红葡萄酒中酚类化合物的快速高效液相色谱分析

阐述了一种新型的可直接而快速分离红葡萄酒中酚类化合物(苯甲酸、黄烷-3-醇、肉桂酸、黄酮醇、花色素)的反相高效液相色谱法。采用的色谱柱可用于低pH环境且能高流速运行，在均含有0.2％三氟乙酸的水和乙腈两相中进行梯度洗脱。为了提高选择性，每种化合物都在其最大吸光度处被检测，从而建立其精密度、线性和灵敏度。尽管这种方法不能检测酒中所有组分，但适用于主要成分的测定和对特殊类别酚类化合物总量的定量分析。     

不同酿酒酵母发酵对红葡萄酒中花色苷组成的影响

比较了不同酿酒酵母菌株发酵对红葡萄酒中花色苷组分的影响,为本土酵母的开发应用提供依据。采用本土自筛酿酒酵母菌株Y17和进口商业酵母菌株F15分别酿造干红葡萄酒,并利用高效液相色谱-质谱联用技术(HPLC-MS)对葡萄酒中的花色苷成分进行检测。结果表明,不同酵母发酵葡萄酒中的花色苷成分种类大体相同,但各种花色苷的含量具有较大差别,本土酵母菌株Y17在发酵生产高花色苷含量葡萄酒方面具有优势。     

固相萃取-高效液相色谱法同时测定葡萄酒中没食子酸等8种多酚类化合物

建立了固相萃取.高效液相色谱光电二极管阵列检测法测定葡萄酒中没食子酸等8种多酚类生物活性化合物的方法.并用此方法测定了市售的7种葡萄酒中该8种生物活性物质的含量.实验确定了葡萄酒样品中的没食子酸等物质的固相萃取方法,通过优化萃取条件,有效的去除了葡萄酒中大量干扰成分.采用HypersilC18柱(250mm×4.6mm,i.d.5μm)分离.以乙腈-0.3%乙酸为流动相,线性梯度洗脱,以保留时间和特征光谱对分离出的组分予以定性确证,用峰面积进行定量.8种组分的质量浓度与其峰面积在一定的范围内有良好的线性关系,相关系数为0.9982～0.9999,8种组分的平均回收率为83.9%～103.7%(相对标准偏差为1.6%～4.6%),检测限为0.2～1.5mg/L.对市售的7种葡萄酒的检测结果表明,多酚类物质作为葡萄酒中重要的生物活性成分,其含量与葡萄酒的酿造方式,葡萄品种,葡萄产地有密切的关系.该方法简便、快速、灵敏,也适用于其它复杂体系中没食子酸等8种生物活性的成分分析.     

Polyphenolic Profile of Red Wines for the Discrimination of Controlled Designation of Origin

The aims were to determine the polyphenolic profile of red wines from Spanish Designation of Origin (DO) Rías Baixas and Ribeira Sacra and to evaluate the feasibility of using polyphenolic profiles and chemometric tools to classify wines for authentication purposes. Trans-resveratrol, oenin, malvin, (+)-catechin, (?)-epicatechin, quercetin and syringic acid were determined in 39 samples. Soft independent modeling of class analogy (SIMCA), linear discriminant analysis (LDA) and support vector machine classification (SVM) were used to classify. For resveratrol, Ribeira Sacra red wines showed higher values than Rías Baixas wines (4.60 and 3.36 mg L^?1, respectively). SVM classification was adequate for 100 % classification of wines by their polyphenolic profile. SIMCA classification was also adequate for wine classification of DO Rías Baixas and Ribeira Sacra wines. As conclusion, polyphenolic profile can be used for classification of DOs. The models can discriminate outside wines. Thus, this approach can be useful for authentication purposes.     

Fining of Red Wines with Pomace Cell Wall Material: Effect on Wine Phenolic Composition

