葡萄酒缩合单宁测定方法的比较研究

目的：对比葡萄酒中测定缩合单宁的甲基纤维素沉淀法(MCP法)和蛋白质沉淀法(A-H法),以寻找一种快速准确的测定方法。方法：采用两种方法测定不同类型、产地、品种葡萄酒的缩合单宁,考察其测定值和变异系数;采用液相色谱-质谱联用法(HPLC-MS法)测定缩合单宁含量,采用吸光度法(A280)测定总酚含量,并与上述两种方法的结果对照。结果：(1)MCP法和A-H法均只适用于红葡萄酒缩合单宁测定,MCP法精度略高但差异不显著。(2)MCP法测定值平均为A-H法的9.13倍,但二者存在较好的线性关系(R2=0.6029)。MCP法与HPLC-MS法线性关系良好(R2=0.7733),A-H法较差(R2=0.4843)。(3)MCP法与总酚存在良好的线性关系(R2=0.9095),A-H法与总酚无显著线性关系(R2=0.2872)。结论：两种方法均能反映红葡萄酒缩合单宁含量,但MCP法与HPLC-MS法、总酚具有更高的一致性,如采用A280测定总酚,应采用MCP法测定缩合单宁。     

Comparison of analytical methods for the determination of condensed tannins in grape skin

Background and Aims: Condensed tannins extracted from grapes are an important organoleptic component of wine. Assessing tannin level in grapes requires an effective analytical method. This study compared the efficacy of three analytical methods. Methods and Results: Condensed tannin levels were measured in 38 grape skin samples by protein and methylcellulose precipitation and by high‐performance liquid chromatography (HPLC)‐phloroglucinolysis. Total phenolics were determined by absorbance at 280 nm. Tannin levels by protein and methylcellulose precipitation were of similar magnitude, while levels determined by HPLC‐phloroglucinolysis were generally higher. No correlation was found between the level of phenolics and tannins by any of the methods employed. Neither was there a correlation between tannin levels determined by HPLC‐phloroglucinolysis and by precipitation, although previously a strong correlation had been reported between protein precipitation and HPLC‐phloroglucinolysis in wine. Conclusions: The ratio of tannin to non‐tannin phenolics is highly variable between cultivars. Each analytical method measures a different fraction of the tannin extracted from grape skin. Significance of the Study: The disparity between analytical methods requires that method selection reflect the decision‐making that will utilise the information produced. For example, protein precipitation of tannins by bovine serum albumin (BSA) has been correlated with perceived astringency; consequently this may be the best indicator of potential mouthfeel.     

Impact of exogenous tannin additions on wine chemistry and wine sensory character

Tannins are an important part of wine quality and are frequently added during winemaking. Tannin additives and their impact on wine are poorly documented. This work sought to characterize a range of enological tannins and their contribution to wine quality. Enological tannins were analysed for protein precipitable tannins and iron reactive phenolics. One tannin product was added to a Merlot wine during barrel ageing, at a range of concentrations from 60 to 300 mg/l. Condensed and hydrolysable tannins were added to Cabernet Sauvignon wine post-pressing at a recommended and excessive rate. Wines were analysed for anthocyanin, small and large polymeric pigment, precipitable tannin, iron reactive phenolics and sensory character. Enological tannins contained 12-48% tannin and recommended additions had little impact on wine tannin. High tannin additions were readily measured in the wines and were discriminated in sensory analysis with lower intensities of most parameters except brown colour, bitterness and earthy character. Recommended addition rates are too low to impact the measured tannin concentration of Merlot and Cabernet Sauvignon wines from Washington (USA). High enological tannin additions had a measureable impact on final wine had a negative impact on sensory character. Tannins are added to wines for a range of reasons and represent one of many input costs in an industry increasingly seeking efficiencies in response to global economic circumstances, over-supply and an ongoing price point squeeze. This research suggests many tannin additions may be unjustified and have limited or negative impacts on quality.     

Microwave Maceration of Pinot Noir Grape Must: Sanitation and Extraction Effects and Wine Phenolics Outcomes

Pinot noir grapes have a unique phenolic profile which can impinge on the extraction and stabilisation of compounds such as anthocyanins and tannins which contribute to the colour and mouthfeel of red wine. This study examined the concentration of phenolic compounds in Pinot noir grape must and wine following application of a novel microwave maceration treatment for red grape must. Microwave maceration was shown to be highly effective for extraction of phenolics from grape solids into grape juice. When juices were fermented to wine, ultraviolet–visible spectrophotometry showed microwave maceration was associated with significantly higher concentrations of total phenolics, anthocyanin, tannin and pigmented tannin in wine at 18 months bottle age, compared with control wine. Mean tannin concentration in microwave treatment wine was 0.60 gm/L at 18 months, compared with 0.14 gm/L in control wine. The microwave treatment was also associated with a substantial and rapid decrease in the grape-associated yeast population, compared with control maceration, and a shorter lag phase at the outset of alcoholic fermentation. Based on this study, microwave maceration warrants further investigation as a potential industrial-scale application in red winemaking.     

