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Polyphenols content in some Italian red wines of different geographical origins
ARTICLE IN PRESS
JOURNAL OF FOOD COMPOSITION AND ANALYSIS
Journal of Food Composition and Analysis 17 (2004) 613–618 www.elsevier.com/locate/jfca
Original Article
Polyphenols content in some Italian red wines of different geographical origins L. Gambelli*, G.P. Santaroni Istituto Nazionale di Ricerca per gli Alimenti e la Nutrizione, Via Ardeatina 546, 00178 Rome, Italy Received 25 November 2002; received in revised form 25 July 2003; accepted 29 September 2003
Abstract Some polyphenols were determined in 10 red wines of different geographical origins and from single and blended vineyards. The principal aim of this study was to verify the possibility of correlating the concentrating levels of these compounds to the geographical origin of wine and to use the properties of these compounds for wine qualification. An HPLC method was used to determine some flavonols (quercetin, myricetin, apigenin, kaempferol), some anthocyanins (malvidin, peonidin, petunidin, cyanidin, delphinidin), some phenolic acids (gallic, caffeic, caffeoyltartaric, p-coumaric, 2,5-di-S-glutationil-caftaric) and the trans-resveratrol. The results showed differences in the concentration levels of a single antioxidant compound ranging in mg/mL for flavonols from o0.2 (kaempferol) to 11.6 (quercetin), for anthocyanins from o0.4 (petunidin) to 139 (malvidin), for phenolic acids from 2.2 (2,5 di-S-glutationil-caftaric) to 90.5 (gallic) and for trans-resveratrol from 0.2 to 3.1. These differences are not related to the geographical origin of wines, but rather to either to ageing or vineyards. This kind of data could be useful for wine commercial qualification, as ‘‘nutritional information’’. r 2003 Elsevier Inc. All rights reserved. Keywords: Nutritional card; Polyphenols; Italian wines
1. Introduction Red wines include a number of polyphenolic constituents, such as monomeric flavonoids, anthocyanins, phenolic acids and polymeric tannins, that can help/affect human health. These compounds are characterized by antioxidant properties that play an inhibitory role at different stages of tumour development (Hertog et al., 1993). They are effective radical scavengers with respect to oxygen free radicals and lipid peroxidation (LDL) (Nardini et al., 1995). Some studies have shown epidemiological evidence that an increased dietary intake of natural polyphenols *Corresponding author. Tel.: +39-06-50-32-412; fax: +39-06-50-31-592. E-mail address: [email protected] (L. Gambelli). 0889-1575/$ - see front matter r 2003 Elsevier Inc. All rights reserved. doi:10.1016/j.jfca.2003.09.010
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reduces the coronary heart disease (CHD), artherosclerosis effect and platelet aggregation (Hollman et al., 1996). Also, they can inhibit and sometimes induce a large variety of mammalian enzyme systems. In France, CHD mortality is lower than in other industrialized countries, even if the dietary intake of saturated fat is higher. Regular consumption of red wine has been hypothesized to be the most likely cause for this phenomenon known as the French paradox (Renaud and Lorgeril, 1992). Polyphenolic compounds are widely distributed in vegetables. They are present in complex polymeric and glycosidic forms, that could not easily be degraded by digestive juices and so their absorption could be limited. In wine, during fermentation, these aggregates are broken down to monomeric forms. The alcohol content of 10% or more contained in most table wines gives stability to phenols present in bottled wines, allowing their absorption (Goldberg, 1995). These beneficial effects are important from a nutritional point of view and so it is necessary to find specific chemical parameters which could be used to develop a ‘‘nutritional card’’ of wine. In this study some polyphenols — flavonoids, anthocyanins, phenolic acids and resveratrol — were determined. These compounds could be key agents of the antioxidant action on the human metabolism pathway, the reason why we wanted to obtain indications to qualify the wine from a nutritional point of view. Also the environmental conditions (temperature, rainfall/humidity, latitude, height above sea level and geochemical characteristics) can affect the vine maturation and consequently the concentration of its antioxidant compounds. We have analysed wines from two Italian regions, Puglia and Molise, that have different environmental characteristics.