Fining is a winemaking technique used to remove unwanted wine components that affect clarification, astringency, color, bitterness, and aroma. One of the objectives of fining is often to reduce the wine tannin content due to its effect on wine astringency. Proteinaceous agents are commonly used with this objective, but problems related with their possible allergenic properties or the excessive enrichment of wine with proteins, which may cause stability and turbidity problems, have led to the search for new fining agents. In this way, the cell wall material from processed grape pomace could be a good alternative since it has a high affinity for tannins. In this work, the effect of cell wall material from processed pomace from Monastrell and Cabernet Sauvignon grapes on the reduction of the phenolic content of red wines is studied and the results are compared with those obtained with commercial fining products. Also, the varietal effect due to the different composition of the cell wall material from these two varieties has been evaluated. The concentration and composition of wine anthocyanins and tannins, before and after the fining process, were analyzed by HPLC and their molecular mass distribution by SEC. The results showed that, at laboratory scale, pomace cell walls have a fining effect that exceeds that of most the protein-based fining agents, even when used at their highest recommended doses. The cell wall material significantly reduced the wine phenolic content, the reduction ranging from 48 to 68% for anthocyanins and from 44 to 64% for tannins, although varietal differences exist regarding the cell wall-binding capacity. Monastrell cell walls exhibited the highest capacity and could be used at much lower doses than those used in this study, reducing the formation of lees and the wine adsorbed on them. The results indicate that this material could be an appropriate alternative for protein-based fining agents in red wine and their use would avoid allergen-related effects.     

Impact of Processing Parameters on the Phenolic Profile of Wines Produced from Hybrid Red Grapes Maréchal Foch,Corot noir,and Marquette

Phenolic extraction in hybrid and interspecific wine grape cultivars is poorly understood, especially in terms of the impact of fermentation and enological conditions on condensed tannins and anthocyanins. Following fractionation via solid‐phase extraction and high‐performance liquid chromatography, phenolic profiles of must and wine from red hybrid grape cultivars Maréchal Foch, Corot noir, and Marquette were examined to assess the impact of enzyme and tannin addition, cold soak, and hot press during vinification. Across cultivars, hot press treatments resulted in the greatest extraction of condensed tannin, anthocyanin, and other monomeric phenolic compounds in musts, and treatments that increased skin contact time or cellular degradation during fermentation produced higher concentrations of tannins, anthocyanins, and flavonols. However, these increases were transient, evincing incomplete carryover into finished wines. Depending on initial must extraction, diglucoside forms of anthocyanins were either selectively extracted or selectively retained throughout fermentation when compared to their monoglucoside counterparts. Typical of hybrid grapes, tannin concentrations across cultivars were low, even under hot press conditions. For condensed tannins and anthocyanins, a cultivar‐specific, stable‐state concentration and phenolic profile emerged regardless of fermentation conditions. Due to the high levels of diglucoside anthocyanins and low levels of condensed tannins, it is expected that the color development and profile in these wines produced from hybrid grape cultivars will be dictated by the monomeric anthocyanins and their potential role in copigmentation processes involving other monomeric phenolic species, as opposed to the formation of polymeric color pigments.     

FTIR Spectroscopy and Direct Orthogonal Signal Correction Preprocessing Applied to Selected Phenolic Compounds in Red Wines

The composition of phenolic compounds plays an important role in food science and nutrition; thus, there is a need of a new method of analysis that is able to speed up the monitoring of product quality parameters. In this view, the amount of selected color components of 145 commercial red wines (total wine color, polymeric pigments, total anthocyanins, and copigmentation index) was investigated using Fourier transform mid-infrared spectroscopy (MIR) combined with partial least squares (PLS) regression. The feasibility of several preprocessing algorithms (first and second derivative, standard normal variate, and direct orthogonal signal correction) was compared in terms of coefficient of determination (R ²) and root mean square error of prediction using an independent test set of wines. The composition of red wines showed great difference in terms of total color (5.07 ± 1.95 AU at 520 nm) compared to copigmentation index (0.66 ± 0.58 AU at 520 nm). The best prediction model was obtained using direct orthogonal signal correction (DOSC) preprocessing. In particular, the prediction of total wine color, total anthocyanins, and polymeric pigments showed a good fitting (R ² ≥ 0.82), whereas copigmentation index was more difficult to be predicted by FTIR (R ² = 0.57). This preliminary study showed the potential of MIR spectroscopy with DOSC–PLS algorithm to successfully analyze selected color components of red wine on a large number of samples in short time with almost no sample preparation and no chemical waste is created.     

