摘要
葡萄酒是一种成分复杂的酒精饮料，具有很高的营养保健价值，而且越来越多的消费者关心其质量保证。但是目前我国对葡萄酒原产地域产品保护的力度不强，葡萄酒原产地命名及其保护制度相关的法律法规还不够完善，国内葡萄酒的整体质量较低，市场上的葡萄酒质量良莠不齐，存在很多以次充好的现象。在此情况下，急需建立一种灵敏、快捷、准确、无损且环保的检测方法来鉴别真伪葡萄酒、不同等级的葡萄酒，乃至不同产地的葡萄酒。三维荧光光谱技术和电子舌技术具有较高的灵敏性、良好的选择性以及对样品的无损坏性，受到广泛的关注和应用。
论文的研究目的是通过三维荧光光谱技术和电子舌技术检测昌黎原产地华夏葡萄酒有限公司和越千年葡萄酒有限公司提供的单品种干红葡萄酒，建立不同品种、不同酿造年份和不同生产厂家干红葡萄酒的三维荧光光谱和电子舌特征图谱，对原产地域葡萄酒进行辨识，并据此建立一种方便快捷、科学可靠的区分鉴别不同葡萄酒的方法，为国家实施原产地域葡萄酒的保护提供科学依据，也为葡萄酒的整体特征评价与分析检测提供新的技术方法。
研究中使用荧光光度计F-7000和多频脉冲电子舌系统分别检测昌黎原产地不同品种、不同酿造年份及不同生产厂家的干红葡萄酒，得到如下结论：
1、三维荧光光谱法分析相同酿造年份的不同品种、不同生产厂家干红葡萄酒
三维荧光光谱技术检测同一酿造年份的不同品种干红葡萄酒得到：2004年及2005年酿造的5种干红葡萄酒所产生荧光峰的数量不同，且各个峰点荧光强度有显著差异。2004．年酿造的干红葡萄酒中佳美激发波长260nm和335nm处产生2个荧光峰；赤霞珠、山普斯、西拉和梅尔诺在激发波长263nm、290nm和329nm左右出现3个荧光峰；2005年酿造干红葡萄酒中佳美在在激发波长269nm和332nm处产生2个荧光峰；西拉在激发波长290nm和329nm处产生2个荧光峰；而赤霞珠、山普斯和梅尔诺分别在激发波长263nm、290nm和329nm左右出现3个荧光峰。各个荧光峰点荧光强度不同
三维荧光光谱技术检测2005年不同生产厂家的干红葡萄酒得到：不同厂家酿造的赤霞珠、梅尔诺干红葡萄酒荧光峰出现在激发波长260 nm、290 nm和329 nm左右出现3个荧光峰，各个荧光峰点的荧光强度有着明显差异。可以区分供试的不同生产厂家的葡萄酒。
三维荧光光谱技术能够通过光谱中的荧光峰数量及不同的荧光强度表征不同品种葡萄酒之间的差异，并以此为依据区分供试的不同品种干红葡萄酒。
2、三维荧光光谱法分析不同酿造年份的赤霞珠干红葡萄酒
分析不同酿造年份的赤霞珠干红葡萄酒的三维荧光光谱表明不同酿造年份酒样由于不同生长年份中以气候为主导因素，使得葡萄原料差异较大，从而引起不同酿造年份酒样中荧光物质差别较大，而不同酿造年份酒样的贮藏时间不同，也会引起不同年份酒样荧光物质成分有所变化，表现在三维荧光光谱上可以看到：1993年酿造酒样在激发波长296nm和326 nm左右出现2个荧光峰；1996年酿造酒样在激发波长329nm左右出现1个荧光峰；2001、2004和2005年酿造的酒样分别在激发波长260nm、290nm和329nm出现3个荧光峰，但是不同酿造年份的酒样各个峰点的荧光强度差异明显。所有酒样都在激发波长329 nm左右有荧光峰出现。结果表明三维荧光光谱可以表征不同酿造年份赤霞珠干红葡萄酒之间的差异，并以此为依据区分供试的不同酿造年份酒样。
3、主成分分析不同品种、不同生产厂家及不同酿造年份干红葡萄酒的三维荧光光谱
主成分分析不同品种、不同生产厂家及不同酿造年份干红葡萄酒的三维荧光光谱数据提取的前三个主成分：主成分1(PC1)、主成分2(PC2)和主成分3(PC3)的信息占有率均达75％以上，PCA得分图表明三维荧光光谱技术可以区分不同品种、不同酿造年份及不同生产厂家的干红葡萄酒。
4、多频脉冲电子舌系统分析昌黎原产地不同品种、不同生长厂家及不同酿造年份干红葡萄酒
本研究通过多频脉冲电子舌系统对昌黎原产地不同品种、不同厂家、不同年份的干红葡萄酒进行区分辨识，以铂电极、金电极、银电极、钛电极、钯电极、镉电极、铝电极和铜电极作为工作电极，每个工作电极在1 Hz，10 Hz和100 Hz三个频率段下进行扫描，数据处理采用主成分分析方法，结果显示以镉电极的1Hz频率段，银电极的100Hz频率段，钛电极100Hz频率段和金电极的10Hz频率段作为多频脉冲电子舌的最佳传感器阵列，对葡萄酒的区分辨识效果较好。
多频脉冲电子舌系统通过选择不同的金属电极作为传感器阵列，结合多元统计方法，在葡萄酒检测方面做了初步探索，为电子舌在此方面的应用提供实验基础与理论依据。
Wine is one of the most complex alcoholic beverages and has very high value ofnutrition and health protection function.More and more consumers concern the objective andauthentic of wine,but the protection of wine is not enough,and the law and regulation aboutwine control of origin are not perfect.The quality of wine is poor in our country,and there aremany adulteration in market.In this