Evolution of polyphenols in red wines from Vitis vinifera L. during aging in the bottle

The evolution of anthocyanins and pyranoanthocyanins (as measured by high-performance liquid chromatography) in young red wines from Vitis vinifera L. cv Tempranillo, Graciano and Cabernet Sauvignon (vintage 2000) from Navarra (Spain) was studied during 26 months of aging in the bottle. For the anthocyanin pigments of grape origin, a progressive decrease in their concentration, corresponding to first-order kinetics, was observed during this period. Independently of the anthocyanin structure studied, grape anthocyanins in Tempranillo wine presented twofold slower kinetics than those in Graciano and Cabernet Sauvignon wines, which exhibited a very similar disappearance rate. Acylated anthocyanins presented a slightly higher disappearance rate than the nonacylated ones, indicating the possible hydrolysis of the former into the latter forms. However, no distinction was observed in the kinetics of the different anthocyanidin forms (delphinidins, petunidins, peonidins and malvidins). These results indicate that during aging under nonoxidative conditions (bottle), the chemical reactivity of grape anthocyanins in wine is influenced by the grape variety, a factor that imposes over the stability associated with the chemical structure of each anthocyanin form. In relation to the evolution of pyranoanthocyanins, anthocyanin–pyruvic acid adducts presented a similar or lower disappearance rate than their corresponding anthocyanin precursors during the first months of aging in the bottle, while anthocyanin–vinylphenol and anthocyanin–vinylflavanol adducts did not exhibit significant variations during the whole period studied.     

几种红葡萄酿酒过程中花色苷组成与CIELab参数的相关分析

采用高效液相色谱-质谱联用技术测定了河北昌黎产区几个酿酒葡萄品种及其品系在葡萄酒酿造过程中的花色苷组成和含量,利用CIELab法分析了葡萄酒颜色参数及变化,采用相关性分析、主成分分析挖掘二者的相互关系。结果表明,发酵过程中同一品种不同品系葡萄酿造的葡萄酒之间花色苷种类相同,二甲花翠素类花色苷的含量远高于其他四类花色苷;不同类型花色苷影响不同的CIELab颜色参数,花色苷的B环修饰与红绿颜色参数a*显著正相关,花色苷的酰基化修饰与黄蓝颜色参数b*显著负相关,聚合花色苷与亮度L*显著负相关。红葡萄酒中花色苷的含量随酿造过程逐渐下降,且在主成分图上分布存在差异。     

Effect of the Prefermentative Addition of Five Enological Tannins on Anthocyanins and Color in Red Wines

Abstract: The effects of prefermentation addition of 5 exogenous tannins with different‐origin anthocyanins and color characteristics were investigated in “Cabernet Sauvignon wines” at the end of alcoholic fermentation and the end of malolactic fermentation, and after 6 mo and 9 mo of bottle aging, respectively. The results showed that the application of GSKT2 could significantly retard the degradation of most anthocyanins in the process of alcoholic fermentation and the decrease of some pyranoanthocyanins during the subsequent 3 stages, thus causing more yellowness of wine in comparison with the control. Three other condensed tannins, GSKT1, QUET, and GSET, had a positive impact only on several anthocyanin components. Four condensed tannins all contributed to more redness, suggesting that the action mechanism might be to protect wine against oxidation or contribute to form copigmented anthocyanidins, or polymeric pigments. The application of FOLT (hydrolysable tannin) did not produce any influence on wine redness even after 9 mo of bottle aging. This work provides some reasons for the reasonable application of tannin additives. Practical Application: The prefermentative application of condensed tannins overall could protect some pigment components from degradation and enhance wine redness. Tannin additives with different origins have different effectiveness. The tannin additive obtained from grape skins, like GSKT2, could produce significant promotion on both redness and yellowness in wine. The prefermentation addition of hydroxylase tannin like FOLT seems not to have a significant effect on wine color.     

