宁夏“贺兰山东麓”葡萄酒香味物质变化规律研究
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摘要
本试验对宁夏贺兰山东麓地区三个红色主栽品种和一个白色主栽品种的一类香气和二类香气进行了检测分析,同时系统研究了干红、干白葡萄酒发酵过程中不同时期、干红葡萄酒转罐过程、瓶贮及陈酿期间风味物质的变化规律。共选取29个干红样品、9个干白样品。采用溶剂萃取法提取香气成分,经气相-质谱-计算机联用(GC-MS)分析,共检测出380种挥发性成分,其中赤霞珠141种,梅尔诺163种,蛇龙珠197种,霞多丽178种。检出率平均占总峰面积的90%左右,不同时期香气成分变化规律各异。主要结果如下:
    检测出红色品种赤霞珠、梅尔诺、蛇龙珠果实挥发性化合物分别是43、47和51种,白色品种霞多丽果实检测出81种,属于烯醛类、醛类、酮类、高级饱和、不饱和脂肪酸类化合物、脂肪酸酯和酚类化合物等。葡萄果实品种间香气成分种类、含量差异很大,其香气前体物的差异必然带来葡萄酒中一类香气、二类香气和三类香气的显著差别。
    首次利用GC-MS检测出蛇龙珠品种果实及干红葡萄酒香气化合物成分与相对含量,通过进行主成分分析,聚类分析及葡萄酒香味成分遗传研究理论参考,认为蛇龙珠品种从反映种群关系的聚类图上,也可证实蛇龙珠与赤霞珠、梅尔诺、霞多丽果实香气成分和葡萄酒香气化合物成分有较大差异。
    干红、干白葡萄酒发酵过程中,检测出赤霞珠、梅尔诺、蛇龙珠、霞多丽香气成分总共有95、99、105和131种。其中只有15、8、17和8种相同成分别伴随在发酵过程中。表明发酵过程中间产物香气变化极大。香气成分变化规律呈现出:总醇类、总脂类含量明显上升,总羧酸类、酮类明显下降。醛类一旦进入发酵则急剧转化,至发酵结束后仅有微量存在或完全消失。杂环类在发酵前期变化剧烈,有无到微量出现,由含量较高到急骤变化消失,至发酵中后期又重新出现;含氮化合物果汁中未检出,随着发酵的后期结束时逐步微量产生等的变化规律。
    分别检测了3个单品种干红葡萄酒香气化合物及相对含量。赤霞珠、梅尔诺、蛇龙珠干红葡萄酒含有57、46和49种香气成分;霞多丽干白葡萄酒分离出33种化学成分。它们主要是脂肪羧酸、脂肪醇、芳香醇、低级脂肪酸、脂肪酮、杂环类(呋喃类、噻吩类)、醚类等。在干红、干白葡萄酒中,相对含量较高的香气成分种类相似,而微量特征香气成分差异较为显著,从而构成各类不同品种葡萄酒独特香气和风格。
    干红葡萄酒转罐、成品酒、瓶贮期间,共检测出赤霞珠酒、梅尔诺、蛇龙珠含有61、59和66种香气成分,其中有31、32、32种香气分别在这三个品种香气成分变化过程中伴随全程。香气变化规律呈现出:各品种间变化规律不统一。赤霞珠醇类物质变化由最高→低→较高,酯类物质由高→低→最高,羧酸类由最低→最高→较低,杂环类由高→低,酮类由低→高,醚类由不存在到转罐、瓶贮逐渐增加的变化规律;梅尔诺香气成分总醇、杂环类含量由最高→低→较高,酯类变化由低→最高→较高,羧酸类与酮类变化
    
    
    由低→高逐步增加,醚类变化由转罐时微量存在到后期转化消失,到瓶贮期又微量生成的变化规律。蛇龙珠醇类物质含量变化递减,羧酸类含量则递增,酯类与酚类变化为先增后减,醚类由无到微量生成的变化规律。瓶贮6个月后其香气成分基本与瓶贮前香气成分种类、含量接近,保持较为稳定的态势。
    陈酿过程中蛇龙珠干红共检测出香气成分37种。2001年干红含有32种,1997年和1994年的分别为32、30种。不同年份陈酿过程中相同的香气化合物成分有25个。表明陈酿过程中,香气成分变化较为平缓。香气成分含量变化规律为:酯类由低→高→较低,醇类由高→低→最高,羧酸类、酮类及杂环类都呈现出由高→低逐渐转化的趋势,醚类化合物由低→高→较高的变化规律。
    研究表明,GC-MS仪器分析能够确保本实验的研究,但如果要确定不同品种、酒种的特征风味物质,还需在对香气成分结构、含量检测分析的基础上,进一步对香气本质的嗅感呈香特性进行分析,同时与香气的感官分析技术相结合做继续深入研究。
The aroma compounds of the main cultivated varieties and their wines from the Ningxia Helan Mountains’s Eastern Region were analyzed by GC-MS . Evolutions during stage of fermentation, racking, bottling, and aging were also studied systematically. The samples of 29 dry red wines and 10 white wines were selected. The aromatic compounds were extracted by solvent extraction and analyzed by GC-MS. Their relative contents were determined by area normalization. The total 380 chemical constituents of volatile compounds were identified and the detection rate was about 90% of the total peak area. In total 141,163,197and 178 kinds aroma were detected from Cabernet Sauvignon, Merlot, Cabernet Gernischt and Chardonnay. The results showed that aromatic compounds from grape varieties and their wines at different stages had different evolutions
    In grapes, 43, 47 and 51 aromatic compounds were found in Cabernet Sauvignon, Merlot, Cabernet Gernischt respectively. There were 81 kinds of aromatic components in Chardonnay. They belonged to olefinic aldehydes, aldehydes, ketones, higher saturated and unsaturated fatty acids, esters, phenols and other chemical groups. The grapes varieties differed widely in the categories and contents of aromatic constituents. As raw materials for dry red and white wine making, the differences in aroma precursors must cause obvious difference in aroma of fermentation and ageing wine.