situation,there needs the technique which should hesensitive,nondestructive,rapid,environmentally friendly to discriminate the adulterate wine,class wines,even the wine with differemt thegeographic origin.Three-dimensionalfluorescence spectroscopy and electronic tongue are selective,sensitive and non-destructivetechnique,and receiving the widespread attention and application.
The objective of the present study was to assess wine from the geographic origin ofChangli County,supplied directly by the Huaxia Winemaking Company and YueqiannianWinemaking Company using three-dimensional fluorescence spectroscopy and electronictongue.In order to discriminate the wine from the geographic origin of Changli County,thethree-dimensional fluorescence spectroscopy and the electronic tongue spectroscopy of thewines with different variety,brewery and vintage were established.According to the result,ascientific method for identifying the wines quickly and reliable was established.The scientificbasis for the protection of wine with the geographic origin was provided,and the newtechnical method also can evaluated and analyze the whole characteristic of wines.
In our study spectrofluorometer(F-7000,Hitachi)and Multi-frequency amplitude pulseelectronic tongue(MFP-ET)were used to analyze the wines from the geographic origin ofChangli County with different variety,brewery and vintage,the result as follow:
1、Three-dimensional fluorescence spectroscopy was used to analyse the wine withdifferent variety and brewery.
Three-dimensional fluorescence spectroscopy with different variety produced in 2004and 2005 had obviously different in the number of fluorescent peaks and the fluorescenceintensity.The wines produced in 2004 were study,and the result showed that Gamay had twofluorescent peaks at excitation wavelength 260nm and 335nm;Cabernet Sauvignon,Shpusi, Syrah and Merlot had three fluorescent peaks at excitation wavelength 263nm、290nm and329nm.The wines produced in 2005 were study,and the result showed that Gamay had twofluorescent peaks at excitation wavelength 260nm and 332nm;Syrah had two fluorescentpeaks at excitation wavelength 290nm and 329nm;Cabernet Sauvignon,Shpusi and Merlothad three fluorescent peaks at excitation wavelength 263nm、290nm and 329nm.Thefluorescence intensity was different with different variety.