2. Materials and methods Ten southern Italian red wines from Puglia and Molise regions were analysed. Red wines of Puglia were: one Montepulciano/Troia (2000 year), one Montepulciano and one Primitivo/Tarantino (1999 year) and one Montepulciano, one Troia and one Montepulciano/ Troia (1998 year). Red wines of Molise were: one Montepulciano (2000 year), one Montepulciano/Aglianico (1999 year), one Montepulciano/Aglianico (1998 year) and one Aglianico (1997 year). The principal differences in the two regions come from climatic conditions, with a mean temperature and rainfall higher in Puglia than in Molise and consequently with the vintage time delayed in Molise as regards Puglia. In addition seven commercial red wines, produced in a similar way, were chosen in order to make a comparison with these less-known southern Italian red wines: Cabernet Sauvignon (Friuli 99, Chile 97, California 94), two Montepulciano (1999 years) one Aglianico (1998 year) and one Troia (1995 year). Standard solutions of myricetin, quercetin, apigenin, kaempferol, resveratrol, gallic acid, caffeic acid and malvidin-3-glucoside were supplied from Sigma-Aldrich. All standards were dissolved in methanol in a linearity range of concentration (5–15 mg/L). Acetonitrile, acetic acid and methanol were obtained from Baker (J.T. Baker, Milan, Italy). Hydrolysis conditions. Flavonols were hydrolysed to aglycons by modifying a method reported by Vuorinen et al. (2000). The method was modified for hydrolysis time (from 1 to 2 h) and temperature (from 85 to 80 C) and for the volume of sample (from 15 to 2 mL). Wine samples
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were hydrolysed in 50% methanol (v/v) containing hydrochloric acid (0.5 m). Samples were filtered through a filter 0.2 mm (Chemtek Analytical s.r.l., Bologna, Italy), prior to the injection of 50 mL to HPLC. The addition method in triplicate was used to evaluate sample recovery that ranged from 80% to 90%. The repeatability was positively controlled by a run of five measures for each compound. Procedure. Flavonols were injected into the column after hydrolysis and eluted with a mobile phase which consisted of solution A, CH3COOH 5% in water, solution B, CH3CN. A step linear gradient starting from 85% solution A up to 80% solution B in 20 min was performed. The flow rate was 1 mL/min. Chromatograms were detected at 370 nm. Phenolic acids, resveratrol and anthocyanins were separated directly without extraction and hydrolysis. They were analysed using a different gradient elution which consisted of CH3COOH 5% (solution A) and CH3CN (solution B) starting from 100% solution A up to 80% solution B in 30 min. The eluting compounds were detected at 280 nm (gallic acid), 313 nm (resveratrol and phenolic acid) and 520 nm (anthocyanins). The flow rate was 1 mL/min. All experimental dates reported were obtained by triplicate determinations. Instrumentation. A C-18 Symmetry column, 5-mm, 4.6 250 mm, from Waters, was used for sample separation. The chromatography apparatus was Dionex and equipped with a GP50 gradient pump, ASI-100 automated sample injector, and a UVD 170S detector. Phenolic acids
Table 1 Levels of anthocyanins (mg/L) expressed as malvidin-3-glucoside equivalents Malvidin Puglia wines Montepulciano/Troia 2000 Montepulciano 1999 Montepulciano/Troia 1998 Troia 1998 Primitivo/Tarantino 1999 Montepulciano 1998
Peonidin
Petunidin
Cyanidin
Delphinidin
92.7 53.7 26.8 23.2 14.9 12.5
13.3 11.7 3.6 2.0 1.3 2.0
0.7 0.4 o0.4 o0.4 o0.4 o0.4
10.1 4.5 3.3 1.1 1.8 o0.4
1.9 1.9 2.5 1.2 0.8 0.42
Molise wines Montepulciano 2000 Montepulciano/Aglianico 1999 Montepulciano/Aglianico 1998 Aglianico 1997
139.0 17.6 9.7 5.2
26.3 2.8 1.8 0.9
2.3 o0.4 o0.4 o0.4
12.3 1.8 1.4 o0.4
2.2 2.7 1.9 2.1
Wines of different origins Cabernet-Sauvignon Friuli 1999 Montepulciano A 1999 Montepulciano 1999 Aglianico 1998 Cabernet-Sauvignon Chile 1997 Troia 1995 Cabernet-Sauvignon California 1994
20.3 17.9 11.9 6.0 1.2 o0.4 0.8
2.1 3.3 2.2 1.0 o0.4 o0.4 o0.4
o0.4 o0.4 o0.4 o0.4 o0.4 o0.4 o0.4
2.1 2.7 1.8 0.9 o0.4 o0.4 o0.4
1.2 1.6 1.9 2.2 1.8 o0.4 o0.4
All data are the mean of triplicate determinations.
