Influence of light exposure, ethanol and copper(II) on the formation of a precursor for xanthylium cations from tartaric acid

The production of xanthylium cation pigments was greatly increased when an aged, tartaric acid buffered, 12% (v/v) aqueous ethanol solution was used in a model white wine system. This suggested the formation of a precursor to the pigments during the ageing of the tartaric acid solution. On examining factors responsible for the generation of tartaric acid oxidation products in wine-like solutions it was observed that on exposure of samples to sunlight, glyoxylic acid, a known precursor to xanthylium cations, was produced. The production of glyoxylic acid was achieved in both the absence and presence of ethanol and copper(II). Hydrogen peroxide was also detected in these solutions. The results were consistent with the presence of glyoxylic acid in the aged tartaric acid buffered, 12% (v/v) aqueous ethanol solution that had frequent aeration and periodic exposure to sunlight throughout its storage. Studies on the role of hydrogen peroxide in the production of glyoxylic acid were also investigated. On the addition of hydrogen peroxide to tartaric acid solutions, with heating at 45°C in darkness, glyoxylic acid was only determined in solutions without ethanol.     

Impact of ascorbic acid on the oxidative colouration and associated reactions of a model wine solution containing (+)−catechin,caffeic acid and iron

Background and Aims: The aim of this study was to examine the oxidative reactions and associated colouration changes relevant to white wine in a synthetic wine system consisting of different combinations of 200 mg/L caffeic acid, 150 mg/L (+)?catechin and 1000 mg/L ascorbic acid, in the presence of 1.5 mg/L iron(II). Method and Results: Reactions were monitored by UV/VIS, CIELab, LC‐DAD and LC‐MS techniques. When ascorbic acid was less than 90% depleted in samples, it induced yellow/green colouration but prevented brown colouration that would otherwise result from catechin‐ and caffeic acid‐derived yellow and red pigments. However, during the loss of ascorbic acid, in the presence of either catechin and/or caffeic acid, reactions were still occurring to ‘prime’ the system for rapid colour formation. When the ascorbic acid was more than 90% depleted, the samples with catechin and/or caffeic acid had an increased rate of brown colouration compared with those to which ascorbic acid was not added. Conclusions: This study demonstrates that ascorbic acid is an effective anti‐browning agent provided it persists in the wine after bottling, but if depleted, serious brown colouration ensues. Significance of the Study: Findings detailed in this report will provide useful guidelines for the more effective use of ascorbic acid as an anti‐browning agent in bottled wine.     

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.     

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.     

Chemistry of copper in white wine: a review

Copper is one element in wine that has considerable notoriety. While current winemaking practice tends to minimise the amount of copper that results from vineyard and winery sources, the addition of copper(II), either as its sulfate or citrate, to remove sulfidic off‐odours may result in an elevated concentration in the finished (bottled) wine. Residual copper in white wine has been linked to oxidative and reductive spoilage processes, although the mechanisms are at times speculative. The presence of copper has been implicated in haze formation (copper casse) and linked to protein instability. More recent concerns include the coexistence of residual copper and hydrogen sulfide in wine stored under low oxygen conditions. The chemistry of copper is important in both white and red wine. While there are some overlapping issues, especially with respect to sulfidic off‐odours, both white and red wine display their own unique chemistry. Thus, this review describes the state of knowledge of copper in white wine, differentiating between evidence‐based claims and speculation. It also identifies areas of research that will provide a much clearer understanding of the role of copper in wine spoilage.     

Examination of the sulfur dioxide–ascorbic acid anti‐oxidant system in a model white wine matrix

The effectiveness of sulfur dioxide in inhibiting the ascorbic acid induced oxidation of (+)‐catechin in a matrix simulating white wine was investigated. At a sulfur dioxide:ascorbic acid mole ratio of 0.8:1.0, sulfur dioxide extended the delay prior to the onset of (+)‐catechin browning as measured by the increase in absorbance at 440 nm from 2 to 4 days post reaction initiation. The lengthening of the pre‐browning period was correlated with an increase in the time required to oxidise ascorbic acid completely, the sequence of events being loss of sulfur dioxide (day 3), loss of ascorbic acid (day 4) and on‐set of (+)‐catechin browning (day 4). Increasing the sulfur dioxide to ascorbic acid mole ratio to 3.0:1.0 inhibited the onset of (+)‐catechin browning over the 14‐day reaction period. This inhibition was achieved at considerable cost to the sulfur dioxide concentration, with the ratio of sulfur dioxide consumed to ascorbic acid oxidised being 1.7 compared with the expected fraction of 1.0. Reasons for the enhanced consumption of sulfur dioxide and the implications of this study for maintenance of quality in white wine production are discussed. Copyright © 2004 Society of Chemical Industry     

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.     