    The aromatic compounds and relative contents in grapes and dry red wine of Carbenet Gernischt were analyzed by GC-MS for the first time. Using principal component analysis, cluster analysis and reference to the theoretical genetic laws for aromatic components , the aromatic composition of Cabernet Gernischt was different greatly from Cabernet Sauvignon, Merlot and Chardonnay in cluster maps.
    During the fermentation of three monovariety dry red wines and one white wine, 95, 99, 105 and 131 aroma components from Cabernet Sauvignon, Merlot, Cabernet Gernischt and Chardonnay were detected by GC-MS respectively. Through fermentation, there were 15, 8, 17 and 8 compounds separately. These indicated that the intermediate products of fermentation changed greatly. The evolution for aroma components was as follow: the relative contents of total ester, total alcohols increased obviously, but organic acids and ketones reduced greatly. Aldehydes transformed acutely once the fermentation began, and disappeared or existed as traces at the end of fermentation; while heterocyclic compounds changed violently in the early stage of fermentation from zero through traces to increasingly higher content, and than degraded totally, but they appeared again in the middle end of fermentation. The compounds containing nitrogen were undetected in the juices but were gradually produced following fermentation.
    From three monovarietal dry red wines and one dry white wine, 57, 46, 49 and 33 aromatic compounds and relative contents were detected separately in Cabernet Sauvignon, Merlot, Cabernet Gernischt and Chardonnay. There were mainly fatty acids, fatty alcohol, aralkanols, fatty ketones, heterocyclic compounds, ethers and other chemical groups. The higher relative contents and patterns of aromatic compounds were similar but characteristic aroma trace components were very different , which lead to a unique aroma and style for different variety wines.
    In racking, finished product and storage in bottle of monovariety dry red wines, 61, 59 and 66 aroma components from Carbenet Sauvignon, Merlot and Cabernet Gernischt were detected by GC-MS respectively. 31, 32 and 32 compounds in common existed through out the three processes. It showed that aroma changes greatly and uncoordinated patterns different each variety wine. The evolution in Cabernet Sauvignon was: alcohols changed in content from very high→low→high; organic acids changed in content from lowest→low→lower; esters were very high→high→super high; heterocyclic compounds degraded;
    
    
    ketones produced esters undetected in the early stage and increased gradually in the st
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