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and derivatives were determined with the same column, but using a different liquid chromatograph HP 1100 equipped with a DAD HP G1315A detector. The DAD detector was necessary to identify derivatives of phenolic acids. Their identification was possible from their specific retention time and from DAD spectra from bibliography.
3. Results and discussion All the experimental data, reported in Tables 1–3, were statistically analysed to correlate the concentration of each compound with the geographic origin of vine, but no significant correlation was found. Nevertheless, from these data it was possible to derive some considerations. The red wine made from Montepulciano grapes showed a higher amount of anthocyanins than other wines obtained from a mixture of grapes from different vineyards such as Aglianico, Troia and Primitivo Tarantino. Table 1 reports the anthocyanin concentrations. They are expressed as malvidin-3-glucoside equivalents because the standards of other compounds were not available. Besides, malvidin-3-glucoside showed higher concentration than other anthocyanins analysed. These results indicated that high amounts of malvidin-3-glucoside are still present in aged wines (Cabernet 94). The petunidin was determined only in young wines (2000 year). Peonidin and
Table 2 Levels of flavonoids and resveratrol (mg/L) Quercetin Puglia wines Montepulciano/Troia 2000 Montepulciano 1999 Montepulciano/Troia 1998 Troia 1998 Primitivo/Tarantino 1999 Montepulciano 1998
Apigenin
Myricetin
Resveratrol
6.3 2.1 1.7 1.8 1.7 1.5
2.2 1.4 1.0 1.8 1.1 1.8
4.4 3.3 2.1 1.7 2.0 2.7
0.4 1.3 1.3 2.2 1.3 2.1
Molise wines Montepulciano 2000 Montepulciano/Aglianico 1999 Montepulciano/Aglianico 1998 Aglianico 1997
11.6 2.8 5.7 6.0
2.9 1.2 1.7 1.7
8.0 3.3 4.5 3.5
1.0 1.6 0.6 0.9
Wines of different origins Cabernet-Sauvignon Friuli 1999 Montepulciano 1999 Montepulciano 1999 Aglianico 1998 Cabernet-Sauvignon Chile 1997 Troia 1995 Cabernet-Sauvignon California 1994
1.8 8.7 2.2 2.5 12.8 2.4 5.3
2.1 2.5 o0.2 1.1 4.7 1.6 3.1
4.1 5.0 1.5 3.2 9.7 3.3 5.0
2.2 1.2 1.0 1.1 o0.2 1.3 3.1
All data are the mean of triplicate determinations.
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Table 3 Level of phenolic acids and derivatives (mg/L) expressed as caffeic acid equivalents Gallic
Caffeic
Caffeoyltartaric
p-Coumaric
Puglia wines Montepulciano/Troia 2000 Montepulciano 1999 Montepulciano/Troia 1998 Troia 1998 Primitivo/Tarantino 1999 Montepulciano 1998
45.0 57.0 66.5 26.3 70.0 13.6
7.6 5.5 17.9 5.7 5.9 7.2
17.4 18.5 4.9 20.7 22.7 10.9
0.9 3.6 11.8 7.6 5.3 10.3
8.7 5.3 1.3 9.6 8.8 6.2
5.0 9.2 2.2 4.3 6.4 3.2
Molise wines Montepulciano 2000 Montepulciano/Aglianico 1999 Montepulciano/Aglianico 1998 Aglianico 1997
62.4 90.5 58.3 61.1
14.7 4.9 4.0 5.1
29.3 24.6 21.7 18.1
3.7 7.9 9.5 4.5
8.6 6.5 9.1 7.9
8.4 7.1 6.2 6.3
26.0 43.2 60.3 62.8 46.0 21.3 33.9
5.1 6.7 6.1 3.8 7.3 2.5 4.9
15.0 37.7 19.8 27.5 12.1 12.9 2.8
3.3 16.0 11.6 6.2 7.7 5.3 9.4
7.2 8.8 6.6 10.9 8.0 5.4 3.0
2.6 4.6 4.3 3.7 3.5 3.1 2.3
Wines of different origins Cabernet-Sauvignon Friuli 1999 Montepulciano 1999 Montepulciano 1999 Aglianico 1998 Cabernet-Sauvignon Chile 1997 Troia 1995 Cabernet-Sauvignon California 1994
p-Coumariltartaric
2,5 di-SGlutationilcaftaric
All data are the mean of triplicate determinations.