添加葡萄籽单宁对橡木桶陈酿‘赤霞珠’和‘马瑟兰’干红葡萄酒香气的影响

采用气相色谱-质谱联用法和感官分析排序法,研究橡木桶陈酿前添加葡萄籽单宁（200 mg/L）对陈酿12 个月后‘赤霞珠’和‘马瑟兰’干红葡萄酒香气组分和感官特征的影响。结果表明：添加葡萄籽单宁对2 个品种葡萄酒香气的影响各异。葡萄籽单宁添加促进了橡木桶陈酿期间‘赤霞珠’葡萄酒中香草酸、香草醛、香草酸乙酯、糠醛、乙酰呋喃和糠醇等橡木来源香气物质的浸出,而抑制‘马瑟兰’干红葡萄酒中糠醛、乙酰呋喃、糠醇、5-甲基糠醛和5-羟甲基糠醛等橡木来源香气物质的浸出。添加葡萄籽单宁后,‘赤霞珠’葡萄酒的生青味和浆果香降低,烘烤味增强,‘马瑟兰’葡萄酒的生青味和花香略有增强,对陈酿型干红葡萄酒的生产具有重要指导作用。     

陕西泾阳赤霞珠葡萄冷冻处理酿酒特性研究

葡萄酒中多酚、单宁等功能性成分主要来源于葡萄果皮中,为提高葡萄酒中的酚类物质含量,改善葡萄酒的口感,试验以陕西泾阳赤霞珠葡萄浆果为原料,分别在-20℃和-35℃两种不同温度下进行冷冻处理葡萄浆果并进行小容器酿酒试验,研究了葡萄原料经冷冻处理后葡萄酒中理化指标的差异变化,以及冷冻处理对葡萄酒感官特性的影响。结果表明：赤霞珠葡萄原料经-20℃和-35℃两种不同温度冷冻处理后,葡萄酒中单宁和总酚物质的含量显著增高,且-20℃冷冻处理后含量最高,其中单宁含量为29.54mg/L,总酚含量为129.71mg/L;葡萄原料经-20℃冷冻处理后,葡萄酒的外观、口感和总体评定显著提高。     

不同单宁提升赤霞珠干红葡萄酒品质的比较分析

本研究以新疆石河子产区所种植的赤霞珠葡萄为实验原料,通过在酒精发酵前分别以两种不同浓度（200 mg/L、400 mg/L）添加4种不同种类的单宁（橡木单宁、缩合单宁、葡萄单宁、鞣花单宁）,探究4种不同种类的单宁在不同添加量下对新疆产区红葡萄酒色泽及口感的影响。结果表明：当所有单宁的添加量在200 mg/L时,葡萄酒的色泽都有所提升,其中添加缩合单宁200 mg/L时,效果最为明显,色度值为21.52,该处理下葡萄酒的色度高出对照组27.25%,且随着陈酿进行到6个月时,添加缩合单宁200 mg/L的葡萄酒色度依然最高,色度值为24.38,且色泽稳定性较好,酒体呈现深宝石红色,香气较浓郁,带有甘草香。实验表明单宁的添加可以改善葡萄酒陈酿后的色泽稳定性,同时使得香气更加浓郁。该实验为新疆石河子产区的实际生产提供理论依据。     

不同皮渣浸渍发酵时间对葡萄酒中缩合单宁构成及感官品质的影响

为明确不同皮渣浸渍时间对葡萄酒中缩合单宁的影响,以赤霞珠和西拉为材料,进行不同浸渍发酵时间处理,对葡萄皮和葡萄籽以及葡萄酒中缩合单宁的含量、组成、缩合单宁以及相关口感指标等进行了分析。结果表明,不同葡萄品种中缩合单宁的初始含量、聚合度及没食子酰化率都有显著差异（P<0.05）。葡萄皮中缩合单宁的平均聚合度显著高于葡萄籽（P<0.05）,而葡萄皮缩合单宁的没食子酰化率则显著低于葡萄籽缩合单宁（P<0.05）。葡萄皮和葡萄籽中缩合单宁组成的最大差异是葡萄籽缩合单宁中不含有（?）-表棓儿茶素亚单元,而且末端单元主要是由（+）-儿茶素、（?）-表儿茶素和（?）-表儿茶素没食子酸酯组成。皮渣浸渍时间对葡萄酒中缩合单宁的组成及含量都有明显影响。随着浸渍时间的延长,葡萄酒中缩合单宁的总含量呈上升趋势,而平均聚合度则呈下降趋势。不同品种的葡萄酒之间缩合单宁含量也存在显著差异（P<0.05）,这与不同葡萄品种中酚类物质的可浸提率有关。葡萄酒中葡萄皮缩合单宁的占比一直显著高于籽粒缩合单宁的占比（P<0.05）,说明葡萄皮中缩合单宁比葡萄籽缩合单宁更容易浸提到葡萄酒中。相对于苦味和酸味,不同浸渍时间处理对葡萄酒的涩味影响更为显著（P<0.05）,综合考虑酒体的丰满度和口感的平衡,皮渣浸渍时间选择14 d左右更好一些。     