Sensory evaluation of bitterness and astringency of 3R(−)-epicatechin and 3S(+)-catechin

Bitterness and astringency of the monomeric flavan-3-o!s ( + )-catechin and (?)-epicatechin were rated using time-intensity (T-I) methodology. Three concentration levels (0.5. 0.9 and 1.2 g liter^?1) oi each compound were assessed, and the parameters time to maximum intensity (TMAX), intensity at the maximum (IMAX) and total duration (TTOT) were extracted from the T-I curves. No differences in TMAX for either bitterness or astringency were found between these chiral isomers or as a function of concentration within a compound. Epicatechin had a significantly higher bitter IMAX than catechin at all three concentration levels, and had a significantly longer TTOT at the two higher concentrations. Epicatechin was more astringent than catechin. but this was only significant at one concentration. Astringency TTOT was longer for epicatechin, although this was nonsignificant at the lowest concentration. The three concentrations of catechin were significantly different for both bitterness and astringency IMAX and TTOT. Epicatechin showed evidence for the astringency response plateauing above the 0.9 g litre^?1 level. n-Propylthiouracil status had no effect on perception of either bitterness or astringency.     

甘氨酸及其小肽铜配合物的可见光谱

利用可见光谱研究了甘氨酸及其二、三肽与铜元素的配位作用 .结果表明 ,氨基酸和二、三肽的配合行为不同 ,而小肽之间配合行为基本相似 .由于晶体场稳定化能效应 (CFSE)的存在 ,配位比对小肽铜配合物的结构和配合程度影响不大 ,一般趋向于 1∶1配位 .pH值对配合反应影响较大 ,以 pH值为 9最佳 .     

The role of light,temperature and wine bottle colour on pigment enhancement in white wine

Pigmentation enhancement in a Chardonnay wine with high flavan-3-ol concentration was examined by irradiating the wine under controlled conditions. Heating the wine in darkness required temperatures in excess of 50 °C before enhanced pigmentation became apparent. It was found that ultraviolet and, to a lesser extent, low wavelength visible light contributed to pigment production. The development of pigmentation depended on wine bottle glass colour: Flint > Arctic Blue > French Green > Antique Green. This is in agreement with the transmission characteristics of the bottles with even the darkest (Antique Green) allowing the transmission of some ultraviolet light. Riboflavin, when added to the wine, degraded rapidly when exposed to radiation <400 nm. The degradation of riboflavin and the onset of colour development depended on the actual amounts as well as the ratio of riboflavin to flavan-3-ol, suggesting that a complex series of reactions are occurring. A degradation product of riboflavin may be contributing to the increase in absorbance in the visible region observed during light exposure.     

乳化剂用量对( )-儿茶素在茶油乳化体系中抗氧活性的影响

基于SPME-GC建立了茶油次级氧化产物中正已醛、2-反-己烯醛、辛醛、壬醛的定量分析方法,以指示物的加标回收率和变异系数(C.V)为指标选用壬醛作为茶油的次级氧化产物指示物,结合初级氧化产物(氢过氧化物)探讨了(+)-儿荼素在茶油乳化体系中乳化剂(吐温20)用量对其抗氧活性的影响。(+)-儿茶素在不同乳化剂用量的茶油乳化体系中的抗氧活性顺序依次为:对照1%吐温201.5%吐温202.5%吐温202%吐温20。结果表明,在茶油乳化体系中(+)-儿茶素的抗氧活性随乳化剂用量的增多而降低。     

向日葵盘低酯果胶对水中重金属铜离子的吸附性能

该研究探讨了向日葵盘中的天然低酯果胶对水溶液中重金属铜离子（Cu2+）的吸附性能,检测了果胶用量、果胶溶液的pH值、吸附温度、吸附时间及共存离子的影响作用。结果表明,随着果胶的用量增加,Cu2+的去除率不断升高,但吸附量先增大后降低。而吸附量和去除率均随吸附温度的升高和时间的延长先增大后不变、随果胶溶液pH值的升高先增大后降低,并受共存离子的影响,随二价金属离子含量的增加而降低。Cu2+初始质量浓度在0~200 mg/L范围时,利用Langmuir等温方程拟合得到向日葵盘果胶对Cu2+的最大吸附量为29.94 mg/g。热力学分析表明该吸附反应是自发的、熵值增加的吸热反应。动力学分析证明该吸附过程遵循准二级动力学方程,以静电吸引作用和络合作用为主要驱动力。可见,向日葵盘低酯果胶具有较强的Cu2+吸附性能,可作为一种安全、高效、环保的生物吸附材料应用在Cu2+废水的处理中。     

In situ measurement of white wine absorbance in clear and in coloured bottles using a modified laboratory spectrophotometer