cyanidin decreased during ageing, but it was still possible to determine their concentration in wines aged 3 years. The delphinidin content was lower than peonidin and cyanidin. This parameter was not influenced by ageing because when we analysed the same wine aged 4 years we observed the same concentration. The decreased concentrations observed during ageing are in agreement with the literature data (La Notte et al., 1992). The concentrations of the anthocyanins were different for wines obtained from vineyards of different geographical origins. Concentrations of quercetin, myricetin and apigenin presented a low variability (Table 2), that could be explained by different varieties of grapes, origin area (climatic conditions, sea level, etc.) and vinification processes. Our results were in agreement with those obtained by Vuorinen et al. (2000) showing a high concentration of quercetin and myricetin in Cabernet Sauvignon (in particular in Cabernet of Chile) and in wines made from Montepulciano and Aglianico grapes. The amount of trans-resveratrol was low and similar in all wines analysed, and it was comparable with the concentration range found in the literature (Dell’oro et al., 1996; Mozzon et al., 1996).
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Only three samples showed concentration of kaempferol higher than the variance line (0.2 mg/L). These results are in agreement with those reported in the literature (Vuorinen et al., 2000; Hertog et al., 1993). Table 3 reports the concentration of some important phenolic acids and derivatives. Derivative compounds and p-coumaric acid are expressed as equivalents of caffeic acid. The importance of these compounds is due to their persistence ‘‘in vivo’’ after wine ingestion (Simonetti et al., 2001). The concentrations of gallic, caffeic, caffeoyltartaric acids were higher than those reported in the literature data (Soleas et al., 1997; Ghiselli et al., 1998). In general the amounts of these phenolic compounds seem independent of both ageing and geographic origins, but cultivar dependent. 4. Conclusion The results obtained show that the concentration of phenolic compounds cannot identify the wines of different geographical origins. Nevertheless, the most important and novel aspect of this work was that these compounds can be used as chemical parameters to identify nutritional properties of wines. They are necessary and sufficient to create an ‘‘identification nutritional card’’. In fact the presence of some antioxidant compounds allows the classification, in an innovative manner, of different wines for their antioxidant properties. Till now these properties have not been used to characterize wines. Private and public laboratories have means to increase the label indications, providing advantages for producers and consumers. References Dell’oro, V., Cravero, M.C., Moraglio, G., 1996. Indagine sul contenuto di resveratrolo in vini piemontesi. Industrie delle bevande, Dicembre, pp. 606–609 Ghiselli, A., Nardini, M., Baldi, A., Scaccini, C., 1998. Antioxidant activity of different phenolic fractions separated from an Italian red wine. Journal of Agricultural and Food Chemistry 47 (2), 361–367. Goldberg, D.M., 1995. Does wine work? Clinical Chemistry 41, 14–16. Hertog, M.G.L., Hollman, P.C.H., Van de putte, B, 1993. Content of potentially anticarcinogenic flavonoids of tea infusions, wine, and fruit juices. Journal of Agricultural and Food Chemistry. 41, 1242–1246. Hollman, P.C.H., Hertog, M.G.L., Katan, M.B., 1996. Analysis and health effects of flavonoids. Food Chemistry 57, 43–46. La Notte, E., Liuzzi, V.A., Esti, M., 1992. I componenti polifenolici del vino. Vignevini 10, 49–55. Mozzon, M., Frega, N., Pallotta, U., 1996. Resveratrol content in some Tuscan wines. Italalian Journal of Food Science. 2, 145–152. Nardini, M., D’aquino, M., Tomassi, G., Gentili, V., Di felice, M., Scaccini, C., 1995. Inhibition of human low density lipoprotein oxidation by caffeic acid and other hydroxycinnamic acid derivates. Free Radical Biology and Medicine. 19, 541–552. Renaud, S., De Lorgeril, M., 1992. Wine, alcohol, platelets, and French paradox for coronary heart disease. The Lancet 339, 1523–1526. Simonetti, P., Bardana, C., Pietta, P., 2001. Plasma levels of caffeic acid and antioxidant status after red wine intake. Journal of Agricultural and Food Chemistry. 49, 5964–5968. Soleas, G.J., Dam, J., Carey, M., Goldberg, D.M., 1997. Toward the fingerprinting of wines: cultivar-related patterns of polyphenolic constituents in Ontario wines. Journal of Agricultural and Food Chemistry. 45, 3871–3880. Vuorinen, H., Maatta, K., Torronen, R., 2000. Content of flavonols myricetin, quercetin, and kaempferol in Finnish berry wine. Journal of Agricultural and Food Chemistry 48, 2675–2680.
