The production of yellow pigments from (+)-catechin and dihydroxyfumaric acid in a model wine system

The oxidation of tartaric acid by hydroxyl radicals, produced by gamma-irradiation of aqueous solutions of tartaric acid, was shown to generate dihydroxyfumaric acid. To confirm the importance of this oxidative degradation pathway in wine oxidation, dihydroxyfumaric acid was itself reacted with (+)-catechin in a wine-like solution and the yellow pigments formed were identified by liquid chromatography mass spectrometry (LC-MS) studies as xanthylium cations. The concentration of these pigments increased if the wine-like system also contained 0.6 mg/L copper(II). The results clearly demonstrate a link between the production of yellow xanthylium cation pigments from (+)-catechin and the degradation of tartaric acid by hydroxyl radicals.     

Impact of the condition of storage of tartaric acid solutions on the production and stability of glyoxylic acid

The production and stability of glyoxylic acid was followed during the storage of tartaric acid solutions under various conditions. The solutions were prepared both with and without ethanol. Quantification of glyoxylic acid and other oxidation products, including hydrogen peroxide and formic acid, were performed using ion exclusion chromatography. Glyoxylic acid was only detected in tartaric acid samples that had been stored outdoors and sunlight was identified as the critical component of outdoor storage that allowed its formation. The hydrogen peroxide and glyoxylic acid generated under these conditions were of limited stability due to their reaction with each other to produce formic acid. The concentration of the glyoxylic acid was greatly increased when ethanol was omitted from the sample matrix. Copper(II) enhanced the stability of glyoxylic acid but slowed its production. The reaction pathway responsible for the sunlight-induced production and subsequent stability of glyoxylic acid is discussed.     

Factors influencing the production and stability of xanthylium cation pigments in a model white wine system

The influence of various wine parameters on the production and stability of xanthylium cation pigments in a wine-like medium is reported. The xanthylium pigments have an absorbance maximum in the visible region at 440 nm that is close to the measured absorbance used by the wine industry to indicate the browning of wine (i.e. 420 nm). The results of this study show that iron is more efficient than copper in both the colouration and production of xanthylium cation pigments in wine-like solutions of tartaric acid and (+)-catechin. The non-flavonoid caffeic acid can inhibit the accumulation of the xanthylium cation pigments, despite the presence of metal ions, and also influence the stability of the pigment. Sunlight leads to a decrease in the concentration of xanthylium cation pigments while a temperature difference of 20 ^oC in the absence of light was observed to have little influence on concentration. The results suggest that the xanthylium cations are more likely to be a transitory species during white wine oxidation rather than accumulating pigments based on their instability with caffeic acid.     

Copper(II)-mediated oxidation of (+)-catechin in a model white wine system

This study was undertaken to establish the role played by copper(II) in enhancing the rate of oxidation of flavanols. A model white wine system consisting of 12% (v/v) aqueous ethanol saturated with potassium hydrogen tartrate and adjusted to pH 3.2 was used to allow experimentation under well-defined conditions. (+)-Catechin was the oxidisable substrate and copper(II) concentrations up to 0.6 mg/L were employed. The model white wines were maintained at 45C to induce the browning process. Under these conditions an increase in absorbance at 440 nm occurred provided the copper(II) concentration was 0.3 mg/L or greater. The coloured species responsible for the increase in absorbance were identified as xanthylium cations, formed by linkage of two (+)-catechin molecules. Glyoxylic acid acted as the bridge between the phloroglucinol-type moiety of the (+)-catechin molecules. The production of the xanthylium cations was inhibited by ethanol and also by mannitol and the implications of these observations for a free-radical induced mechanism are discussed.     

