葡萄酒中溶解氧与酚类物质的研究进展

微量溶解氧对葡萄酒的成熟起着十分重要的作用。简要介绍了葡萄酒中主要酚类物质——单宁和花色素苷。着重论述了在微量溶解氧条件下。单宁和花色素苷向更稳定色素转化的三种基本途径，以及葡萄酒中酚类物质的变化对葡萄酒品质的影响。最后。展望了溶解氧在葡萄酒熟化过程中的应用前景以及应注意的问题。     

Characterization of Uva Longanesi Red Wine by Selected Parameters Related to Astringency

This research represents a first attempt to chemically characterize wines produced from the autochthonous grape variety, Uva Longanesi, based upon the phenolic compounds responsible for its high astringency as confirmed by preliminary sensory analysis. In addition, a wine produced from Sangiovese, the most popular grape variety in the Emilia-Romagna region, was analyzed for comparative purposes. Results showed that Uva Longanesi wine had a higher pH, alcohol concentration, and total dry extract than the Sangiovese wine. With regards to phenolic constituents, the Uva Longanesi wine had higher color parameters and greater concentrations of total phenolics, including monomeric anthocyanins, small polymeric pigments, and tannins. The phenolic composition of Uva Longanesi wine was found to be responsible for the high reactivity of the wine during fining trials.     

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.     

Analysis of pigmented polymers in red wine by reverse phase HPLC

A reverse phase HPLC method has been developed for the quantitative analysis of pigmented poly-phenolic polymers in red wines. Pigmented polymers were well separated from anthocyanins and other simple wine pigments and eluted last as a single peak. The polymeric and polyphenolic nature of this peak was confirmed by its precipitation with gelatine and its behaviour during ultrafiltration and chromato-graphy on Sephadex LH20. This method correlates well with spectrophotometric measures of total pigmented polymers and indices of wine age. The proportion of the pigmented material incorporated into polymers increased with increasing wine age.     

Anthocyanin composition and content in grape berry skin in Vitis germplasm

The composition and content of anthocyanins were surveyed by HPLC–MS for assessing genotypic variation in berry skin of 110 grape cultivars, including 3 species and 5 interspecific hybrids. Twenty-nine anthocyanins were identified. For total anthocyanin content, Vitis vinifera and hybrids of Vitis labrusca and V. vinifera were low, and in general, wild species and rootstock were higher than interspecific hybrids, and wine grapes were higher than table grapes in the same species. As regards the composition of anthocyanins, malvidin-derivatives were the most abundant anthocyanins in the majority of germplasms. All anthocyanins were monoglucoside derivatives in V. vinifera, but all the other Vitis germplasms had both mono- and di-glucoside derivatives. Moreover, peonidin-derivatives and malvidin 3-O-glucoside were, respectively, main anthocyanins in table and wine grapes of V. vinifera. Via principal component analysis, the distribution of the cultivars in a scatter plot depended upon their total anthocyanins content, mono- and di-glucoside derivatives.     

Influence of different aging systems and oak woods on aged wine color and anthocyanin composition

The evolution of a red wine, Cigales appellation in origin, was studied during its storage in three different aging systems (barrels, chips, and staves) made of different kinds of oak wood (American, French, and Hungarian). The results obtained were analyzed in order to determine the content of anthocyanins in wine according to the aging system used. The studied variables were monoglucosides of delphidin, cyanindin, peonidin, petunidin and malvidin (as acetic and p-coumaric esters), as well as vitisin A, malvidin-3-O-caffeylglucoside, and color variables. The relationship between the anthocyanins and color variables stressed the importance of these compounds during the formation of pigments characteristic of aged wine, and highlighted how they are affected by the aging system chosen.Analysis of the results allowed us to define the evolution of the wine accordingly to the aging system and the botanical species of wood used. Wine treated with chips evolved more quickly than wines treated with the other two systems, because there was a higher loss of anthocyanins and an increase in brownish tonalities. On the other hand, wine treated with Hungarian oak wood suffered a slightly higher loss of anthocyanins than those aged with French and American oak wood.     