JOURNAL OF FOOD COMPOSITION AND ANALYSIS
Journal of Food Composition and Analysis 17 (2004) 613–618 www.elsevier.com/locate/jfca
Original Article
Polyphenols content in some Italian red wines of different geographical origins L. Gambelli*, G.P. Santaroni Istituto Nazionale di Ricerca per gli Alimenti e la Nutrizione, Via Ardeatina 546, 00178 Rome, Italy Received 25 November 2002; received in revised form 25 July 2003; accepted 29 September 2003
Abstract Some polyphenols were determined in 10 red wines of different geographical origins and from single and blended vineyards. The principal aim of this study was to verify the possibility of correlating the concentrating levels of these compounds to the geographical origin of wine and to use the properties of these compounds for wine qualification. An HPLC method was used to determine some flavonols (quercetin, myricetin, apigenin, kaempferol), some anthocyanins (malvidin, peonidin, petunidin, cyanidin, delphinidin), some phenolic acids (gallic, caffeic, caffeoyltartaric, p-coumaric, 2,5-di-S-glutationil-caftaric) and the trans-resveratrol. The results showed differences in the concentration levels of a single antioxidant compound ranging in mg/mL for flavonols from o0.2 (kaempferol) to 11.6 (quercetin), for anthocyanins from o0.4 (petunidin) to 139 (malvidin), for phenolic acids from 2.2 (2,5 di-S-glutationil-caftaric) to 90.5 (gallic) and for trans-resveratrol from 0.2 to 3.1. These differences are not related to the geographical origin of wines, but rather to either to ageing or vineyards. This kind of data could be useful for wine commercial qualification, as ‘‘nutritional information’’. r 2003 Elsevier Inc. All rights reserved. Keywords: Nutritional card; Polyphenols; Italian wines
1. Introduction Red wines include a number of polyphenolic constituents, such as monomeric flavonoids, anthocyanins, phenolic acids and polymeric tannins, that can help/affect human health. These compounds are characterized by antioxidant properties that play an inhibitory role at different stages of tumour development (Hertog et al., 1993). They are effective radical scavengers with respect to oxygen free radicals and lipid peroxidation (LDL) (Nardini et al., 1995). Some studies have shown epidemiological evidence that an increased dietary intake of natural polyphenols *Corresponding author. Tel.: +39-06-50-32-412; fax: +39-06-50-31-592. E-mail address: [email protected] (L. Gambelli). 0889-1575/$ - see front matter r 2003 Elsevier Inc. All rights reserved. doi:10.1016/j.jfca.2003.09.010
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reduces the coronary heart disease (CHD), artherosclerosis effect and platelet aggregation (Hollman et al., 1996). Also, they can inhibit and sometimes induce a large variety of mammalian enzyme systems. In France, CHD mortality is lower than in other industrialized countries, even if the dietary intake of saturated fat is higher. Regular consumption of red wine has been hypothesized to be the most likely cause for this phenomenon known as the French paradox (Renaud and Lorgeril, 1992). Polyphenolic compounds are widely distributed in vegetables. They are present in complex polymeric and glycosidic forms, that could not easily be degraded by digestive juices and so their absorption could be limited. In wine, during fermentation, these aggregates are broken down to monomeric forms. The alcohol content of 10% or more contained in most table wines gives stability to phenols present in bottled wines, allowing their absorption (Goldberg, 1995). These beneficial effects are important from a nutritional point of view and so it is necessary to find specific chemical parameters which could be used to develop a ‘‘nutritional card’’ of wine. In this study some polyphenols — flavonoids, anthocyanins, phenolic acids and resveratrol — were determined. These compounds could be key agents of the antioxidant action on the human metabolism pathway, the reason why we wanted to obtain indications to qualify the wine from a nutritional point of view. Also the environmental conditions (temperature, rainfall/humidity, latitude, height above sea level and geochemical characteristics) can affect the vine maturation and consequently the concentration of its antioxidant compounds. We have analysed wines from two Italian regions, Puglia and Molise, that have different environmental characteristics.