Formation of new stable pigments from condensation reaction between malvidin 3-glucoside and (−)-epicatechin mediated by acetaldehyde: Effect of tartaric acid concentration

The objective of this work was to study the effect of tartaric acid concentration on the condensation reaction between malvidin 3-glucoside (Mv-glc) and flavanols mediated by acetaldehyde in the model solution. The model wine solutions were prepared by 12% ethanol in water (v/v) with two different l-tartaric acid concentrations (5 g/l and 25 g/l, respectively) and at two different pH values (3.2 and 1.7, respectively). Four new pigments were detected in model wine solutions containing Mv-glc, (−)-epicatechin and acetaldehyde. By reverse-phase HPLC-DAD, ESI-MS and MSⁿ fragmentation analysis, the four new pigments were tentatively identified as four isomers of hydroxyethyl malvidin-3-glucoside-ethyl-flavanol. The decrease in the concentration of Mv-glc and (−)-epicatechin and the increase in the concentration of the new identified pigments were more pronounced at higher tartaric acid concentration. At pH 1.7, although the two well-recognized ethyl-linked Mv-glc-flavanol isomers were quantitatively the major pigmented products in the reaction solution throughout the assay period, they appeared less stable than the four new pigments. At pH 3.2, the rate of formation of ethyl-linked Mv-glc-flavanol pigments was much slower than at pH 1.7, whereas the four new pigments were quantitatively the predominant pigmented products at the latter stage of the reaction.     

Preliminary studies on acidity-astringency interactions in model solutions and wines

Intensity of astringency in model solutions and wines varying in total acid and total phenols was evaluated by paired comparisons by 10 trained judges. Model solutions consisted of tannic (500, 1000, 2000 mg litre^?1) and tartaric (0, 2, 4, 6 g litre^?1) acids dissolved in aqueous solutions of ethanol (120 ml litre^?1) and sucrose (5 g litre^?1). Wine solutions were prepared by addition of citric acid (0, 0.5, 1, 2, 3 g litre^?1 as tartaric acid) to a high phenol-red wine (2645 mg litre^?1 GAE) and a moderate phenol-white wine (800 mg litre^?1 GAE). At all three levels of tannic acid, astringency of model solutions increased significantly (P<0.001) with tartaric acid concentration. Astringency of white wine also increased significantly (P<0.05) with citric acid concentration. A negative linear relation was found between relative astringency and pH at a given tannin level for both model solutions and white wine. As pH was reduced, more phenolic molecules were in the phenol form thereby increasing the likelihood of hydrogen bonding between hydroxyl groups of wine tannins and ketoimide groups of mouth proteins. The preliminary hypothesis that hydrogen bonding is the main reaction involved in the formation of protein-tannin complexes resulting in the sensation of astringency was reinforced.     

Light-induced changes in bottled white wine and underlying photochemical mechanisms

Bottled white wine may be exposed to UV-visible light for considerable periods of time before it is consumed. Light exposure may induce an off-flavor known as “sunlight” flavor, bleach the color of the wine, and/or increase browning and deplete sulfur dioxide. The changes that occur in bottled white wine exposed to light depend on the wine composition, the irradiation conditions, and the light exposure time. The light-induced changes in the aroma, volatile composition, color, and concentrations of oxygen and sulfur dioxide in bottled white wine are reviewed. In addition, the photochemical reactions thought to have a role in these changes are described. These include the riboflavin-sensitized oxidation of methionine, resulting in the formation of methanethiol and dimethyl disulfide, and the photodegradation of iron(III) tartrate, which gives rise to glyoxylic acid, an aldehyde known to react with flavan-3-ols to form yellow xanthylium cation pigments.     