用HPLC分析赤霞珠干红葡萄酒中花色素苷成分

赤霞珠是酿造干红葡萄酒的优良传统品种。以HPLC方法对不同产地赤霞珠干红葡萄酒中花色素苷的组分进行了研究。结果表明，不同产地的赤霞珠干红葡萄酒中都含有：花翠素3-O-葡萄糖苷，花青素3-O-葡萄糖苷，3’-甲花翠素3-O-葡萄糖苷，甲基花青素3-O-葡萄糖苷，二甲花翠素3-O-葡萄糖苷，甲基花青素3-O-（6-O-乙酰)-葡萄糖苷，二甲花翠素3-O-(6-O-乙酰)-葡萄糖苷，甲基花青素3-O-(6-O-对香豆酰)-葡萄糖苷，二甲花翠素3-O-(6-O-对香豆酰)一葡萄糖苷等9种花色素苷，而其中的二甲花翠素3-O-葡萄糖苷(46．75％-60．31％)和二甲花翠素3-O-（6-O-乙酰)葡萄糖苷(22．37％-29．03％)是赤霞珠葡萄酒中的主要花色素苷。赤霞珠葡萄酒中甲基花青素3-O-(6-O-乙酰)葡萄糖苷和二甲花翠素3-O-(6-O-乙酰)葡萄糖苷的总量与甲基花青素3-O-(6-O-对香豆酰)葡萄糖苷和二甲花翠素3-O-(6-O-香豆酰)葡萄糖苷的总量比率存在大于3这一经验值，为3．92～7．40。     

Relationship between Sensory Perception,Volatile and Phenolic Components in Commercial Spanish Red Wines from Different Regions

Polyphenols are an important fraction of the non-volatile components in the red wine matrix, and they are influenced in quantity and composition at all stages from the grape growing conditions until the time the wine is consumed. Evidence of their interaction with volatiles has been found, and this should affect wine flavour. A range of 12 commercial Spanish red wines from different regions and ages was analysed for their sensory properties, volatile composition in solution and headspace, and their non-volatile phenolic components. Maturation was the most important effect on sensory perception, while the chemical data showed also individual differences between the wines and their regions of production. Headspace volatiles and the phenolic fraction showed better correlations with the sensory perception, but volatiles in solution did not give a good prediction, though there were changes related to maturation. Some flavour components showed changes in their volatile behaviour in the matured wines. This supports the hypothesis that changes in the behaviour of the volatile fraction are related to the evolution of phenolic compounds.     

Effects of Vinification Techniques Combined with UV‐C Irradiation on Phenolic Contents of Red Wines

Red wines are typically high in phenolic and antioxidant capacity and both of which can be increased by vinification techniques. This study employed 3 vinification techniques to assess the increase in phenolic compounds and antioxidant capacity. Wines were obtained from Bo?azkere grape cultivar by techniques of classical maceration, cold maceration combined with ultraviolet light (UV) irradiation, and thermovinification combined with UV irradiation and changes in phenolic contents were examined. Total phenolic and anthocyanin contents and trolox equivalent antioxidant capacity of wines were measured spectrophotometrically and phenolic contents (+)‐catechin, (–)‐epicatechin, rutin, quercetin, trans‐resveratrol, and cis‐resveratrol were measured by High Pressure Liquid Chromatography with Diode Array Detection (HPLC‐DAD). As a result of the study, the highest phenolic content except for quercetin was measured in the wines obtained by thermovinification combined with UV irradiation. We demonstrated that the highest phenolic compounds with health effect, total phenolic compounds, total anthocyanin, and antioxidant activity were obtained from thermovinification with UV‐C treatment than classical wine making.     

Inhibition ofIn VitroHuman LDL Oxidation by Phenolic Antioxidants from Grapes and Wines

Current research suggests that wine contains substances that may reduce the mortality rate from coronary diseases. The oxidation of low-density lipoprotein (LDL) is thought to be a key step in the development of atherosclerosis. Phenolic fractions of a Petite Syrah wine were evaluated for their antioxidant activity in inhibiting LDL oxidation in vitro . The more active fractions contained components of the catechin family. The catechin oligomers and the procyanidin dimers (B₂, B₃, B₄, B₆, B₈) and trimers (C₁, C₂) were extracted, isolated and purified from grapes seeds. These compounds were tested for their inhibition of LDL oxidation, along with other monomeric wine phenolics. The procyanidin dimers B₂ and B₈, and trimer C₁, and the monomers catechin, epicatechin and myricetin had the highest antioxidant activity. The procyanidin dimers B₃, B₄ and C₂ and the monomers gallic acid, quercetin, caffeic acid, and rutin, and a group of compounds that included the dimer B₆, ellagic acid, sinapic acid, cyanidin had lower antioxidant activity and α-tocopherol had the least activity. Thus, the numerous phenolic compounds found in wine are potent antioxidants in inhibiting LDL oxidation in vitro .     

