 mg for
catechins (sum of monomers, procyanidin dimers and red wines, 2.7 mg for white wines and 3.1 mg for rose
trimers analysed) – 557.9 mg/L, but there were consid- wines. These results are in agreement with other results
erable differences between the red wines. Levels in the obtained by Teissedre and Landrault (2000) in function
white and rose wines were lower: 15.2 and 17.1 mg/L, of red varieties wineswith an average of catechin and
respectively. procyanidin daily intake of 50 mg/person for syrah to
All the compounds studied were present in each of 130 mg for egiodola.
the 95 red wines analysed. For the monomers, the mean
concentration (sum of (+)-catechin and ())-epicatechin)
was 190.2 mg/L. The quantity of procyanidin dimers 6. Fate of catechins and procyanidins in the plasma after
(sum of B1, B2, B3 and B4) was 274.3 mg/L and that of foods and beverages consumption
procyanidin trimers (sum of C1 and C2) was 93.4 mg/L.
The white wines (n ¼ 57) and rose wines (n ¼ 8) showed Although epidemiological studies note a correlation
low concentrations of monomers (15.1 and 17.1 mg/L, between the reduction of risk of coronary artery disease
respectively). The mean contents of catechin monomers, and the regular, moderate consumption of wine, no
procyanidin dimers and trimers and for each compound causal relationship has been demonstrated. The flavo-
is also indicated in Table 2. noids from foods and beverages constitute a consider-
The presence of dimers and trimers in the white and able LDL antioxidant and platelet anti-aggregant
rose wines could not be determined through direct in- potential, but it is difficult to know whether this po-
jection in HPLC since the levels of these compounds tential is slightly, partially or totally realised during
were at the limit of detection by UV. In Fig. 4 we metabolism. It would appear necessary, therefore, to
compare the levels of catechins and procyanidins from supply irrefutable biochemical proof of the envisaged
different kinds of beverages with results obtained by De protective mechanisms. Although compounds such as
Pascual-Teresa et al. (2000) and Carando and Teissedre (+)-catechin, ())-epicatechin, procyanidin dimers B1,
(1999) and it appears clearly that major sources are: red B2, B3, B4 and trimers C1, C2 inhibit LDL oxidation in
wine (55.7 mg/100 mL), green tea (42 mg/100 mL) and vitro (Teissedre et al., 1996), no account can be taken of
black tea ( 25 mg/100 mL). Beer, coffee and white wine the large variability in the composition of blood plasma
indicated the lowest levels. in order to verify whether these compounds or their
metabolites can be sufficiently active in vivo to afford
protection, even though epidemiological studies suggest
5. Estimation of catechin and procyanidin intake in that they do. Current research concerns the fate of these
moderate wine consumers in France compounds in human plasma after wine consumption.
The intestinal flora (which varies in function of the
Over the last few years, the consumption of wine in environment of the population groups) is likely to
France has fallen considerably. In 1986, the mean con- metabolise some of these compounds. The first step
242 C. Auger et al. / Food Research International 37 (2004) 233–245

consists of identifying the intact molecules and/or their randomized cross-over design with one-week intervals.
metabolites in the plasma. This analysis is very delicate Blood samples were drawn before and up to 8 h after tea
to carry out since these compounds have different sta- consumption. The consumption of green tea (0.9 g total
bilities depending on the physical and biological condi- catechins) or black tea (0.3 g total catechins) resulted in
tions. A method associates a simple, rapid phase of a rapid increase of catechin levels in blood with an av-
plasma sample preparation with a highly sensitive de- erage maximum change from baseline (CVM) of 0.46
tection method: fluorescence (Carando, Teissedre, & lmol/L (13%) after ingestion of green tea and 0.10 lmol/
Cabanis, 1998). This method has enabled us to identify L (13%) in case of black tea. These maximum changes
(+)-catechin in plasma and to quantify it for several were reached after (mean (SEM)) t ¼ 2:3 h (0.2) and
persons having consumed wine with their meal with a t ¼ 2:2 h (0.2) for green and black tea, respectively.
very large variability in plasma (+)-catechin concentra- Blood levels rapidly declined with an elimination rate
tions (260–810 ng/mL). It was found in Ruidavets, Te- (mean (CVM)) of t1=2 ¼ 4:8 h (5%) for green tea and
issedre, Carando, Ferrieres, and Cabanis (2000) that in t1=2 ¼ 6:9 h (8%) for black tea. Addition of semi-
182 subjects consuming Mediterranean foodstuffs, the skimmed milk to black tea (100 mL in 600 mL ) did not
highest concentration level of (+)-catechin in plasma significantly affect the blood catechin levels (areas under
was observed when wine, fruit and vegetable were con- the curves (mean CVM)) of 0.53 h lmol/L (11%) vs 0.60
sumed. Among these vegetal foodstuffs, red wine ap- h lmol/L (9%) for black tea and black tea with milk,
pears to be the most effective to produce this effect in a respectively. Catechins from green tea and black tea
sample of free-living population in the south of France. were rapidly absorbed and milk does not impair the
If as, reported, antioxidant flavonoids, especially cate- bioavailability of tea catechins.