冷浸渍及单宁处理提升赤霞珠葡萄酒的品质

为研究冷浸渍及单宁处理对赤霞珠葡萄酒颜色稳定性的影响,以和硕产区赤霞珠葡萄酒为对象,通过发酵前赤霞珠葡萄冷浸渍(8℃下,4 d、8 d、12 d)及发酵过程中添加不同浓度的VR单宁(TANIN VR COLOR,0.10、0.20、0.30 g/L)处理,对赤霞珠葡萄酒的基础理化指标、酚类物质以及CIELab颜色参数进行分析。研究发现,冷浸渍处理(4 d、8 d、12 d)与对照组相比总酸含量分别提升了17.63%、15.70%、26.96%,经过不同浓度(0.10、0.20、0.30 g/L)VR单宁处理的葡萄酒总酸含量分别增加了1.33%、16.74%、13.04%;随着冷浸渍时间的延长,葡萄酒中的单宁和总酚的含量有所增加,而花色苷含量在冷浸渍8 d时达到了最大值111.04 mg/L,添加0.20 g/L VR单宁的酒样单宁、总酚及总花色苷含量分别高于对照组28.40%、26.78%、25.42%;冷浸渍8 d的葡萄酒a^*值和Cab值最高,分别为38.85和42.29,而添加了0.20 g/L VR单宁的葡萄酒b^*值和Hab值与对照组相比分别降低了1.61%、1.84%。综合比较表明,冷浸渍8 d和添加0.20 g/L VR单宁的工艺处理可以有效地提升赤霞珠干红葡萄酒的颜色稳定性。     

Analysis of grape and wine tannins: Methods, applications and challenges

Tannins are polyphenolic secondary metabolites, which can be found in many higher plants and are identified by their ability to complex with and precipitate proteins. This key property is believed to be responsible for the mouth‐feel and astringency caused by wine tannins. The analysis of tannins is of interest to practitioners in a diverse range of fields, including chemistry, pharmacology, food science, animal nutrition, ecology and plant physiology. There is a desire within the Australian wine industry to exploit objective tannin measures to complement human sensory assessment for style and quality specifications. This review, therefore, concentrates on grape‐derived condensed tannins, also known as proanthocyanidins, and wine tannins formed from grape tannins. We summarise recent advances with the development of analytical methods for the quantification of tannins, review techniques for the structural characterisation of tannin molecules and emphasise the need to refine these techniques.     

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.     

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.     

红葡萄酒中单宁分析方法与感官收敛性的关系

研究目的是使用多种分析方法评价红葡萄酒收敛性与单宁浓度之间的相互关系。选择40个红葡萄酒样品,使用不同的分析方法测定单宁含量,包括在280nm处的吸光度、4-二甲基氨基肉桂醛、蛋白质沉淀、间苯三酚反应以及凝胶渗透色谱法,结果显示：红葡萄酒中单宁测定方法与感官收敛性之间存在明显差异。感官收敛性与蛋白质沉淀方法的相关性最大（r^2=0.82）,其次为间苯三酚法（r^2=0.73）和凝胶渗透色谱法（r^2=0.74）,表明蛋白质沉淀法是感官收敛性最有用的分析方法。     

Characterisation of the main enzymatic activities present in six commercial macerating enzymes and their effects on extracting colour during winemaking of Monastrell grapes

Numerous studies have reported on the use of enzymes in wineries to facilitate the extraction of grape phenolics and to aid colour stability, although no clear conclusions were reached. Information concerning the enzymatic activities of industrial preparations is very difficult to obtain despite its importance. The aim of this work was to characterise and quantify the activities of six macerating enzyme preparations to optimise their use, and to study their effect on the chromatic characteristics of a Monastrell wine. The results indicate that differences exist in the type of enzymatic activities present in the preparations and in their concentration. The chromatic characteristics of the resulting wines, both at the end of alcoholic fermentation and after 12 months of storage in stainless steel tanks, showed differences with the use of the different maceration enzymes when comparing with control wine, although very little differences were observed between the different enzyme treatments. The enzyme-treated wines showed, at the end of alcoholic fermentation, a higher OD₂₈₀ and tannin content, and after 12 months, a higher colour intensity too. The main effect of all the preparations was an increase in the total phenol content, probably by facilitating the release of skin tannins.     