贺兰山东麓新红葡萄酒颜色品质综合评价与相关性分析

采用高效液相色谱法测定葡萄酒中6种花色苷组分及含量。结果表明,葡萄酒颜色感官得分与花翠素（Dp）、花色苷总含量（ACY）呈极显著正相关（P＜0.01）,与3'甲基花翠素（Pt）、3'5'-二甲基花翠素（Mv）、总色素（WCA）呈显著正相关（P＜0.05）,与花葵素（Pg）、花青素（Cy）、3'甲基花青素（Pn）不相关（P＞0.05）。通过主成分分析,将15个颜色参数简化为3种主成分,第一主成分是由Dp、Cy、3'甲基花翠素（Pt）、Pg、Mv、颜色感官评分（S.V）、红/绿色分量（a*）、饱和度（c*）、聚合色素（PPC）、总色素（WCA）、葡萄酒颜色（WC）11个相关程度较高的变量所构成,第二主成分是由蓝/黄色分量（b*）和色调（H*）构成,第三主成分是由Pn和L*构成,累积贡献率达78.72%,并得到3个主成分和15种颜色参数的线性组合关系。     

Chromatic characteristics and anthocyanin profile of a micro-oxygenated red wine after oak or bottle maturation

Micro-oxygenation (MOX) was applied to a red wine for 5 months following the end of alcoholic fermentation and then both a non-oxygenated control wine and the micro-oxygenated wine were matured in oak barrels or bottles. The concentration of anthocyanin and anthocyanin-derived compounds and the chromatic characteristics of the control and micro-oxygenated wines after the maturation period were studied. Anthocyanin and anthocyanin-derived compounds composition were determined by liquid chromatography-mass spectrometry; and, together with monomeric anthocyanins, compounds including direct anthocyanin-flavanol adducts, ethyl-linked anthocyanin-flavanol compounds, and pyranoanthocyanins were identified. The results showed that the improvements in the chromatic characteristics obtained by applying the MOX technique to Monastrell wines were maintained after an aging period in bottle or barrel. The color intensity of wines increased during maturation in oak barrels, whereas the color of the bottled wines decreased, although MOX wines always showed higher color intensity than the respective control wines. Bottled wines also showed a higher increase in tint and a lower quantity of compounds resistant to SO₂ discoloration than oak matured wines, indicating that the formation of these compounds is favored by the oxidative conditions in oak barrels.     

‘桂葡6号’葡萄酒花色苷组分HPLC-MS分析

利用高效液相色谱-质谱联用技术测定野生资源‘桂葡6号’乙醇发酵结束和瓶储3?个月的葡萄酒中花色苷类物质的组成及含量,并与欧亚种‘赤霞珠’进行对比。结果发现,‘桂葡6号’乙醇发酵结束和瓶储3?个月酒样中花色苷总量为548.94?g/L和427.89?g/L,分别是同期‘赤霞珠’的1.2?倍和2.7?倍左右。‘桂葡6号’乙醇发酵结束和瓶储3?个月酒样中分别检测到25?种和19?种花色苷,双糖苷是其中最主要的花色苷类型,含量最高的是甲基花青素-3,5-O-双葡萄糖苷。与欧亚种‘赤霞珠’相比,瓶储3?个月‘桂葡6号’酒样中3’,5’-羟基取代花色苷比例较高,而酰基化、甲基化和吡喃型花色苷比例较低。‘桂葡6号’花色苷组成及含量与欧亚种‘赤霞珠’差异明显,这由其品种特性决定。?     