Three-dimensional fluorescence spectroscopy was applied to analyze the wine producedin 2005 with different brewery.The result showed that Cabernet Sauvignon and Merlot hadthree fluorescent peaks at excitation wavelength 263nm、290nm and 329nm,and thefluorescence intensity was obvious distinctness with different brewery.
Three-dimensional fluorescence spectroscopy can discriminate the wines with differentvariety and brewery by means of the number of fluorescent peaks and the fluorescenceintensity.
2、Three-dimensional fluorescence spectroscopy was used to analyse the wine ofCabernet Sauvignon with different vintage.
Three-dimensional fluorescence spectroscopy was applied to analyze the wines ofCabernet Sauvignon with different vintage.The result showed that the number and theintensity of fluorescence peaks were different because of climate change every year.Thethree-dimensional fluorescence spectroscopy showed that Cabernet Sauvignon produced in1993 had two fluorescent peaks at excitation wavelength 296nm and 326nm;CabernetSauvignon produced in 1996 had one fluorescent peak at excitation wavelength 329nm;Cabernet Sauvignon produced in 2001,2003,2004 and 2005 had three fluorescent peaks atexcitation wavelength 260nm,29nm and 329nm.The fluorescence intensity was obviouslydifferent with different vintage,so three-dimensional fluorescence spectroscopy can be usedto discriminate wines with different vintage.
3、Principal component analysis was used to analyze the three-dimensionalfluorescence spectroscopy of wines with different variety,brewery and vintage.
Principal component analysis was applied to analyze the three-dimensional fluorescencespectroscopy of wines with different variety,brewery and vintage,and the principalcomponent PC1,PC2 and PC3 were extracted.The information quantity of PC1,PC2 andPC3 was 75 percent of the total variance,and the score map of PCA showed that the three-dimensional fluorescence spectroscopy could be applied to discriminate the wines withdifferent variety,brewery and vintage.
4、Multi-frequency amplitude pulse electronic tongue(MFP-ET)analyzed the winewith different variety,brewery and vintage from the geographic origin of ChangliCounty
The wines with different variety,brewery and vintage were analyzed using MFP-ETthrough a sensor array of platinum,gold,silver,titanium,palladium,cadmium,aluminumand cuprum electrodes under the mentioned three frequency segments of 1 Hz,10 Hz and 100Hz.Principal component analysis was used to process the data.The results showed that thewine could be successfully discriminated by combining together gold electrode in 10 Hz,silver electrode in 100 Hz,cadmium electrode in 1 Hz and titanium electrode in 100 Hz.
MFP-ET based on selecting the appropriate sensor array which was composed of thedifferent non-modified metal electrodes and combining together the different frequencysegments of multifrequency large amplitude pulse voltammetry,and showed a promisingapplication in qualitative and quantitative analysis of wine.