chin and procyanidins, have a significant protective Warden, Smith, Beecher, Balentine, and Clevidence
effect against CHD red wine and some fruits and vege- (2001) reported clinical data demonstrating that bio-
tables, owing to their flavonoids, may provide the availability of the individual catechins and other poly-
highest protection among all the Mediterranean food- phenolic components of tea are limited. This study
stuffs which have been tested. assessed the apparent bioavailability of the prominent
As it has been indicated early (Das & Griffiths, 1969), catechins from black tea in humans drinking tea
the dependance of the bacteriological intestinal flora can throughout the day. After 5 days of consuming a low
contribute to several possible metabolites from pheno- flavonoid diet, subjects drank a black tea preparation
lics that can be formed and absorbedas phenolics acids containing 15.48, 36.54, 16.74 and 31.14 mg of ())-epi-
(free or as sulfate or glucuronides conjugates) or lac- gallocatechin (EGC), ())-epicatechin (EC), ())-epigal-
tones derivatives. locatechin gallate (EGCG) and ())-epicatechin gallate
Catechins monomers metabolisms studies from food (ECG), respectively, at four time points (0, 2, 4 and 6 h).
and beverages are in agreement. In Yang, Chen, Lee, Blood, urine and fecal specimens were collected over a
Balentine, Kuo, and Schantz (1998), human blood and 24- to 72-h period and catechins were quantified by
urina levels of catechins after decaffeinated green tea HPLC with coularray detection. Plasma concentrations
solids intake in water: 1.5, 3 and 4.5 g by human subjects of EGC, EC and EGCG increased significantly relative
were investigated and maximum plasma concentrations to baseline (P < 0:05). Plasma EGC, EC and EGCG
of 326 ng/mL of epigallocatechin-3-gallate, 550 ng/mL peaked after 5 h, whereas ECG peaked at 24 h. Urinary
of epigallocatechin and 190 ng/mL of epicatechin ap- excretion of EGC and EC, which peaked at 5 h, was
pears at 1.4 and 2.4 h. An excretion of epigallocatechin increased relative to baseline amounts (P < 0:05) and
and epicatechin in urina of 90% of the total amount fecal excretion of all four catechins was increased rela-
excreted within 8 h was also found. In another study by tive to baseline (P < 0:05). Approximately 1.68% of in-
Pietta, Simonetti, Gardana, Brusamolino, Morazzoni, gested catechins were present in the plasma, urine and
and Bombardelli (1998) catechin after green tea intake feces, and the apparent bioavailability of the gallated
by humans volunteers were detemined with a maximum catechins was lower than the nongallated forms. Thus,
plasma concentration of 2 lM. Urina at 6 or 48 h catechins were bioavailable. However, unless they are
contained catechin metabolites (total content 60 mg): rapidly metabolized or sequestered, the catechins ap-
hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, peared to be absorbed in amounts that were small rel-
3,methoxy-4-hydroxyhippuric acid and 3,methoxy-4- ative to intake.
hydroxybenzoic acid. (+)-Catechin metabolism following red wine intake
To assess the blood concentration of catechins fol- (120mL containing 34 mg of catechin/subject) was
lowing green or black tea ingestion and the effect of studied by Donovan, Bell, and Waterhouse (1999). A
addition of milk to black tea, Van Het Hof, Kivits, maximum plasma level of 80 nmol was found for cate-
Weststrate, and Tijburg (1998) gave 12 volunteers (seven chin at 1, 3 h, and 20 nmol for a metabolite: 30 -O-
females and five males) a single dose (3 g) of tea solids methylcatechin. The levels were found independant of
from green tea, black tea and black tea with milk in a ethanol presence but total catechin between individuals
C. Auger et al. / Food Research International 37 (2004) 233–245 243

varied from 50 to 176 nmol. In the case of chocolate, 0.213% GSE [0.082% procyanidins in the diet (w/w)] for
Wang et al. (2000) demonstrated that ())-epicatechin 27 days. The GSE significantly prevented and postponed
was present in human plasma following a consumption development of cataract formation by evaluation of slit
of 27, 53 or 80 g of chocolate (5.3 total procyanidin mg/ lamp observations of the rats eyes. Lens weight and
g) of which 1.3 mg was ())-epicatechin. A maximum malondialdehyde concentration in the lens and plasma
plasma average levels at 2 h for ())-epicatechin with: cholesteryl ester hydroperoxide (ChE-OOH) level in-
133, 258 and 355 nmol/L were found for the respec- duced by CuSO4 were significantly lower in the GSE
tive doses of chocolate consumption for 20 subjects. group compared with the control group. The rats were
Dose-dependant increases in plasma epicatechin were also fed for 14 days either the diet containing 0.085%
associated with increases in antioxidant capacity and procyanidin dimer to tetramer fraction (0.085% as the
reduction in lipid oxidation. procyanidins), the diet containing 0.090% procyanidin
Procyanidins metabolism is more controversial than pentamer to heptamer fraction (0.085% as the procy-
for catechins monomers. For example, Donovan, anidins), or the diet containing 0.093% procyanidin
Manach, Rios, Morand, Scalbert, and Remesy (2002) oligomers more than decamer fraction (0.085% as the
gave procyanidin B3 (20 mg) and grape seed extracts procyanidins). The ChE-OOH levels in the procyanidin
(200 or 400 mg) containing catechin, epicatechin and pentamer to heptamer and procyanidin oligomers more
procyanidins dimers B1, B2, B3 and B4 to rats in a than decamer groups were significantly lower than in the
single meal and realized after 3, 9 and 24 h an analysis of procyanidin dimer to tetramer group. These results
plasma and urine. Catechin and epicatechin were pres- suggested that procyanidins and their antioxidative
ent in free and conjugated forms in plasma (20 and 15 metabolites prevented the progression of cataract for-
lmol/L) and urine (30–45% excreted). But procyanidins mation by their antioxidative action. The larger molec-
were not detected in plasma and urine and were not ular procyanidins in the GSE might contribute to this
cleaved into bioavailable monomers. In another study anti-cataract activity.