2. Materials and methods Ten southern Italian red wines from Puglia and Molise regions were analysed. Red wines of Puglia were: one Montepulciano/Troia (2000 year), one Montepulciano and one Primitivo/Tarantino (1999 year) and one Montepulciano, one Troia and one Montepulciano/ Troia (1998 year). Red wines of Molise were: one Montepulciano (2000 year), one Montepulciano/Aglianico (1999 year), one Montepulciano/Aglianico (1998 year) and one Aglianico (1997 year). The principal differences in the two regions come from climatic conditions, with a mean temperature and rainfall higher in Puglia than in Molise and consequently with the vintage time delayed in Molise as regards Puglia. In addition seven commercial red wines, produced in a similar way, were chosen in order to make a comparison with these less-known southern Italian red wines: Cabernet Sauvignon (Friuli 99, Chile 97, California 94), two Montepulciano (1999 years) one Aglianico (1998 year) and one Troia (1995 year). Standard solutions of myricetin, quercetin, apigenin, kaempferol, resveratrol, gallic acid, caffeic acid and malvidin-3-glucoside were supplied from Sigma-Aldrich. All standards were dissolved in methanol in a linearity range of concentration (5–15 mg/L). Acetonitrile, acetic acid and methanol were obtained from Baker (J.T. Baker, Milan, Italy). Hydrolysis conditions. Flavonols were hydrolysed to aglycons by modifying a method reported by Vuorinen et al. (2000). The method was modified for hydrolysis time (from 1 to 2 h) and temperature (from 85 to 80 C) and for the volume of sample (from 15 to 2 mL). Wine samples
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were hydrolysed in 50% methanol (v/v) containing hydrochloric acid (0.5 m). Samples were filtered through a filter 0.2 mm (Chemtek Analytical s.r.l., Bologna, Italy), prior to the injection of 50 mL to HPLC. The addition method in triplicate was used to evaluate sample recovery that ranged from 80% to 90%. The repeatability was positively controlled by a run of five measures for each compound. Procedure. Flavonols were injected into the column after hydrolysis and eluted with a mobile phase which consisted of solution A, CH3COOH 5% in water, solution B, CH3CN. A step linear gradient starting from 85% solution A up to 80% solution B in 20 min was performed. The flow rate was 1 mL/min. Chromatograms were detected at 370 nm. Phenolic acids, resveratrol and anthocyanins were separated directly without extraction and hydrolysis. They were analysed using a different gradient elution which consisted of CH3COOH 5% (solution A) and CH3CN (solution B) starting from 100% solution A up to 80% solution B in 30 min. The eluting compounds were detected at 280 nm (gallic acid), 313 nm (resveratrol and phenolic acid) and 520 nm (anthocyanins). The flow rate was 1 mL/min. All experimental dates reported were obtained by triplicate determinations. Instrumentation. A C-18 Symmetry column, 5-mm, 4.6 250 mm, from Waters, was used for sample separation. The chromatography apparatus was Dionex and equipped with a GP50 gradient pump, ASI-100 automated sample injector, and a UVD 170S detector. Phenolic acids
Table 1 Levels of anthocyanins (mg/L) expressed as malvidin-3-glucoside equivalents Malvidin Puglia wines Montepulciano/Troia 2000 Montepulciano 1999 Montepulciano/Troia 1998 Troia 1998 Primitivo/Tarantino 1999 Montepulciano 1998
Peonidin
Petunidin
Cyanidin
Delphinidin
92.7 53.7 26.8 23.2 14.9 12.5
13.3 11.7 3.6 2.0 1.3 2.0
0.7 0.4 o0.4 o0.4 o0.4 o0.4
10.1 4.5 3.3 1.1 1.8 o0.4
1.9 1.9 2.5 1.2 0.8 0.42
Molise wines Montepulciano 2000 Montepulciano/Aglianico 1999 Montepulciano/Aglianico 1998 Aglianico 1997
139.0 17.6 9.7 5.2
26.3 2.8 1.8 0.9
2.3 o0.4 o0.4 o0.4
12.3 1.8 1.4 o0.4
2.2 2.7 1.9 2.1
Wines of different origins Cabernet-Sauvignon Friuli 1999 Montepulciano A 1999 Montepulciano 1999 Aglianico 1998 Cabernet-Sauvignon Chile 1997 Troia 1995 Cabernet-Sauvignon California 1994
20.3 17.9 11.9 6.0 1.2 o0.4 0.8
2.1 3.3 2.2 1.0 o0.4 o0.4 o0.4
o0.4 o0.4 o0.4 o0.4 o0.4 o0.4 o0.4
2.1 2.7 1.8 0.9 o0.4 o0.4 o0.4
1.2 1.6 1.9 2.2 1.8 o0.4 o0.4
All data are the mean of triplicate determinations.