引文
[1]孙方勋编著．世界葡萄酒和蒸馏酒知识[M]．北京：中国轻工业出版社，1993
[2]李华，王华，袁春龙等编著．葡萄酒化学[M]．北京：科学出版社，2005
[3]Gholami M.Biosynthesis of flavour compounds in muscat cordor blano grape berries[J].Australian Journal of Grape and Wine Research,1995,1:19～24
[4]马佩选．葡萄酒质量与检验[M]．北京：中国计量出版社，2002
[5]丁燕，赵新节．酚类物质的结构与性质及其与葡萄及葡萄酒的关系[J]．中外葡萄与葡萄酒，2003，(01)：13～17
[6]刘树文，李华，房玉林．葡萄酒的营养与保健[J]．酿酒，1999，134(5)：40～42
[7]李华编著．葡萄集约化栽培手册[M]．西安：西安地图出版社，2001
[8]李华主编．葡萄与葡萄酒研究进展[M]．西安：陕西人民出版社，2000
[9]翟衡，杜金华等著．酿酒葡萄栽培及加工技术[M]．北京：中国农业出版社，2001
[10]刘玉田，徐滋恒等著．现代葡萄酒酿造技术[M]．山东：山东科学技术出版社，1990
[11]陶永胜，李华等．葡萄酒中主要的黄酮类化合物及其分析方法[J]．中外葡萄与葡萄酒，2001，(4)：14～17
[12]Helena Vuorinen,Kaisu maatta et al.Content of the flavonols myrietin,quercetin and kaempferol in finish berry wines[J].Journal of agriculture and food chemistry,2000(48):2675～2680
[13]Stephane Carando,Pierre-Louis Teissedre,and Laurence Pascual-Martinez,et al.Levels of flavan-3-los in French wines[J].Journal of agriculture and food chemistry,1999,47:161～166
[14]刘树文，何玲等．葡萄果实中花色素合成及其影响因素[J]．中外葡萄与葡萄酒，1999(2)：79～81
[15]Hanson K.R.,HavirE A.,Inconn E E.et al.The Biochemistry of plants vlo Ⅶ secondary plant products[J].Springer-verlag,1981:329～402
[16]邓军哲，屈慧鸽．葡萄花色素的研究概况[J]．中外葡萄与葡萄酒，1996，13(2)：25～27
[17]Celestino Santos-Buelga,Augsustin Scalbert.Proanthocyanidins and tannin-like compounds-nature,occurrence,dietary intake and effects on nutrion and health[J].Journal of science of food and agriculture,2000,80:1094～1117
[18]顾国贤主编．酿造酒工艺学[M]．北京：中国农业出版社，1996．10
[19]狄莹，石碧．植物单宁化学研究进展[J]．化学通报，1999，3
[20]戴蕴青，韩雅珊，惠柏棣．红葡萄酒中白藜芦醇及其糖苷异构体的反相HPLC分析[J]．中国农业大学学报，2002，7(4)：14～18
[21]郭景南，刘崇怀，潘兴．葡萄属白藜芦醇研究进展[J]．果树学报，2002，19(3)：199～204
[22]戴群，赵光熬．HPLC测定葡萄酒中活性物质——白藜芦醇的含量[J]．工业微生物，1999，29(3)：22～24
[23]李霞．白藜芦醇[J]．精细与专用化学品，2002，(3／4)：14～20
[24]李华．现代葡萄酒工艺学[M]．西安：陕西人民出版社，2000
[25]尉亚辉，刘兴旺，李华．白藜芦醇的研究进展[J]．西北农业大学学报，1999，27(2)：188～195
[26]冯永红，许实波．白藜芦醇药理研究进展[J]．国外医药(植物药分册)，1996，11(4)：155～ 157
[27]E．T．塞默(美)著，陈祖福，林丽英等译．香味与香料化学—嗅觉的科学[M]．北京：科学出版社，1989
[28]黄梅丽，姜汝焘，江小梅．食品色香味化学[M]．轻工业出版社，1984
[29]周志红，骆世明，牟子平．番茄植株中几种化学成分的化感效应[J]．华南农业大学学报，1998：19(3)：56～60
[30]Alessandro Baldi,Annalisa Romani,Nadia Mulinacci,et al.HPLC/MS application to anthocyanins of vitis vinifera L[J].J.Agric.Food Chem,1995,43:2104～2109
[31]Corrado Di Natale,Roberto Paolesse,Antonella Macagnano.Application of a combined artificial olfaction and taste system to the quantification of relevant compounds in red wine[J].Sensors and Actuators B,2000,69:342～347
[32]Olusola Lamikanra,Casey C.Grimm,Inyang D.Inyang.Formation and occurrence of flavour components in Noble muscadine wine[J].Food Chemistry,1996,56(4):373～376
