Evolution of 49 Phenolic Compounds in Shortly-Aged Red Wines Made from Cabernet Gernischt (Vitis Vinifera L

Food Sci. Biotechnol. Vol. 18, No. 4, pp. 1001 ~ 1012 (2009) ⓒ The Korean Society of Food Science and Technology Evolution of 49 Phenolic Compounds in Shortly-aged Red Wines Made from Cabernet Gernischt (Vitis vinifera L. cv.) Zheng Li, Qiu-Hong Pan, Zan-Min Jin, Jian-Jun He, Na-Na Liang, and Chang-Qing Duan* Center for Viticulture and Enology, College of Food Science and Nutritional Engineering, China Agricultural University, Beijing 100083, PR China Abstract A total of 49 phenolic compounds were identified from the aged red wines made from Cabernet Gernischt (Vitis vinifera L. cv.) grapes, a Chinese characteristic variety, including 13 anthocyanins, 4 pryanocyanins, 4 flavan-3-ol monomers, 6 flavan-3-ol polymers, 7 flavonols, 6 hydroxybenzoic acids, 5 hydroxycinnamic acids, 3 stilbenes, and 1 polymeric pigment. Evolution of these compounds was investigated in wines aged 1 to 13 months. Variance analysis showed that the levels of most phenolics existed significant difference in between wines aged 3 and 9 months. Cluster analysis indicated that 2 groups could be distinguished, one corresponding to wines aged 1 to 3 months and the other to wines aged 4 to 13 months. It was thus suggested that there were 2 key-stages for the development of fine wine quality, at the aged 3 and 9 months, respectively. This work would provide some helpful information for quality control in wine production. Keywords: Cabernet Gernischt, aged wine, phenolic compound, evolution, high performance liquid chromatography coupled with tandem mass spectrometry Introduction 3-ols in red wine and correlation with wine age (12), the evolutions of low molecular weight phenolic compounds Phenolic compounds in red wines mainly contain such as gallic acids and caffeic acids (13,14), as well as the anthocyanins, flavonols, flavan-3-ols, phenolic acids effects of oak barrel compounds and sorption behaviors on (including hydroxybenzoic acids and hydroxycinnamic evolution of phenolic compounds (15), have been reported. acids), and stilbenes. Except anthocyanins, the others are The previous studies are mainly paid to non-anthocyanin called as non-anthocyanin phenolics. All these compounds phenolics in white wines, for they are closely related to are extracted into wine during fermentation and closely browning of white wines (16-18). Non-anthocyanin phenolics related to the quality of wine. It has been known that also play important roles in constituting the organoleptic phenolic compounds not only contribute wine to color, properties of red wines. Baranac et al. (19) reported that flavor, astringency, and bitterness, which constitute essential flavonols are considered to be the best cofactors present in sensory prosperities, but also endow wine with abundant the phenolic composition of red wines. Darias-Martín et al. nutritional and healthy functions (1,2). (20) and Bloonfield et al. (21) also mentioned that flavan- Many factors can influence the phenolic composition 3-ols and hydroxycinamic acids (caffeic, ρ-coumaric, and and magnitude of wines, including grape variety, the ferulic acids) can act as cofactors for copigmentation. In technology applied in winemaking, and the reactions that the aged red wines, it has been known that a change of the take place during aging. Many published works have been color hue from purple-red to red, and then to yellow-red reported that phenolic profiles of wines differ from grape tonalities involves the formation of polymeric anthocyanins variety to variety (3-5). Moreover, Alamo et al. (6) from the covalent linking of monomeric anthocyanins reported that even for different aging containers, behavior (22,23). As mentioned above, previous studies involving of phenolic reactions in the aged wines also shows the non-anthocyanin phenolics in red wines mainly focus remarkable different, which will lead to generation of on the identification and content evolution of copigmentation- different organoleptic characteristics of wines. Therefore, related compounds, and on the fermentation process. Few for a wine made from special single variety, special were reported to date concerning the evolution of non- enological process and aging technology are required in anthocyanin phenolics during aging, especially the change order to fully exploit the characteristics of this variety. of non-copigmented phenolics. Phenolic compounds during wine aging are not always Cabernet Gernischt (Vitis vinifera L. cv.) is a Chinese changeless. Many previous studies have been reported on characteristic variety that might have been imported from the evolution of anthocyanins profiles, containing the Europe in 1894 and naturally selected in China. The red effects of copigmentation on wine color (7,8), the formation wines made from Cabernet Gernischt are getting popular of pyranoanthocyanins and their influence factors in