Effect of the modifier (Graciano vs. Cabernet Sauvignon) on blends of Tempranillo wine during ageing in the bottle. I. Anthocyanins, pyranoanthocyanins and non-anthocyanin phenolics

The effect of Graciano (GRA) (Spanish valuable variety of limited production) vs. Cabernet Sauvignon (CS) (world wide known French variety) wines on the anthocyanin, pyranoanthocyanin and non-anthocyanin phenolic composition of wines from Tempranillo (TEM-base wine) (largely cultivated Spanish variety) was studied in wine blends prepared with 25% and 10% (v/v) of each modifier after 4, 6, 9, 16.5 and 23 months of ageing in the bottle. Blending mainly resulted in a higher concentration of peonidin anthocyanins for the TEM-GRA blends, of acetyl-glucoside anthocyanins and anthocyanin-pyruvic acid adducts for the TEM-CS blends, and of flavanols for the blends with both GRA and CS varieties, giving rise to wines with a more balanced anthocyanin/flavanol ratio. Blending also enhanced the changes expected to occur in the phenolic compounds during ageing in the bottle. Particularly, anthocyanins and flavanols in the blends disappeared faster than in the base wine, and this was more pronounced for the 75:25 than for the 90:10 blends. These effects were similar for both modifier wines, independent of the specific changes produced in the anthocyanin profile of the base wine, but coincided with the similar optimization of the anthocyanin/flavanol ratio provided by both Graciano and Cabernet Sauvignon wines.     

Effect of Oak Chips on Evolution of Phenolic Compounds and Color Attributes of Bog Bilberry Syrup Wine During Bottle‐Aging

This study investigated the evolution of phenolic compounds of bog bilberry syrup wine during a bottle‐aging process, and further estimated the oak chip treatment on the wine color alteration. The wine was macerated with oak chips (2 or 5 g/L under light or medium toasting level) for 20 d and then bottle‐aged for 6 mo. Results showed that the oak chip treatment significantly increased the content of phenolic compounds and enhanced the copigmented anthocyanin level before aging. It also resulted in an increase on a^* and C^* but a decrease on L^*, b^*, and H^* of the wine. During aging process, a content decrease of total phenol and antioxidant capacity of the wine was observed. Phenolic acids, flavonol glycosides, and anthocyanins reduced the content, whereas flavonol increased the content. Free and copigmented anthocyanin levels decreased, whereas polymerized anthocyanins level increased. This process caused an increase on L^*, b^*, and H^*, but a decrease on a^* and C^*. The oak chip treatment delayed the wine color change and its effect was mainly depended on the addition amount. Partial least square regression revealed that flavonol glycosides, phenolic acids, and anthocyanins displayed a positive correlation with L^*, b^*, and H^*, but a negative correlation with a^* and C^*. Quercetin‐3‐O‐glucuronide, myricetin‐3‐O‐galactoside, chlorogenic acid, and quercetin exerted a more important effect on the color alteration in wine.     

Changes in the color components and phenolic content of red wines from Vitis vinifera L. Cv. “Tempranillo” during vinification and aging

Changes in phenolics and color components during vinification and aging of Tempranillo wines were studied. Different phenolics display different diffusion into the must, and with the exception of proanthocyanidins and acetyl-glucoside anthocyanins, with maximum concentration at the end of postmaceration, the rest of the unacylated and coumarated anthocyanins, monomeric flavanols, and hydroxycinnamic acids reached their maximum at the end of alcoholic fermentation. This resulted in a significant increase in both wine color and stable color, mainly due to the formation of copigmentation complexes, although polymeric pigment formation was also important. Malolactic fermentation produced a significant decrease in flavonoid content while nonflavonoid concentrations were maintained, prompting a considerable loss in wine color, despite the dramatic increase in bisulfite-stable color. Wine oak aging did not produce any significant change in the studied parameters, while bottle aging reduced the level of monomeric anthocyanins and flavanols, and hydroxycinnamic acids. However, wine color remained stable due to a significant increase in stable color. Polymerization reactions of anthocyanins prevailed over pigment degradation reactions, and copigmentation was still relevant after 2 years of bottle aging.     

红葡萄酒花色苷结构和颜色的关系研究进展

花色苷是红葡萄酒颜色的主要物质基础.本文根据花色苷结构,对其进行了分类,即基本花色苷(非酰化花色苷)、酰化花色苷、吡喃花色苷和聚合花色苷;并对其结构和颜色的关系进行了综述讨论,为葡萄酒颜色机理的研究提供参考.     