贮藏及热处理对桑葚酒中多酚类物质含量的影响

为研究桑葚酒在4,25和45℃的贮藏温度下贮藏10 d后多酚类物质含量的变化情况,通过检测总酚含量、总黄酮含量、花青素保留率、羟基自由基清除率四个指标来确定桑葚酒的最佳贮藏温度。通过对桑葚酒进行热处理,检测桑葚酒在60,70和80℃的温度下花青素保留率随加热时间的变化规律。结果表明:桑葚酒适宜在25℃的贮藏温度下贮藏;桑葚酒在热处理过程中的花青素保留率随热处理温度的提高和加热时间的延长而下降,桑葚酒中花青素热降解动力学模型符合一级反应规律,动力学方程为t=(lnC0-lnCt)/[(1.71×10^5)×exp(-5014.43/T)。此次研究为桑葚酒的贮藏和生产开发提供了一定理论基础。     

RELATIONSHIP BETWEEN ANTHOCYANIN PATTERNS AND ANTIOXIDANT CAPACITY IN MULBERRY WINE DURING STORAGE

Mulberry wine stored for 1, 3, and 12 months was used to investigate the relationship between wine color, copigmentation, polymerization of anthocyanins, and the antioxidant capacity of the wine. Color density, patterns of anthocyanins (monomeric, copigmented and polymeric) and antioxidant capacity were measured. The results show that copigmented and polymeric anthocyanins in mulberry wine increased from 0% and 16.63% to 20.93% and 30.44%, respectively, while monomeric anthocyanins decreased from 83.37% to 48.63%. The 1,1,Diphenyl‐2‐picryl‐hydrazyl (DPPH) radical scavenging ability increased after storage and was highly correlated with the polymeric anthocyanin content (r = 0.98). The ferric reducing ability of plasma (FRAP) reducing power decreased on storage. Sephadex G25 was used to separate the pigments into three different molecular sizes. The largest molecules were in Fraction I, which contained the polymerized anthocyanins and was associated with the DPPH scavenging activity. Fraction II, intermediate in size, contained the copigmented anthocyanins. Fraction III, the smallest in size, was composed of the monomeric anthocyanins and was associated with the FRAP activity.     

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。     

A quarter century of wine pigment discovery

The red grape berry pigments, anthocyanins, were characterized in the early 20th century, but investigations of wine pigments were stymied during that era. The question of their identity was a major challenge for wine chemists. A number of techniques showed that the pigments were polymeric in nature. Some structures were postulated by mid-century based on reactions between anthocyanins and condensed tannin, and later postulated wine pigments were observed in model reactions. Some related compounds were then observed in wine. By the end of the 20th century, the ionization of non-volatiles for mass spectrometry opened the door to these compounds. In addition, a new class of compounds was observed, the pyranoanthocyanins, a product of fermentation and aging metabolites with anthocyanins. These compounds possess the pigment stability to SO₂ and pH change that is characteristic of aged red wine. Aging experiments show a dynamic situation with shifts in the population of pigment classes over time. The very large number of diverse pigments explains why it has been so difficult to answer the century-old question of the structure of wine pigments. Our current understanding is founded on the use of mass spectral analysis using electrospray and related ionization techniques over the last 25 years. Future progress will rely on more sophisticated analysis of this very complex mixture of substances. © 2019 Society of Chemical Industry     

Grape and wine polymeric polyphenols: Their importance in enology

Phenolic compounds are important constituents of red wine, contributing to its sensory properties and antioxidant activity. Owing to the diversity and structural complexity, study of these compounds was mainly limited, during the last three decades, on their low-molecular-mass compounds or simple phenolic compounds. Only in recent years, much attention has been paid to highly polymerized polyphenols in grape and red wines. The reason for this is largely due to the development of analytical techniques, especially those of HPLC-ESI-MS, permitting the structural characterization of highly polymerized polyphenols. Furthermore, the knowledge on the biological properties of polymeric polyphenols of red wine is very limited. Grape polyphenols mainly consist of proanthocyanidins (oligomers and polymers) and anthocyanins, and low amount of other phenolics. Red wine polyphenols include both grape polyphenols and new phenolic products formed from them during winemaking process. This leads to a great diversity of new polyphenols and makes wine polyphenol composition more complex. The present paper summarizes the advances in the research of polymeric polyphenols in grape and red wine and their important role in Enology. Scientific results indicate that polymeric polyphenols, as the major polyphenols in grape and red wine, play a major role in red wine sensory properties, color stability and antioxidant activities.     