[33]Maria Pilar Marti,Montserrat Mestres,Cristina Sala.Solid-phase microextraction and gas chromatography olfactometry analysis of successively diluted samples.A new approach of the aroma extract dilution analysis applied to the characterization of wine aroma[J].Agric Food Chem,2003,51:7861～7865
[34]Boudhrioua N.,Giampaoli P.,Bonazzi C..Changes in aromatic components of banana during ripening and air-drying[J].Lebensm.-Wiss.u.-Technol,2003,36:633～642
[35]Serkan Selli,Turgut Cabaroglu.Effect of contact on the aroma composition of the musts of Vitis vinifera L.cv.Muscat of Bomova and Narince grown in Turkey[J].Food chemistry,2003,(81):341～347
[36]Rapp A.Aroma compounds of wine[M].Weinwirtschaft Technik,1989,1125:23～227
[37]Lee Seung-Joo,Noble Ann C..Characterization of odor-active compounds in CalifomianChardonnay wines using GC-Olfactometry and GC-Mass spectrometry[J].J.Agric Food Chem,2003,51:8036～8044
[38]Spayd S.E.,Tarara J M.,Mee D.L et al.Separation of sunlight and temperature effects on the composition of Vitis vinifera cv.Merlot berryes[J].Am.J.Enol.Vitic,2002,53(3):171～182
[39]Catherine Peyrot Des Gachons,Takatoshi Tominaga,Denis Dubourdieu.Sulfur aroma precursor present in S-glutathione conjugate form:indentification of S-3-(hexan-1-ol)-glutathione in must from Vitis vinifera L.cv Sauvignon Blanc[J].J.Agric.Food Chem.2002,50:4076～4079
[40]F.Bonilla,Mayen M.,Merida J.and Medina M.Yeast used as fining treatment to correct browning in white wines[J].J.Agric.Food Chem.2001,49:1928～1933
[41]Munoz O.,Sep(?)lveda M.,Schwartz M.Effects of enzymatic treatment on anthocyanic pigments from grapes skin from chilean wine[J].Food Chemistry,2004,87:487～490
[42]Buratti S.,Benedetti S.,Scampicchio M.Characterization and classification of Italian Barbera wines by using an electronic nose and an amperometric electronic tongue[J].Analytica Chimica Acta,2004,525～133～139
[43]李华，胡博然，杨新元．蛇龙珠红葡萄酒香气成分的GC／MS分析[J]．分析测试学报，2004，23(1)：85～87
[44]陕西师范大学，河北师范大学等合编．有机分析教程[M]．西安：陕西师范大学出版社，1987
[45]周同惠主编．生物医药色谱新进展(第二卷)[M]．西安：西北大学出版社，1995
[46]黎盛臣．抗寒抗旱葡萄新品种—北醇[J]．植物学通报，1983，1(2)：28～30
[47]Jewell William T.,Ebeler Susan E.Tyrosinase biosensor for the measurement of wine polyphenolics[J].Am.J.Enol.Vitic,2001,52(3):219～222
[48]白雪莲，章华伟．葡萄酒香气及其呈香物质的研究进展[J]．山西食品工业，2005，2：26～30
[49]李和，李玉帼．植物油中常见的几种植物甾醇的薄层色谱分离与鉴别[J]．中国油脂，1997，22(2)：20
[50]唐健．柚子的香气[J]．北京日化，1996,(2)：39～42
[51]王德峰编著．食用香味料制备与应用手册[M]．北京：中国轻工业出版社，2000
[52]魏云慧，齐刚．动态顶空气相色谱质谱法测定葡萄酒中微量成分[J]．酿酒，2004，32(3)：90～9l
[53]孙健，李楠，邢国秀等．茶多酚高效液相指纹谱-分光光度法质量分析研究[J]．食品科学，2001，22(11)：63～65
[54]杨金辉，张承聪，杨文凡等．烟草中2种多酚的HPLC测定方法[J]．云南大学学报(自然科学版)，2000，22(3)：223～224
[55]钱晓红，谢剑炜．现代仪器分析在生物医学研究中的应用[M]．北京：化学工业出版社．2003