Xanthylium salts formation involved in wine colour changes

Summary The reaction of (+)-catechin in wine-like model solution was investigated. First appearance of colourless dimeric compounds consisting of two flavanol units linked by carboxy-methine bridge was observed. Their isolation and further incubation was found to yield two types of yellowish pigments showing visible absorption maxima at 440 and 460 nm, respectively. Mass spectroscopy (MS) spectral analysis showed that the first type were xanthylium salt pigments formed by dehydration of the colourless compounds followed by an oxidation process. The loss of a water molecule was shown to take place between two A ring hydroxyl groups of the colourless dimers. The second type were shown to be ester derivatives of the first ones. Thus ethylester of xanthylium salt was obtained and fully characterized by mass and nuclear magnetic resonance (NMR) spectroscopy. Esterification was found to involve the colourless compound before dehydration and thus a general scheme for xanthylium salt formation was postulated. The proposed scheme constitutes a new xanthylium formation pathway as up to now only anthocyanin-flavanol reactions were supposed to form xanthylium salt derivatives during wine ageing. This work also provides new support to the contribution of xanthylium salt in colour evolution observed during wine ageing which is generally expressed in an increase of absorption in the 400–500 nm, region of xanthylium salt absorption maxima.     

红毛丹果皮色素及其稳定性的研究

红毛丹(Nephelium lappaceum L.)果皮含有较高的色素。为综合利用植物色素资源,对红毛丹果皮色素进行提取与纯化,并从光照、温度、pH 值、氧化与还原介质、防腐剂、酸味剂、糖类、VC 和金属离子方面对该色素的稳定性进行研究。结果表明：红毛丹色素属花色苷类;对自然光、高温、H2O2 和Na2SO3 的耐受性较差,在pH3 以下色泽较稳定;低浓度防腐剂苯甲酸钠对色素稳定性影响较小,柠檬酸具有一定的增色作用;乳酸、葡萄糖和蔗糖、VC 对色素的稳定性无明显的影响,但Fe3+、Fe2+、Pb2+、Sn2+ 对该色素稳定性起不利的作用。该研究为开发植物新的天然色素产品提供理论参考。     

Effect of copper on oxidation of (+)-catechin in a model solution system

Summary Autoxidation of ( +)‐catechin in a model solution system, containing cupric ions, was monitored by high‐performance liquid chromatography with diode array detection. The rate of (+)‐catechin oxidation and the extent of browning increased with the copper concentration, showing an effect of copper on browning of flavanols. The progression of the reaction showed that the appearance of new compounds, which were initially absent in the mixture, was concomitant with (+)‐catechin decrease. Numerous reaction products, including both colourless compounds and pigments absorbing at 440, 460 and 550 nm, were detected. Among the colourless derivatives, four dimeric compounds, consisting of two catechin units linked by a carboxymethine bridge, were detected. Their formation involved the condensation of flavanols, mediated by glyoxylic acid, following a mechanism similar to that previously observed with iron. The yellowish compounds that were detected were identified as xanthylium salts and their corresponding esters, showing absorption maxima at 440 and 460 nm, respectively. Comparison of the results obtained with those reported with iron showed that copper ions play similar roles in enhancing the oxidation rate of (+)‐catechin and flavanols.     

Influence of aerobic and anaerobic conditions and yeasts on the reaction between (+)-catechin and glyoxylic acid

The reaction between (+)-catechin and glyoxylic acid in wine model solutions was studied under aerobic and anaerobic conditions in the presence and absence of yeasts with a view to determine their contributions to browning of white wine. Under aerobic conditions, the presence of yeasts reduced the production of colored products, the formation rate of which was similar to that observed under anaerobic conditions and in the absence of yeasts. These results reveal that yeasts and intermediate reaction products compete for oxygen. In the absence of oxygen, the production of colored compounds was even smaller in presence of yeasts, as a result of their ability to retain browning products as they form. Because the absence of oxygen not inhibited the formation of intermediate products resulting from oxidation reactions, an alternative oxidation pathway are proposed acting the glyoxylic acid as oxidant. In the usual concentrations of catechin in white wines, the studied reaction of (+)-catechin-glyoxylic acid can contribute significantly to the alteration of the wine color.     