Effects of pH,sulphur dioxide,alcohol content,temperature and storage time on colour composition of a young Portuguese red table wine

In a young Portuguese red table wine (Douro Valley) a significant relationship between the colour composition (anthocyanins, polymeric pigment, colour density) and five parameters (pH, SO₂, alcohol, temperature, time of storage) were found. Higher temperature increased the loss of individual and total anthocyanins (as measured fay HPLC) during the ageing, while the wines with higher SO₂ content contained a greater amount of anthocyanins. Malvidin 3-glucoside acetate was the only anthocyanin not affected by the SO₂ content, but its concentration was related with the interaction term (time of storage × SO₂ content). Peonidin and malvidin 3-glucoside-p-coumarate were the two anthocyanins affected by the quadratic term of temperature. Three different groups of equations corresponding to the three different states of the glucoside moiety were found. The polymeric pigment absorbance increases daring conservation and with higher temperature, while the pH and SO₂ content decreased the polymeric pigment formation. The colour density of the experimental wine was related significantly to the changes of the coloured anthocyanins and to the polymeric pigment content.     

Berry skin thickness as main texture parameter to predict anthocyanin extractability in winegrapes

Red grapes are the only source of anthocyanins in wines and therefore the assessment of their extractability is important for wine quality. To date, a mathematical equation relating skin mechanical properties and anthocyanin extractability has never been performed for different ripening stages and vineyards located in a given production area. The main aim of this work was to assess anthocyanin extractability attempting to its relation with skin textural parameters. Morphological parameters, skin texture characteristics, total anthocyanin contents and extractability percentages were determined in Mencía grape berries (Vitis vinifera L.) from several vineyards and calibrated according to their density at three amounts of soluble solids. Skin mechanical properties were measured by Texture Analysis; a rapid and low-cost analytical technique. In most vineyards, an increasing tendency of texture parameter values was observed with the ripening stage but the differences were not statistically significant. The accumulation of anthocyanins in berry skin usually increased with the ripening stage. Anthocyanin extractability was no influenced by ripening stages for each vineyard studied. The study allowed to establish a skin texture parameter as predictor of anthocyanin extractability for a given production area. Thinner skins seem to be characterized by a greater release of red pigments.     

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.     

赤霞珠葡萄酒酿造过程中花色苷及颜色参数变化规律

为分析葡萄酒酿造过程中颜色品质变化规律,在葡萄酒酿造过程和贮藏期阶段性采集样品,监测了6种花色苷：矢车菊色素（Cy）、芍药色素（Pn）、飞燕草色素（Dp）、矮牵牛色素 （Pt）、锦葵色素（Mv）、天竺葵色素（Pg）以及花色苷总含量（ACY）、色度、色调、聚合色素（PPC）、葡萄酒颜色（WC）、总色素（WCA）的变化规律。结果表明,在葡萄酒酿制和贮藏阶段,不同品种葡萄酒花色苷各组分均呈现先上升,在苹果酸乳酸发酵阶段结束前达到最高而后开始呈下降趋势,在贮藏阶段后期趋于稳定。Dp、Cy、Pg、Pn、Mv、ACY、色度、WCA、WC之间均呈显著正相关（P＜0.05）,与色调不相关。PPC与色调和WC呈显著正相关（P＜0.05）。Dp、Cy占ACY的比例均呈波浪形递增趋势,Pt、Pg、Mv占ACY的比例变化不明显,维持动态稳定的趋势,Pn占ACY的比例均呈波浪形递减趋势。     