Comparison of fining red wines with purified grape pomace versus commercial fining agents: effect on wine chromatic characteristics and phenolic content

The large quantity of grape pomace (seeds, skin, and peduncle) produced during the winemaking process can be a problem and the search for procedures which could permit their valorisation is considered an important issue. This study investigates the use of purified grape pomace as a fining agent for reducing the level of some wine phenolic compounds, especially tannins. For this, purified grape pomace was applied to three young red wines of different phenolic composition and the results were compared with the effect of some common commercial fining agents. The results demonstrated that grape pomace can be used to decrease the wine tannin content with similar results to those obtained with casein, while also reducing anthocyanin content although to a similar extent to when bentonite is used. The effect of purified Monastrell grapes pomace is similar in the three different studied wines although it affected the most to wines with high monomeric anthocyanin content.     

Tannin–protein interaction is more closely associated with astringency than tannin–protein precipitation: experience with two oenological tannins and a gelatin

Relative abilities of two commercial oenological tannins to interact with a single oenological gelatin were compared with their relative abilities to elicit astringency. A trained sensory panel assessed astringency, whereas the interaction between tannins and gelatin was estimated by observing the ability of tannins both to interfere with gelatin diffusion on a cellulose membrane and to form tannin–gelatin precipitates. HPLC‐DAD chromatography and spectroscopic analysis showed that one of the commercial tannins was a hydrolysable tannin, while the other one was a condensed. The majority of the sensory panelists recognised the hydrolysable tannin as far more astringent than the condensed. The more astringent oenological tannin was found to interfere markedly with gelatin diffusion on a cellulose membrane, but it failed to produce tannin–gelatin precipitation. The condensed oenological tannin both interfered with gelatin diffusion and was a powerful gelatin‐precipitant. This study supports the hypothesis that astringency correlates better with tannin–gelatin interaction than tannin–gelatin precipitation.     

Review: Condensed tannin and grape cell wall interactions and their impact on tannin extractability into wine

It has been suggested that tannin extraction from grape berries into wine is limited by tannin binding to cell walls. Here we review the current state of knowledge and identify gaps in research that would enable characterisation of these interactions. Such characterisation could improve tannin extraction management in winemaking. The work identified in this review supports the hypothesis that tannin–cell wall interactions are formed by hydrogen bonding and hydrophobic interactions with the binding capacity of the cell walls influenced by tannin and polysaccharide structure and composition. Cell wall changes during berry development may increase the tannin-binding capacity of cell walls, while tannin structure may also influence its affinity for cell wall material. This review also identifies the need to investigate cultural and environmental factors that affect tannin and polysaccharide composition, to characterise the tannin-binding capacity of cell walls and to develop methods for assessing tannin-binding capacity of fruit prior to harvest. It is envisaged that a detailed understanding of tannin interactions with other components in the grape would lead to a predictive model for extractability of condensed tannins into wine.     

Selective removal of tannins from medicinal plant extracts using a collagen fiber adsorbent

A novel adsorbent, used for the selective removal of tannins from medicinal plant extracts, was prepared from bovine skin collagen fiber. Some typical active constituents of medicinal plants were selected as probe molecules to investigate the adsorption selectivity of the collagen fiber adsorbent to tannins. In batch adsorption experiments, the extent of adsorption of condensed tannins, including larch tannin, black wattle tannin and bayberry tannin, was 100%. The extent of adsorption of tannic acid and the hydrolyzable tannins was also 100%. In contrast, for the most active constituents of medicinal plants, their amounts adsorbed by collagen fiber adsorbent were limited. For procyanidin, the common active constituents in medicinal plant extracts, its extent of adsorption was also low, although it has a similar basic structure to condensed tannins. In comparison with traditionally used polyamide adsorbent, the collagen fiber adsorbent exhibited an obvious advantage in adsorption selectivity over tannins. Therefore, this study provides a novel and effective method for selective removal of tannins from medicinal plant extracts. Copyright © 2005 Society of Chemical Industry     

Oenological tannins: a review

This review is a state‐of‐the‐art summary of current literature on the commercial oenological tannins that are often added to wine. These tannins can come from different origins, which affect their composition and characteristics. The two main sources of oenological tannins are grapes and oak wood. This review describes methods to quantify and characterise oenological tannins and indicates that these methods also need to be improved. These tannins have different interactions with proteins as well as with wine components such as anthocyanins and other phenolics in wine. The suppliers of commercial tannins often emphasise that these products can stabilise colour in red wine and influence the mouthfeel of the wine, among other things. The literature, however, suggests that the addition of these tannins often does not lead to large differences in the chemical profile of the wine and sometimes even leads to unwanted sensory characters being observed in the wine. More research clearly is needed regarding the role of oenological tannins in wine.