Maillard Browning in Ethanolic Solution

ABSTRACT: Maillard browning in ethanolic solutions of a 0.2 M glucose-0.2 M glycine (G-G) system in a heat treatment becomes more pronounced with an increase in ethanol concentration (0% to 50%, v/v). Extents of browning, as measured by absorbance at 420 nm, of a fructose-glycine system in aqueous and 50% ethanolic solutions buffered at pH 4.3 are very close after the treatment, whereas that of the G-G system in 50% ethanolic solution is much enhanced. A higher hydroxymethylfurfural (HMF) content is present in the ethanolic G-G system, suggesting the involvement of ethanol in the G-G reaction to form HMF. Evidence also shows that ethanol inhibits the formation of HMF in an ethanolic solution containing glucose alone. Much more HMF is formed in the pH 4.3 buffered G-G system in an ethanolic solution at a water activity (a_w) above 0.81 or at an ethanol concentration below 30% than in a glycerolic solution at the same a_w. We propose that the reduction of a_w is not the sole major mechanism for ethanol to accelerate HMF formation and Maillard browning in G-G solution.     

Headspace concentrations of ethyl esters at different alcoholic strengths

Ester concentrations in the headspace influence the aroma character of alcoholic drinks. Activity coefficients for esters showed log-linear decreases as ethanol concentration was increased from 17% (v/v), with rates inversely related to ester acid chain length. At concentrations below 17% (v/v) the activity coefficient remained constant. This could be related to structural changes in ethanol/water mixtures. Below 17% (v/v), ethanol forms a monodispersed aqueous solution. Above 17% (v/v), ethanol molecules cluster to reduce hydrophobic hydration and esters partition into these ethanol-rich clusters, where the lower ester interfacial tension reduces the free energy of mixing and hence the activity coefficient. The increased solubility of the ester reduced the headspace concentration of the esters, and hence total ester content may not be a good indicator of their flavour impact. © 1998 SCI.     

甘蔗渣固定化酵母酿造百香果果酒的研究

以甘蔗渣为载体吸附固定酿酒酵母（Saccharomyces cerevisiae）YJSF190,并以游离酵母作为对照,采用固定化酵母酿造百香果果酒,比较两种酵母发酵果酒中的乙醇、残糖、有机酸和乙酸乙酯含量。结果表明,游离酵母酿造百香果果酒乙醇产量为96.36 g/L,乙醇产出速率为2.01 g/（L·h）,总残糖含量为5.14 g/L,乙酸乙酯含量为14.3 mg/L,乙酸、草酸、酒石酸、苹果酸、柠檬酸、琥珀酸含量分别为21.67 g/L、0.44 g/L、0.91 g/L、3.80 g/L、44.54 g/L、3.16 g/L;固定化酵母酿造果酒乙醇产量为98.22～124.37 g/L,乙醇产出速率为2.05～3.11 g/（L·h）,总残糖含量为3.62～4.09 g/L,乙酸乙酯含量为15.7～22.86 mg/L;乙酸、草酸、酒石酸、苹果酸、柠檬酸、琥珀酸含量分别为15.11～20.18 g/L、0.27～0.44 g/L、0.78～0.96 g/L、2.61～3.80 g/L、33.40～45.83 g/L、2.22～2.68 g/L。表明固定化酵母可应用于酿造百香果果酒。     

Wine bottle colour and oxidative spoilage: Whole bottle light exposure experiments under controlled and uncontrolled temperature conditions

Exposure of a Chardonnay wine to light from a mercury vapour lamp under controlled temperature conditions showed that colour enhancement was dependent on bottle colour. The increase in colouration was Antique Green < French Green < Arctic Blue < Flint, in agreement with the transmission characteristics of each bottle type. Xanthylium pigments were identified as one component contributing to the observed enhancement of colour. The presence of oxygen was shown to be a critical factor to initiate the formation of these xanthylium pigments during light exposure. Without temperature control, wine colour development was highest in Antique Green and lowest in Flint. This alternate order reflects the ability of the darker bottles to retain heat longer than lighter coloured ones as confirmed by surface temperature decay rates. Specific pigments contributing to the wine colour enhancement in uncontrolled temperature/light exposure experiments could not be identified, although tentative evidence was obtained for the presence of flavan-3-ol based compounds. The different bottle glass surfaces did not influence the rate of loss of dissolved oxygen or oxidation of ascorbic acid. The potential to develop the results obtained in this study to identify markers for light and/or temperature exposure of white wines is discussed.     