wines with customers owing to attractive color and fine taste. The (9-11). Moreover, formation of ethylidene-bridged flavan- objective of the present study is to identify major phenolic compounds in aged Cabernet Gernischt wine by high *Corresponding author: Tel: +86-10-62737136; Fax: +86-10-62737136 performance liquid chromatography (HPLC)-coupled with E-mail: [email protected] tandem mass spectrometry (MS/MS) and to investigate the Received March 7, 2009; Revised April 21, 2009; evolutions of these phenolic compounds during the oak Accepted April 26, 2009 barrel aging. Through this work, we intended to uncover 1001 1002 Z. Li et al. the correlation of evolution of various phenolic compounds then were directly used for analysis of high performance during red wine aging and to elucidate possible mechanism liquid chromatography (HPLC)-coupled with tandem mass of wine quality development in aging wine. spectrometry (MS/MS) without dilution. For non-anthocyanin phenolics (including flavan-3-ols, Materials and Methods flavonols, hydroxybenzoic acids, hydroxycinnamic acids, and stilbenes), a total of 100 mL wine sample were diluted Winemaking Fully-ripen ‘Cabernet Gernischt’ grape with the same volume of purified water, and then extracted berries (Vitis vinifera L. cv.) were harvested from a thrice with 80 mL of ethyl acetate (analytical grade). The commercial vineyard in Changyu castle (Hebei, China) in ethyl acetate phase of the combined extracts was removed Oct. 2004 on the basis of similar size and absence of by a rotary evaporation at 28ºC and the remainder was physical injuries or infections. These berries were divided resolved in methanol (chromatography grade) up to a final into 3 groups, which were named as T1, T2, and T3 volume of 5 mL. The final samples were filtered by 0.22- respectively. Each group with about 10,000 kg berries was µm organic membranes prior to analysis by HPLC-MS/ applied for winemaking and all the treatments were MS. controlled under identical conditions. After stemming and Quantitative analyses by HPLC-MS/MS: For anthocyanins, crushing, a pectic enzyme (EX-V; Lallemand Co., Toulous, An Agilent 1100 series LC-MSD trap VL, equipped with France, 20 g/L) and an amount of 60 mg/L of SO2 were a G1379A degasser, a G1311A QuatPump, a G1313A added to the must with skin maceration. The fermentation ALS, a G1316A column, a G1315B DAD and a Kromasil- was then performed at 26-28ºC with a commercial C18 column (250×4mm, 6.5µm), was used. The solvents Saccharomyces cereviside yeast (BM; Lallemand Co., 0.20 were (A) 6%(v/v) acetonitrile containing 2%(v/v) formic kg/kL) and Oenococcus oeni lactic acid bacteria (Vitilactic- acid, and (B) 54%(v/v) acetonitrile containing 2%(v/v) D; Martia Vialatte, France. 10 g/kL). The wine-making formic acid. The gradient was from 10% B for 1 min, from strictly obeyed the manufacture techniques of red wine 10 to 25% B for 17 min, isocratic 25% B for 2 min, from made from ‘Carbernet Gernischt’ in China Changyu 25 to 40% for 10 min, from 40 to 70% for 5 min, from 70 Winery Co., Ltd. in 2004. After the end of fermentation to 100% for 5 min, at a flow rate of 1.0 mL/min. Injection (including alcohol and malolactic fermentations), some volumes were 30 µL, and the detection wavelength was conventional parameters were assessed and shown in Table 525 nm. The column temperature was 50ºC. MS conditions 1. The results indicated that these wines could reach the were as follows: electrospray ionization (ESI), positive ion standard and had similar physicochemical parameters. model; nebulizer, 35 psi; dry gas flow, 10 L/min; dry gas These wine samples were subsequently aged for a period temperature, 325ºC; Scan, 100-1,000 m/z. of 13 months in new French Allier MT+ oak barrels. The For non-anthocyanins phenolic compounds, an Agilent aging conditions were controlled at 16ºC and with a 1200 series, equipped with a G1322A degasser, a G1312B humidity of 80%. Wine aging samples to be analyzed were Bin pump, a G1367C HiP-ALS, a G1316B TCC, a taken about 500 mL from the barrels after 1, 2, 3, 4, 5, 9, G1314C VWD, and a ZORBAX SB-C18 column (3×50 and 13 months of aging, respectively, and were mm, 1.8 µm) were used. The solvents were (A) 10%(v/v) immediately used for the following analyses. acetic acid, and (B) 90%(v/v) acetonitrile containing 10%(v/v) acetic acid. The elution gradient was from 5 to Chemicals and standards The standards, malvidin-3-O- 8% B for 5 min, from 8 to 12% B for 2 min, from 12 to glucoside, catechin, quercetin, gallic aid, caffeic acid, and 18% for 5 min, from 18 to 22% for 5 min, from 22 to 35% resveratrol, were all purchased from Sigma-Aldrich (St. for 2 min, from 35 to 100% B for 2 min, 100% B for 4 min Louis, MO, USA). Methanol, formic acid, acetic acid, and and from 100 to 5% B for 2 min, as well as at a flow rate acetonitrile glacial acetic acid (HPLC grade) were obtained of 1.0 mL/min.

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