Comparison and Chemometric Analysis of the Phenolic Compounds and Organic Acids Composition of Chinese Wines

Characteristics of 106 wines from 5 major grape varieties and 3 typical geographic regions in China were investigated by means of profiling of organic acids and phenolic compounds analysis. An ultra‐performance liquid chromatography method was developed and thus, large number of samples could be determined in a quick and reliable way. The results showed that different origins and varieties were characteristic of various profiles of organic acid and phenolic compounds. In order to investigate possible correlation between organic acids and phenolic compounds content and grape variety and/or geographical origin, analysis of variance and linear discriminant analysis (LDA) were conducted. A satisfactory LDA result for red wines according to geographic origin was obtained, in which the correct classification was 100% and the leave‐one‐out validation accuracy was 90%. The corresponding results of white wines were 91% and 86%, respectively. When LDA was processed, according to grape varieties, the proportionality of successfully classified wines was 96%, while the leave‐one‐out validation accuracy was 94%. The organic acids and phenolic compounds profiles were useful in the classification of Chinese wines according to grape variety and geographic origin.     

葡萄酒中14种单体酚的高效液相色谱测定

建立一种新的、同时测定葡萄酒中14种单体酚含量的高效液相色谱法。采用ZORBAXSB-C18色谱柱(4.6mm×250mm,5μm),乙腈-冰醋酸-水溶液为流动相,梯度洗脱,流速为1.0mL/min,柱温30℃,检测波长280nm。测定6种不同地区、不同年份的赤霞珠干红葡萄酒中14种单体酚的含量。结果表明,不同地区相同品种葡萄酒中没食子酸、儿茶素、表儿茶素3种单体酚含量均较高,但14种单体酚含量各不相同,同地区不同年份的赤霞珠葡萄酒单体酚含量亦有差别,葡萄酒中几种主要单体酚随时间的变化含量均有降低,同时伴随着部分单体酚含量的增加。     

Changes of Phenolic Acids During Aging of Organic Wines

Grapes (Vitis vinifera L. origin var: Carignane, Cabernet Sauvignon, Merlot, Grenache, Columbard, and Semillon) were cultivated and processed according to accepted organic agriculture and organic wine techniques. Aged wines (5 years) were evaluated for changes of their phenolic acids. The highest reduction of gallic acid concentrations were determined in Cabernet Sauvignon (24.36 mg/L) and Carignane (16.00 mg/L) wines. The quantities of p-hydroxybenzoic acid decreased mostly in Carignane (22.47 mg/L) and Columbard (20.84 mg/L) wines. The decreases of syringic acid were dominant in Cabernet Sauvignon (2.34 mg/L) and Carignane (1.69 mg/L) wines. In the case of ferulic acid, the highest reduction was determined in Cabernet Sauvignon (3.97 mg/L) wines. The decreases of p-coumaric acid contents were the same and mostly in Merlot (1.06 mg/L) and Grenache (1.035 mg/L) wines. The principal component analyses results demonstrated the relations among aged wines produced from different grape varieties and their phenolic acids. The distribution of data was accumulated into two groups. The first group included total phenols, gallic acid, p-hydroxybenzoic acid, syringic acid, p-coumaric acid, and Merlot/Carignane/Grenache wines. The second one included ferulic acid and Cabernet Sauvignon wine.     

Detection of Enocyanin in Cranberry Juice Cocktail by HPLC Anthocyanin Profile

Adulteration of cranberry juice products by enocyanin, a colorant from grapes, was detected by comparing HPLC chromatographic profiles of cranberry anthocyanins with those from enocyanin. Two peaks present in all enocyanin samples but not in cranberries were identified as delphinidin-3-glucoside and petunidin-3-glucoside. A group of unidentified pigments which eluted after the cranberry pigments was also present in enocyanin. It was possible by considering differences in the chromatograms to detect replacement of 5% or more of the expected amount of cranberry juice in cranberry juice cocktail by a solution of enocyanin. A CG-50 column was used to concentrate the pigments followed by chromatography on a polymer styrene column at pH 1.6. The method gives reliable results even on samples 18 months of age.     

气相色谱-质谱法分析比较不同酵母发酵红树莓果酒的香气成分

以红树莓为原料,选取1203、1399、SY、RW、F151、F152 6 种果酒酵母进行发酵,通过顶空-固相微萃取法和气相色谱-质谱联用法分别对6 种果酒香气成分萃取、鉴定、分析和比较。结果表明：6 种酵母发酵的酒液中共检测出159 种香气成分,分别为45、56、67、58、66、39 种,其中相同成分占13 种。6 种果酒中的主要香气成分分别为乙醇、癸酸乙酯、辛酸乙酯、癸酸乙酯、癸酸乙酯、癸酸乙酯,含量依次为15.73%、22.05%、15.74%、18.38%、19.14%、15.24%。通过仪器测定和嗅闻感官综合判断,果酒酵母1399发酵的红树莓果酒香气较好,适宜大众口味。