[56]杨祖英，马永建，常风启．食品检验[M]．化学工业出版社．2001
[57]孟兆玲，齐元英，柳仁民．高效液相色谱-质谱联用技术的应用进展[J]．化学分析计量，2006，15(6)：99～103
[58]周同惠主编．生物医药色谱新进展(第二卷)[M]．西安：西北大学出版社，1995
[59]Bakker Johanna,Timberlake Colin F.The distribution of anthocyanins in grape skin extracts of Port wine cultivars as determined by high performance liquid chromatography[J].J.Sci.Food Agric.,1985,36:1315～1324
[60]Ibem-Gomez M.,Andres-Lacueva C.,Lamuela-Rarentos R.M.,et al.Rapid HPLC analysis of phenolics compounds in red wines[J].Am.J.Enol.Vitic.,2002,53(3):218～221
[61]Philippe Jeandet,Anne Celine Breuil,Marielle Adrian,et al.HPLC analysis of grapevine phytoalexins coupling photodiode array detection and fluorometry[J].Anal.Chem.,1997,69:5172～5177
[62]Marce R,M.,Calull M.,Borrull F.,et al.Determination of Major Carboxylic Acids in Wine by an Optimized HPLC Method with Linear Gradient Elution[J].Am.J.Enol.Vitic,1990,41(4):289～294
[63]关家锐，邓丛蕊，王吉顺等．衍生化反相高效液相色谱测定葡萄酒中存在桃酸的研究[J]．色谱，1993，11(5)：282～285
[64]王吉顺，关家锐．反相高效液相色谱法直接测定葡萄酒中非挥发酸[J]．色谱，1993，11(3)：183～184
[65]张学俊．折光率检测器离子交换HPLC法测定葡萄酒和葡萄汁中重要的有机糖、甘油和乙醇[J]．食品科学，1997，18(9)：51～55
[66]张军，韩英素，高年发等．HPLC法测定葡萄酒中有机酸的色谱条件研究[J]．酿酒科技，2004，122(2)：91～93．
[67]Bakker J,Preston N W,Timberlake C F.The determinition of anthoeyanins in aging red wines:Comparison of HPLC and Spectral Methods[J].Am J Enol Vitic,1986,37(2):121～126
[68]Johanna B,Colin FT.The distribution of anthocyanins in grape skin extracts of Port wine cultivars as determined by high performance liquid chromatography[J].Journal Science Food Agriculture,1985,36:1315～1324
[69]Bakker J,Timberlake CF.Isolation,identification,and characterization of new color-stable anthocyanins occurring in some red wines[J].Journal of Agricultural and Food Chemistry,1997,45:35～43
[70]张学俊，关仁安．葡萄酒中酚类的高效液相色谱分析[J]．分析化学1998，26(12)：15～23
[71]刘保东，王维，关家锐等．葡萄酒游离氨基酸的高效液相色谱法测定[J]．分析测试学报，1997，16(6)：5～7
[72]卫锋，陈明生，于玲等．高效液相色谱一荧检测法测定葡萄酒中总亚硫酸盐[J]．色谱，1999，17(6)：583～585
[73]于贞，赵光鳌，李记明等．用HPLC法测定干红葡萄酒中的酚类物质[J]．酿酒，2002，29(2)：88～89
[74]吕九如主编．仪器分析[M]．西安：陕西师范大学出版社，1993
[75]李文武，李宇飞，丁立生等．葡萄属低聚芪含量的HPLC测定[J]．中草药，1998，29(5)：301～303
[76]Lamuela-Raventos R.M.,Waterhouse.A.L Occurrences of resveratrol in slected California wines by a new HPLC method[J].Agric Food Chem,1993,41(4):521～523
[77]McMurtrey K.D.,Minn J.,Pobanz K.,et al.Analysis of wines for Resveratrol using direct in jection high-pressure liquid chromatography with electrochemical detection[J].Agric Food Chem.,1994,42(10):2077～2080
[78]Pezet R.,Pont V.,Cuenat P.Method to determine resveratrol and pterostilbene in grape berries and wines uising high performance liquid chromatography and highly sensitive fluri metric detection[J].Chromatogr.A.1994,663:191～1975