Application of a Novel Small-Scale Sample Cleanup Procedure Prior to MALDI-TOF-MS for Rapid Pigment Fingerprinting of Red Wines

This study evaluates the anthocyanin and derived pigment composition of Vitis vinifera red wines of Vranec, Merlot, and Cabernet Sauvignon produced in 2006, 2007, and 2008 vintages from the Tikve? wine region in the Republic of Macedonia. Their profile was established using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) technique. A total of 22 anthocyanins and derived pigments have been identified in the samples including 10 anthocyanins, 1 ethyl-bridged flavanol–anthocyanin adduct, and 11 pyranoanthocyanins. MALDI-TOF-MS analysis was performed after solid-phase extraction of the wines by using, for the first time, the Zip-Tip® C18 stationary phase, introducing a novel small-scale sample cleanup procedure prior to the rapid MALDI-TOF-MS fingerprinting of wine samples. 2′,4′,6′-Trihydroxyacetophenone (dissolved in acetonitrile/water 1:1, v/v) was used as a matrix. The qualitative screening of anthocyanins and derived pigments with MALDI-TOF-MS confirmed the presence of glucoside, acetylglucoside, and p-coumaroylglucoside derivatives of anthocyanins in the wine samples. Furthermore, pyranoanthocyanins formed by reactions of anthocyanins with pyruvic acid and acetaldehyde, as well as flavanol–pyranoanthocyanins and ethyl-bridged flavan-3-ol-anthocyanin adduct pigments have been detected in the samples.     

吡喃花色苷结构及其性质研究进展

吡喃花色苷是近年来率先发现于陈酿红酒中的花色苷衍生物。吡喃花色苷不仅能在一定程度上影响红酒的颜色与风味,而且其更好的稳定性也为花色苷结构修饰提供了新的思路。本文旨在综述目前常见吡喃花色苷结构特征、形成途径及其相应的理化性质,并阐述吡喃花色苷结构与色泽特征、生物活性之间的关系,以期为吡喃花色苷的定向合成与生物活性方面的应用提供参考。     

Identification of novel pyranoanthocyanins in berry juices

In most fruit and berry products the attractive red color is unstable and easily susceptible to degradation. The colors of strawberry and raspberry juices can be enhanced and stabilized by the addition of cinnamic acids. The aim of this study was to identify the novel anthocyanin products responsible for the improved juice color. The pyranoanthocyanins formed were detected using high-performance liquid chromatography, and the fractions from this were analyzed using a nano-ESI tandem MS technique. The pyranoanthocyanins identified were formed from reactions of the main anthocyanins of strawberry and raspberry juices with ferulic acid or sinapic acid. The new anthocyanin derivatives were the 4-vinylguaiacol and 4-vinylsyringol adducts of pelargonidin and cyanidin. This is the first time that pelargonidin 3-glucoside-based vinylphenol pyranoanthocyanins and pyranoanthocyanins with more complex sugar residues have been found. This is also the first time pyranoanthocyanins have been detected in strawberry and raspberry juices.     