In situ absorbance of visible light by white wine in bottles was determined with a modified spectrophotometer. A linear correlation was obtained between absorbance at 420 nm (A₄₂₀) measured in a cuvette (10 mm pathlength) and absorbance of that same wine measured in a 750 mL Flint bottle (colourless transparent glass). In addition, 5 types of coloured bottles, Emerald Green, Classic Green, French Green, Georgia Green and Cobalt Blue , also yielded strong correlations. A₄₂₀ of white wine in bottles of Antique Green or Amber glass could not be measured directly due to a strong absorbance of that wavelength by the glass. However, a strong correlation was established between measurement of A₄₂₀ (cuvette) and A₅₄₀ for white wine in Antique Green bottles and between A₄₂₀ (cuvette) and either A₅₄₀ or A₆₀₀ for white wine in Amber bottles. The method employed a standard UV-Visible spectrophotometer with an inexpensive modified sample port, and proved applicable to bottles with diameters ranging from 62 mm (375 mL capacity half bottles) up to 81 mm (750 mL capacity Burgundy bottles). In situ absorbance measurements plus subsequent chemical analysis and sensory assessment of a Chardonnay wine in Antique Green bottles showed that the method provided an estimate of oxidation in this white wine. Wine absorbance spectra over the full visible range were obtained in the Flint bottle. Measurements of the absorbance of visible light by the glass of empty bottles could also be obtained and used as a form of quality control for glass bottle manufacture.     

芥子酸模拟体系化学氧化褐变反应

为了明确芥子酸化学氧化的影响因素,为今后更好地控制果蔬及其制品的褐变提供理论依据,本实验以芥子酸建立模拟体系,采用紫外可见分光光度计法在315、420 nm处分别测定芥子酸浓度及氧化产物褐变度。结果表明,对芥子酸化学氧化进行反应动力学拟合,确定符合一级反应动力学模型,其中在p H10.0条件下反应速率最大(5.38 h^-1)。正交实验结果表明,温度在0.05水平对芥子酸化学氧化褐变度影响显著,p H在0.1水平对芥子酸化学氧化褐变度影响显著,浓度在0.1水平对芥子酸化学氧化褐变度影响不显著。芥子酸在90℃比40、25℃更容易发生化学氧化,在p H10.0比p H3.7、7.0条件更容易发生化学氧化。芥子酸在高温碱性环境下更易氧化褐变,针对这一特点,在果蔬的加工过程中为尽可能避免褐变的发生,应尽量避免高温高碱等加工操作。      

低（无）醇葡萄酒研发进展

低（无）醇葡萄酒在保证低酒精度的同时保留了葡萄酒的营养价值,受到广大消费者的青睐。该文对低（无）醇葡萄酒不同的生产技术进行概述,并对近年来低（无）醇葡萄酒品质研究进展进行了综合分析,旨在为研究该方向的诸多学者提供理论参考。     

氧化乳糖与Fe(II)盐配合物特性

通过化学方法得到多活性反应基团的氧化乳糖,研究其与Fe(II)配位性能。利用pH值滴定法测定氧化乳糖在不同温度下的加质子常数及其与Fe(II)配位的稳定常数。结果表明温度越低,加质子常数和配合物稳定常数值都更高,说明温度越低,配离子稳定性越大或形成的配合物越难离解。红外光谱证明氧化乳糖和Fe(II)盐溶液确实发生了反应,同时根据所得的13CNMR图谱可以知道具体发生反应的C位,最后根据Job法测得配合物发生反应的配合比接近1∶1,同时推测出反应结构式。     

Yellow discoloration of the liposome system of cuttlefish (Sepia pharaonis) as influenced by lipid oxidation

Lipid oxidation, discoloration, loss of amine groups and pyrrolization of the liposome systems of cuttlefish (Sepia pharaonis) in the presence of FeCl₃ and ascorbic acid were studied. Thiobarbituric acid-reactive substances (TBARS) and the b^∗-value of cuttlefish liposomes increased with a coincidental decrease in amine groups when the incubation temperatures (0, 4, 25, and 37 °C) and incubation times (0–24 h) were increased (p < 0.05). As lipid oxidation and yellow pigment formation in the cuttlefish liposome proceeded, a loss of amine groups and pyrrolization were also detected. The effects of FeCl₃ and ascorbic acid, at different concentrations, on TBARS production, b^∗-value, loss of amine groups and pyrrolization of cuttlefish liposome were also investigated. Both FeCl₃ and ascorbic acid showed prooxidative effects in cuttlefish liposome in a concentration-dependent manner. Sodium chloride (0–2%) reduced TBARS, b^∗-values and pyrrole compounds. These results suggest a positive correlation between lipid oxidation and the development of yellow pigments in cuttlefish phospholipids.