Effect of light,pH, metal ions and antioxidants on the colour stability of norbixin in aqueous solution

Norbixin, a carotenoid extracted from the seeds of the annatto (Bixa orellana) plant, can be used in aqueous food applications, where other carotenoids are too hydrophobic to solubilise in a water environment. The aim of this work was to investigate the effect of pH, antioxidants and transition metal ions with and without hydrogen peroxide (H₂O₂) on the stability of norbixin in aqueous solutions as well as determining the interaction between these factors and light. The stability of norbixin in buffered aqueous solution stored in light or in the dark was evaluated using absorbance spectrophotometry. Light, reduced pH and metal ions both with and without H₂O₂ increased the bleaching of norbixin, whereas chelators and the natural antioxidants, ascorbic acid and tocopherol, reduced the bleaching of norbixin. Light significantly increased the loss of norbixin alone and in combination with the other factors.     

羽衣甘蓝叶片色素的基本特性及其稳定性研究

在提取纯化的基础上分析羽衣甘蓝叶片色素的基本特性及其稳定性。结果表明：羽衣甘蓝叶片色素为紫红色,极易溶于水等极性溶剂,在pH2.0 的水溶液中于540nm 波长下有最大吸收峰值。羽衣甘蓝叶片色素的颜色和吸光度受溶液pH 值变化的影响。在pH2.0 的水溶液中,羽衣甘蓝叶片色素的耐光性较好,但不耐受50℃以上的温度。酸味剂柠檬酸、苹果酸、乳酸,糖类物质蔗糖、葡萄糖、乳糖和表面活性剂SDS 对羽衣甘蓝叶片色素均有非常明显的增色与护色作用,使该色素的稳定性增强。但糖类物质会随着时间的延长(6d 以后),对色素的增色、护色作用逐渐减弱,并又逐渐出现减色作用。     

Study of Two Different Immobilized Acid Proteases for Wine Application

This study compares the hydrolytic efficiency in model wine (pH 3.2 tartaric acid buffer with 12% v/v ethanol) of two immobilized enzymes. Food-grade acid proteases (from Aspergillus saitoi and stem bromelain) were covalently immobilized on two solid supports, aminopropyl controlled pore glass beads and Eupergit®C. The effects of pore diameter, immobilization procedure, and protein properties on the activity of biocatalysts were evaluated to determine the feasibility of immobilized proteases in wine. The results expressed in terms of yield of immobilized enzyme, enzyme activity, and kinetic parameters (V_max and K_m) demonstrated that the best performance of both proteases was when immobilized in Eupergit®C.     

有机酸含量对葡萄酒发酵的影响

为了考察有机酸含量对葡萄酒发酵的影响,在初始有机酸含量分别为4 g/L、7 g/L和10 g/L的模拟葡萄汁中接种酵母,于25℃发酵,比较不同初始有机酸含量对葡萄酒发酵过程中酵母生长、降糖、有机酸及挥发性化合物含量的影响。结果表明,初始有机酸含量7 g/L时酵母生长和耗糖最慢,乙醇和乙醛产生量最低;随初始有机酸含量升高,pH值、酒石酸、苹果酸、乳酸、乙酸、总酸、乙酸乙酯和总酯含量呈下降趋势;琥珀酸、正丙醇、异丁醇、异戊醇及总高级醇含量呈上升趋势;但对β-苯乙醇、正丁醇及丁酸乙酯含量影响较小。初始有机酸含量10 g/L的葡萄酒发酵过程酵母生长快、降糖最快,产酸含量适中,同时香气较好。因此,葡萄酒发酵的适宜初始有机酸含量为10 g/L。