贺兰山东麓赤霞珠干红葡萄酒陈酿过程中颜色变化研究

研究贺兰山东麓赤霞珠干红葡萄酒陈酿过程颜色特性和花色苷变化规律。以贺兰山东麓同一酒庄10个垂直年份(2005—2006年、2008—2015年)赤霞珠干红葡萄酒为实验材料,测定其CIELab颜色空间参数,利用光谱和液相色谱方法量化分析葡萄酒样品中花色苷的组成和含量。结果表明,随着酒龄的增加,明亮度L*、黄色色调b*呈增加趋势,红色色调a*呈降低趋势;综合指标色调角H*ab呈增加趋势,在陈酿前4年增量明显,在陈酿第8年之后趋于稳定。反映在葡萄酒颜色上,供试酒样在前4年由紫红色迅速向黄红色转变,8年后稳定在棕红色;葡萄酒总花色苷的含量呈下降趋势,最高为2015年酒样197.85 mg/L,在陈酿前4年迅速下降至71.18 mg/L;陈酿第8年下降至16.53 mg/L并趋于稳定,其变化规律与颜色“黄移”规律一致。从颜色的变化来看,贺兰山东麓的赤霞珠干红葡萄酒与法国波尔多地区相比稳定性略差,与之前对宁夏产区葡萄酒颜色稳定性的研究结果相一致。实验建立了酒龄与色调角、总花色苷含量间的回归方程,拟合度好,可以作为判定贺兰山东麓赤霞珠干红葡萄酒酒龄的简便方法。     

吡喃花色苷类衍生物家族的研究进展

吡喃花色苷是近些年发现于果酒（如红葡萄酒）中的新型花色苷衍生物,是酒体最重要的呈色物质之一。吡喃花色苷家族具有第四个吡喃环的基本特征,是在发酵、陈酿过程中由浆果花色苷与葡萄糖发酵代谢的中间产物及（或）浆果中其他酚类成分经环加合反应形成的一系列天然色素物质。本文将系统介绍吡喃花色苷家族及其第二代衍生物家族的种类、分子结构、形成机制、稳定性与色度特征、抗氧化及抗肿瘤等生物活性。多种不同类型的吡喃花色苷家族不仅是重要呈色物质,而且具有较高的稳定性、良好的色泽特征及较强的功能活性,本文为进一步开展吡喃花色苷类衍生物的结构与其稳定性、色泽和功能性质关系的研究及其在葡萄酒产业和食品加工业中的应用提供有益的参考。     

橡木桶对葡萄酒陈酿中花色苷的影响

采用高效液相色谱对两种赤霞珠干红葡萄酒在陈酿过程中花色苷的变化进行分析,发现二甲花翠素3-O-葡萄糖苷、二甲花翠素3-O-乙酰葡萄糖苷和花翠素3-O-葡萄糖苷是戎子酒庄赤霞珠干红葡萄酒的主要呈色花色苷。陈酿过程中,2号酒的总花色苷下降高于1号酒;1号酒二甲花翠素3-O-肉桂酰葡萄糖苷的下降率最高,2号酒甲基花青素3-O-肉桂酰葡萄糖苷的下降最高;不同型橡木桶对酒中花色苷的降低区别较为明显;三种呈色花色苷的下降与总花色苷下降高度相关。     

5 个调色葡萄品种酚类物质轮廓分析

对调色葡萄品种‘烟73’、‘烟74’、‘Kolor’、‘Tintorera’和‘Dornfelder’成熟期果实和小规模发酵的葡萄酒进行基本理化指标和酚类物质分析。结果表明,‘Kolor’和‘烟73’果实花色苷含量较高,均超过4?000?mg/kg（以果实鲜质量计）;‘Tintorera’和‘烟73’果实黄酮醇含量较低,分别为43.99?mg/kg和59.6?mg/kg（以果实鲜质量计）;‘Dornfelder’果皮黄烷醇含量最低。在5?个调色葡萄酿造的葡萄酒中,‘烟73’的花色苷质量浓度最高（1?827.87?mg/L）;‘Tintorera’葡萄酒中黄酮醇（19.87?mg/L）、黄烷醇（35.34?mg/L）和酚酸（43.77?mg/L）质量浓度都低于其他品种。对果实花色苷含量进行主成分分析,能将大部分品种很好地区分。在此基础上构建正交偏最小二乘判别分析模型,能将各品种的果皮和果肉很好地区分,筛选出的差异物质大多为F3’5’H羟基取代花色苷。利用葡萄果实和葡萄酒中共同的酚类物质构建Pearson相关系数模型,结果显示,有70.37%的物质具有较强的相关性。本研究针对调色葡萄的酚类物质轮廓进行分析,能为干红葡萄酒以颜色和辅色为目的的调配提供基础。     