[79]王华，尉亚辉，王庆俐等．葡萄酒中白藜芦醇的HPLC测定[J]．西北农业大学学报，1999，27(4)：83～87
[80]韩雅珊，陈雷，戴蕴青．高效液相色谱法测定葡萄酒中白藜芦醇[J]．色谱，1999，17(4)：366～368
[81]Demyttenaere C.R.Flavour analysis of Greek white wine by solid phase micro-extraction capillary gas chromatography mass spectrometry[J].Journal of Chromatography A,2003,985:233～246
[82]Peinado Rafael A.,Moreno Juan,Bueno Juan E.,et al.Comparative study of aromatic compounds in two young white wine subjected to prefermentative cryomaceration[J].Food Chemistry,2004,84:585～590
[83]Sylvie Roussel,Veronique Bellon-Maurel,Jean-Michel Roger,et al.Authenticating white grape must variety with chassification models based on aroma sensors,FT-IR and UV spectrometry[J].Journal of Food Engeering,2003,60:407～419
[84]杨祖英，马永建，常风启．食品检验[M]．北京：化学工业出版社，200l
[85]于静，李景明，吴继红等．葡萄酒芳香物质的检验[J]．中外葡萄与葡萄酒，2005，(3)：48～51
[86]陈美霞，陈学森，陈传铭．杏果实香气成分的气相色谱-质谱分析[J]．色谱，2004，22(6)：665
[87]杜英峰，张兰桐．现代分离技术在中药研究中的应用[J]．河北医科大学学报，2005，26(1)：71～73
[88]Lamikanra Olusola,Grimm Casey C.,Inyang D.Formation and occurrence of flavor components in Noble muscadine wine[J].Food Chemistry,1996,56(4):373～376
[89]马亭，李攻科，李晓东等．葡萄酒中白藜芦醇的固相萃取GC／MS法测定及其生理活性的初步研究 [J]．高等学校化学学报，2000，21(7)：1023～1027
[90]Goldberg D.M,J.Yan,E.Ng,et al.Aglobal survey of transresveratrol concentrations in commercial wines[J].Am.J.Enol.Vitic,1995,46(2):159～165
[91]段民孝，赵久然，郭景伦等．近红外光谱分析技术研究进展及其在作物育种中的应用前景[J]． http://www.agrieasy.com/dongtai/jinhongwai-yuzhong-duanma.htm
[92]MBlanco,IVillarroya.NIR spectroscopy:a rapid-response analytical tool[J].Trends in analytical chemistry,2002,21(4):240～250
[93]刘全．近红外光谱技术及在中药生产过程质量分析中的应用研究[D]．浙江大学硕士学位论文，2004
[94]张军，陈瑾仙．近红外光谱分析仪的发展及在农产品、食品中的应用[J]．光机电信息，2003，5：24～29
[95]Tipparat P.,LapanantnoppakhunS.,Jakmunee J.,et al.Determination of ethanol in liquor by near-infrared spectrophotometry with flow in jection[J].Talanta,2001,53(6):1199～1204
[96]Sauvage L.,Frank D.,Stearne J.,et al.Tracemetal studies of selected white wines:an alternative approach[J].Analytica Chimica Acta,2002,458(1):223～230
[97]Cozzolino D.,Kwiatkowsk M.J.,Parker M.,et al.Prediction of phenolic compounds in red wine fermentations by visible and near infrared spectroscopy[J].Analytica Chimica Acta,2004,513(1):73～80
[98]Cozzolino D.,Smyth Heather E.,Lattey Kate A.,et al.Relationship between sensory analysis and near infrared spectroscopy in Australian Riesling and Chardonnay wines[J].Analytica Chimica Acta,2005,539(1-2):341～348
[99]Liu L.,Cozzolino D.,Cynkar W.U.,et al.Preliminary study on the application of visible-near infrared spectroscopy and chemometrics to classify Riesling wines from different countries[J].Food Chemistry,2008,106(2):781～786