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and derivatives were determined with the same column, but using a different liquid chromatograph HP 1100 equipped with a DAD HP G1315A detector. The DAD detector was necessary to identify derivatives of phenolic acids. Their identification was possible from their specific retention time and from DAD spectra from bibliography.
3. Results and discussion All the experimental data, reported in Tables 1–3, were statistically analysed to correlate the concentration of each compound with the geographic origin of vine, but no significant correlation was found. Nevertheless, from these data it was possible to derive some considerations. The red wine made from Montepulciano grapes showed a higher amount of anthocyanins than other wines obtained from a mixture of grapes from different vineyards such as Aglianico, Troia and Primitivo Tarantino. Table 1 reports the anthocyanin concentrations. They are expressed as malvidin-3-glucoside equivalents because the standards of other compounds were not available. Besides, malvidin-3-glucoside showed higher concentration than other anthocyanins analysed. These results indicated that high amounts of malvidin-3-glucoside are still present in aged wines (Cabernet 94). The petunidin was determined only in young wines (2000 year). Peonidin and
Table 2 Levels of flavonoids and resveratrol (mg/L) Quercetin Puglia wines Montepulciano/Troia 2000 Montepulciano 1999 Montepulciano/Troia 1998 Troia 1998 Primitivo/Tarantino 1999 Montepulciano 1998
Apigenin
Myricetin
Resveratrol
6.3 2.1 1.7 1.8 1.7 1.5
2.2 1.4 1.0 1.8 1.1 1.8
4.4 3.3 2.1 1.7 2.0 2.7
0.4 1.3 1.3 2.2 1.3 2.1
Molise wines Montepulciano 2000 Montepulciano/Aglianico 1999 Montepulciano/Aglianico 1998 Aglianico 1997
11.6 2.8 5.7 6.0
2.9 1.2 1.7 1.7
8.0 3.3 4.5 3.5
1.0 1.6 0.6 0.9
Wines of different origins Cabernet-Sauvignon Friuli 1999 Montepulciano 1999 Montepulciano 1999 Aglianico 1998 Cabernet-Sauvignon Chile 1997 Troia 1995 Cabernet-Sauvignon California 1994
1.8 8.7 2.2 2.5 12.8 2.4 5.3
2.1 2.5 o0.2 1.1 4.7 1.6 3.1
4.1 5.0 1.5 3.2 9.7 3.3 5.0
2.2 1.2 1.0 1.1 o0.2 1.3 3.1
All data are the mean of triplicate determinations.
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Table 3 Level of phenolic acids and derivatives (mg/L) expressed as caffeic acid equivalents Gallic
Caffeic
Caffeoyltartaric
p-Coumaric
Puglia wines Montepulciano/Troia 2000 Montepulciano 1999 Montepulciano/Troia 1998 Troia 1998 Primitivo/Tarantino 1999 Montepulciano 1998
45.0 57.0 66.5 26.3 70.0 13.6
7.6 5.5 17.9 5.7 5.9 7.2
17.4 18.5 4.9 20.7 22.7 10.9
0.9 3.6 11.8 7.6 5.3 10.3
8.7 5.3 1.3 9.6 8.8 6.2
5.0 9.2 2.2 4.3 6.4 3.2
Molise wines Montepulciano 2000 Montepulciano/Aglianico 1999 Montepulciano/Aglianico 1998 Aglianico 1997
62.4 90.5 58.3 61.1
14.7 4.9 4.0 5.1
29.3 24.6 21.7 18.1
3.7 7.9 9.5 4.5
8.6 6.5 9.1 7.9
8.4 7.1 6.2 6.3
26.0 43.2 60.3 62.8 46.0 21.3 33.9
5.1 6.7 6.1 3.8 7.3 2.5 4.9
15.0 37.7 19.8 27.5 12.1 12.9 2.8
3.3 16.0 11.6 6.2 7.7 5.3 9.4
7.2 8.8 6.6 10.9 8.0 5.4 3.0
2.6 4.6 4.3 3.7 3.5 3.1 2.3
Wines of different origins Cabernet-Sauvignon Friuli 1999 Montepulciano 1999 Montepulciano 1999 Aglianico 1998 Cabernet-Sauvignon Chile 1997 Troia 1995 Cabernet-Sauvignon California 1994
p-Coumariltartaric
2,5 di-SGlutationilcaftaric
All data are the mean of triplicate determinations.