中国东亚种红葡萄酒的颜色特征及酚类组成研究

为探究东亚种红葡萄酒的颜色特征以及酚类物质轮廓,采用分光光度法、酶标仪和高效液相色谱-串联质谱（HPLC-MS/MS）技术分别对3款东亚种、3款欧亚种及2款杂交种（山葡萄×欧亚种）红葡萄酒的颜色和酚类物质组成进行分析,并对其花色苷衍生物进行鉴定。结果表明,与欧亚种红葡萄酒相比,东亚种红葡萄酒的辅色花色苷含量较高（55.63%～55.66%）,而聚合花色苷含量较低（19.63%～27.01%）,并且花色苷含量较为丰富（399.30～829.95 mg/L）,以花色素-3,5-O-双葡萄糖苷为主（＞97.50%）,酰化花色苷较低（＜21.78%）。花色苷衍生物检测结果表明,东亚种红葡萄酒中的花色苷与（表）儿茶素聚合产物和吡喃花色苷的含量极低（痕量水平）。东亚种红葡萄酒在非花色苷酚组成上的突出特点为单体和二聚体黄烷醇的含量极低,因此其对酒体颜色的潜在影响可能较小。     

红葡萄酒中花色苷衍生物结构研究进展

颜色是影响红葡萄酒感官质量的重要指标之一,红葡萄酒颜色的深浅不仅决定着葡萄酒的感官品质,而且 对葡萄酒内在品质也有较大影响。花色苷是红葡萄酒中一种重要的水溶性天然色素,具有多种重要的生理功能和生 物活性。近年来发现的一些花色苷衍生物作为花色苷家族重要的补充,其种类、状态和含量对红葡萄酒的色泽特征 和陈酿潜能起到重要的作用。本文系统介绍了在红葡萄酒中发现的主要花色苷以及不同类型花色苷衍生物的结构特 征、形成途径和理化性质,以期为葡萄酒中花色苷衍生物的结构研究提供有益参考。     

Effect of the modifier (Graciano vs. Cabernet sauvignon) on blends of Tempranillo wine during ageing in the bottle. II. Colour and overall appreciation

The effect of Graciano (GRA) (Spanish valuable variety of limited production) vs. Cabernet Sauvignon (CS) (world-wide known French variety) on the colour of wines from Tempranillo (TEM-base wine) (largely cultivated Spanish variety), was studied in wine blends prepared with 25% and 10% (v/v) of each modifier after 4, 6, 9, 16.5 and 23 months of ageing in the bottle. Although possessing pH values very similar to the base wine, the blends of TEM with GRA or CS wines showed chromatic changes (higher a*, C*, CI, %red and %dA, and lower h, %yellow, tint and L*) that were perceptible by the human eye, even when using as little as 10% of modifier wine. However, no differences in colour parameters were found between the TEM-GRA (90:10) and the TEM-CS (90:10) blends, and between the TEM-GRA (75:25) and the TEM-CS (75:25) ones, this being consistent with the results relating to the temporal evolution of anthocyanins and flavanols (Part I). Moreover, the results of the principal component analysis indicated that the degree of interrelation existing between the colour parameters and the phenolic components during ageing in the bottle was similar for the TEM-GRA and TEM-CS blends. From a practical point of view, the ANOVA analysis also demonstrated that for any of the modifier wines used, certain colour parameters and phenolic components allowed differentiation between the base wine and the 75:25 blends, whereas others allowed differentiation between the base wine and both the 90:10 and 75:25 blends, during the ageing period studied. Some similarities between GRA and CS as modifier wines of TEM blends were also found in terms of their organoleptic characteristics, also demonstrating that both varieties could render blended wines with better overall quality attributes than the base wine after 23 months of ageing in the bottle.