体外模拟人肠道微生物对葡萄酒花色苷稳定性的影响

目的 研究miR-499a-5p对过氧化氢(H₂O₂)诱导的心肌细胞H9c2增殖、凋亡的影响,并探讨其作用机制。方法 用细胞计数试剂盒(CCK-8)检测不同浓度H₂O₂(100、200、400、800 μmol/L)处理6 h的H9c2细胞的存活率,筛选400 μmol/L H₂O₂处理的H9c2细胞作为模型组。将模型组细胞分为miR-NC组、miR-499a-5p组、si-NC组、si-APC组、miR-499a-5p+pcDNA组、miR-499a-5p+pcDNA-APC组,用流式细胞术、免疫印迹(Western blot)、酶联免疫吸附试验(ELISA)检测各组细胞的存活率、凋亡率、活性氧(ROS)、超氧化物歧化酶(SOD)、丙二醛(MDA)及增殖凋亡相关蛋白增殖细胞核抗原(PCNA)、细胞周期蛋白依靠性激酶抑制剂(P21)、B淋巴细胞瘤-2基因(Bcl-2)、Bcl-2相关的X基因(Bax)的表达。结果 H₂O₂(100、200、400、800 μmol/L)呈浓度依赖性抑制H9c2细胞的存活,最适浓度为400 μmol/L。模型组细胞中miR-499a-5p表达显著降低,APC表达显著升高;过表达miR-499a-5p、抑制APC均可明显减轻H₂O₂诱导的H9c2细胞的增殖抑制、凋亡促进和氧化应激作用,并且miR-499a-5p还可靶向抑制APC。过表达APC逆转了miR-499a-5p对H₂O₂诱导的心肌细胞损伤。结论 miR-499a-5p可调控H₂O₂诱导的心肌细胞增殖、凋亡和氧化应激,其机制与靶向抑制APC有关,将可为氧化应激引起的心肌细胞损伤的治疗提供新靶点。     

Composition and colour stability of anthocyanins extracted from fermented purple sweet potato culture

The components and colour stability of anthocyanins in purple sweet potato were investigated. Anthocyanins were extracted from fermented purple sweet potato culture fermented by Suzhou wine starter (Rhizopus 3.851, 3.866 and Saccharomyces cerevisiae). In these purple sweet potato anthocyanins (PSPAs), five major anthocyanins were detected by high performance liquid chromatography (HPLC). Cyanidin and peonidin were found to be the major anthocyanidins in PSPAs by acid hydrolysis of anthocyanins. PSPAs were more stable under the acid conditions (pH 2.0-4.0) than the subacid conditions (pH 5.0-6.0) as per UV-Vis absorption spectra and CIELAB colour coordinates.     

Practical interventions that influence the sensory attributes of red wines related to the phenolic composition of grapes: a review

The phenolic composition of red wines is complex and intimately involved in colour, taste, mouth‐feel and aroma. There have been significant advances in knowledge of compounds with relatively simple structures, but understanding of those with more complex and probably diverse structures is challenging. A number of phenolic compounds may form temporary complexes with anthocyanins and/or be involved in reactions that lead to relatively stable coloured compounds. A wide range of phenolic compounds is implicated in the oral sensory attributes of red wines. Of particular importance are flavan‐3‐ols, including proanthocyanidins (PAs). The generally observed decline in the extractability of PAs during berry ripening is due to binding with cell wall material, which may occur within the developing berry and also from tissues brought into contact during processing. Studies have shown that exposure/reduced vigour results in an increasing proportion of skin PAs being extractable during wine making. Temperature and light influence anthocyanin with temperature probably being more important and the most sensitive stage being 1–3 weeks after véraison. Skin PAs are extracted earlier than those from seeds during wine‐making. Recent results suggest some rearrangement of skin and/or seed PAs occurs during vinification which involves the cleavage of large polymers or the aggregation of small ones. The polymeric material is particularly influential in wine astringency and is transformed by incorporation of anthocyanins into tannin‐like compounds during wine‐making and storage. Although some grape‐derived phenolic compounds contribute to the aroma of red wines, likely of greater importance are the effects of nonvolatile phenolics on the volatility of a diverse range of aroma compounds. Advances in analytical techniques are likely to provide greater insights into the structures and conformations of phenolic polymers and the role of cell wall material in relation to phenolic extraction and reaction during vinification. In relation to aroma, much more research is required to reveal the details of the interactions involving phenolics with volatile compounds. It seems likely that the ability to influence the relative extraction and subsequent reaction of skin and seed phenolics is important in the production of full colour, aromatic and long‐lived wines.     

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.