cyanidin decreased during ageing, but it was still possible to determine their concentration in wines aged 3 years. The delphinidin content was lower than peonidin and cyanidin. This parameter was not influenced by ageing because when we analysed the same wine aged 4 years we observed the same concentration. The decreased concentrations observed during ageing are in agreement with the literature data (La Notte et al., 1992). The concentrations of the anthocyanins were different for wines obtained from vineyards of different geographical origins. Concentrations of quercetin, myricetin and apigenin presented a low variability (Table 2), that could be explained by different varieties of grapes, origin area (climatic conditions, sea level, etc.) and vinification processes. Our results were in agreement with those obtained by Vuorinen et al. (2000) showing a high concentration of quercetin and myricetin in Cabernet Sauvignon (in particular in Cabernet of Chile) and in wines made from Montepulciano and Aglianico grapes. The amount of trans-resveratrol was low and similar in all wines analysed, and it was comparable with the concentration range found in the literature (Dell’oro et al., 1996; Mozzon et al., 1996).
ARTICLE IN PRESS 618
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Only three samples showed concentration of kaempferol higher than the variance line (0.2 mg/L). These results are in agreement with those reported in the literature (Vuorinen et al., 2000; Hertog et al., 1993). Table 3 reports the concentration of some important phenolic acids and derivatives. Derivative compounds and p-coumaric acid are expressed as equivalents of caffeic acid. The importance of these compounds is due to their persistence ‘‘in vivo’’ after wine ingestion (Simonetti et al., 2001). The concentrations of gallic, caffeic, caffeoyltartaric acids were higher than those reported in the literature data (Soleas et al., 1997; Ghiselli et al., 1998). In general the amounts of these phenolic compounds seem independent of both ageing and geographic origins, but cultivar dependent. 4. Conclusion The results obtained show that the concentration of phenolic compounds cannot identify the wines of different geographical origins. Nevertheless, the most important and novel aspect of this work was that these compounds can be used as chemical parameters to identify nutritional properties of wines. They are necessary and sufficient to create an ‘‘identification nutritional card’’. In fact the presence of some antioxidant compounds allows the classification, in an innovative manner, of different wines for their antioxidant properties. Till now these properties have not been used to characterize wines. Private and public laboratories have means to increase the label indications, providing advantages for producers and consumers. References Dell’oro, V., Cravero, M.C., Moraglio, G., 1996. Indagine sul contenuto di resveratrolo in vini piemontesi. Industrie delle bevande, Dicembre, pp. 606–609 Ghiselli, A., Nardini, M., Baldi, A., Scaccini, C., 1998. Antioxidant activity of different phenolic fractions separated from an Italian red wine. Journal of Agricultural and Food Chemistry 47 (2), 361–367. Goldberg, D.M., 1995. Does wine work? Clinical Chemistry 41, 14–16. Hertog, M.G.L., Hollman, P.C.H., Van de putte, B, 1993. Content of potentially anticarcinogenic flavonoids of tea infusions, wine, and fruit juices. Journal of Agricultural and Food Chemistry. 41, 1242–1246. Hollman, P.C.H., Hertog, M.G.L., Katan, M.B., 1996. Analysis and health effects of flavonoids. Food Chemistry 57, 43–46. La Notte, E., Liuzzi, V.A., Esti, M., 1992. I componenti polifenolici del vino. Vignevini 10, 49–55. Mozzon, M., Frega, N., Pallotta, U., 1996. Resveratrol content in some Tuscan wines. Italalian Journal of Food Science. 2, 145–152. Nardini, M., D’aquino, M., Tomassi, G., Gentili, V., Di felice, M., Scaccini, C., 1995. Inhibition of human low density lipoprotein oxidation by caffeic acid and other hydroxycinnamic acid derivates. Free Radical Biology and Medicine. 19, 541–552. Renaud, S., De Lorgeril, M., 1992. Wine, alcohol, platelets, and French paradox for coronary heart disease. The Lancet 339, 1523–1526. Simonetti, P., Bardana, C., Pietta, P., 2001. Plasma levels of caffeic acid and antioxidant status after red wine intake. Journal of Agricultural and Food Chemistry. 49, 5964–5968. Soleas, G.J., Dam, J., Carey, M., Goldberg, D.M., 1997. Toward the fingerprinting of wines: cultivar-related patterns of polyphenolic constituents in Ontario wines. Journal of Agricultural and Food Chemistry. 45, 3871–3880. Vuorinen, H., Maatta, K., Torronen, R., 2000. Content of flavonols myricetin, quercetin, and kaempferol in Finnish berry wine. Journal of Agricultural and Food Chemistry 48, 2675–2680.