by Spencer, Schroeter, Shenoy, Srai, Debnam, and Rice-
Evans (2001), epicatechin was found to be a primary
bioavailable form of procyanidin dimers B2 and B5
(extracted from cocoa powder) after transfer across the 7. Conclusions and prospects
small intestine. Dimers B2 and B5 (1%) were transferred
to the serosal part of enterocytes. The perfusion of di- This estimation of catechin and procyanidin intake
mers resulted in 95.8% of unmetabolised/unconjugated need to be investigate in function of nutrition type.
epicatechin monomer on the serosal side and 3.2% of Furthermore, it would be desirable to extend this esti-
methylated dimer was found. The methylation of dimer mation to the non-flavonoid components of foods and
was realized by catechol-O-methyltransferase (COMT). beverages. However, it will also be very important in the
Another investigation concerns procyanidin dimer B2 future to obtain data on the fate and bio-availability of
absorption (extracted from cocoa powder) by Baba, these compounds in the plasma. Catechins and procy-
Oakabe, Natsume, and Terao (2002). An oral adminis- anidins contribute to dietary intake of antioxidants. A
tration of dimer B2: 50 mg/kg to Sprague–Dawley male lot of various catechins and procyanidins can be found
rats was realized with collection of bloods samples at 30 in mediterranean diets. The richest products in catechins
min, 1, 2, 3 and 5 h, and urine from 0 to 18 h. Specific and procyanidins are: red wine, teas, fruits (as plum,
enzymes as sulfatase and b-glucuronidase were used to apples, strawberry, cherry and others berries, peach),
treat plasma and urine prior to extraction analysis to beans and grains (particularly broad bean, lentil and
research catechins and procyanidins. The use of HPLC- chocolate). Further research will focus on the identifi-
MS conducted to maximum peak levels of procyanidin cation and quantification of new procyanidins (trimers,
B2 (0.5 lM), epicatechin (0.2 lM) and 30 -O-methylepi- tetramers, pentamers, etc.) and their potential antioxi-
catechin (0.15 lM) found at 30 min in plasma. Identi- dant activity in foods and beverages. The maximum
fication by HPLC-MS permited to detect procyanidin intake of catechins and procyanidins is observed with
B2 (83 nmol/L), epicatechin (free 12.5 nmol/L or con- red wine around 100 mg/day/person. Catechins mono-
jugated 29.6 nmol/L) and 30 -O-methylepicatechin (free mers: (+)-catechin and ())-epicatechin are absorbed
12.8 nmol/L or conjugated 13.9 nmol/L) excreted in with formation of specific metabolites. Metabolism of
urine within 18 h. procyanidins is actually unclear and more research is
Recently Yamakoshi, Saito, Kataoka, and Tokutake needed concerning this class of flavonoids. Are procy-
(2002) observed the effect of procyanidins on cataract anidins directly absorbed, metabolised/conjugated or
formation. The anti-cataract activity of grape seed cleaved in monomers? All catechins, procyanidins and
extract (GSE, which contains 38.5% procyanidins) in metabolites absorbed can contribute to increased anti-
hereditary cataractous rats (ICR/f rats) was tested. The oxidant capacity of plasma. Their cardioprotective ef-
ICR/f rats were fed a standard diet containing 0 or fects stem from the ability to inhibit lipid peroxidation,
244 C. Auger et al. / Food Research International 37 (2004) 233–245

chelate redox-active metals and attenuate other pro- Giovannelli, L., Testa, G., De Filippo, C., Cheynier, V., Clifford,
cesses involving reactive oxygen species. M. N., & Dolara, P. (2000). Effect of complex polyphenols
and tannins from red wine on DNA oxidative damage of rat
colon mucosa in vivo. European Journal of Nutrition, 39, 207–
212.
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