[100]Urbano-Cuadrado M.,Luque de Castro M.D.,P(?)rez-Juan P.M.,et al.Near infrared reflectance spectroscopy and multivariate analysis in enology:Determination or screening of fifteen parameters in different types of wines[J].Analytica Chimica Acta,2004,527(1):81～88
[101]罗红群，刘绍璞．多波长叠加近红外吸收光谱法直接测定酒精饮料中的乙醇[J]．分析化学研究简报，1998，26(1)：97～99
[102]Liu Fei,He Yong,Wang Li,et al.Feasibility of the use of visible and near infrared spectroscopy to assess soluble solids content and pH office wines[J].Journal of Food Engineering,2007,83(3):430～435
[103]Frazier R.A.Recent advances in capillary electrophoresis methods for food analysis[J].Electrophoresis,2003,24(22-23):4095～4105
[104]孟祥平，刘建学．毛细管电泳在食品分析中的应用进展[J]．食品与发酵工业，2005，31(11)：88～92
[105]Cristina T.da Costa,Perek.Horton,Margolis Sam A.Analysis of anthocyanins in food by liquid chromatography,liquid chrooatogaphy-mass pectrometry and capillary electrophoress[J].Journal of chromatography A.,2000,881(1-2):403～410
[106]Chu Qingyi,Mary O.,Dwyer,Michael G.Direct analysis of resveratrol in wine by micellar electrokin-eticcapillary electrophoresis[J].Agric.Food Chem,1998,46:509～513
[107]Gu Xuelin,Greasy Le.,April Kester,et al.Capillary electrophoretic determination of resveratrol in wines[J].Agric.Food Chem.,1999,47:3223～3227
[108]李华，张予林，袁春龙等．葡萄与葡萄酒中白藜芦醇分析方法的研究现状[J]．中国食品学报，2005，5(1)：104～108
[109]Prasongsidh B.C.,Skurrray G.R.Capillary electrophdresis analysis of trans-and cis-resveratrol,quercetin,catechin and gallic acid in wine[J].Food Chem,1998,62(3):355～358
[110]Gonz(?)lez-Pelas E.,Leache C.,L(?)pez de Cerain A.,Lizarraga E.Comparison between capillary electrophoresis and HPLC-FL for ochratoxin A quantification in wine[J].Food Chemistry,2006,97(2):349～354
[111]郝俊光，王玉洁，和强等．介绍一种快速测定敏感多酚的新方法[J]．酿酒科技，2002，4：79～80
[112]Donata Favretto,Ficeardo Flamini.Application of electrospray ionization mass spectrometry to the study of grape antocyanins[J].Am.J.Enol.Vitic.,2000,51(1):55～64
[113]Wang Jian,Sporns Peter.Analysis of anthocyanins in red wine and fruit juice[J].J.Agric.Food Chem.,1999,47:2009～2015
[114]Gao L.,Mazza G..Rapid method for complete chemical characterization of simple and acylated anthocyanins by high performance liquid chromatography and capillary gas-liquid chromatography[J].J.Agric.Food Chem,1994,42:118～125
[115]Wu Qingli,Wang Mingfu,Simon James E.Determination of proanthocyanidins in grape products by liquid chromatography/mass spectrometric detection under low collision energy[J].Anal.Chem,2003,75:2440～2444
[116]Iztok Jo(?)e Ko(?)ir,Jurkica Kidric.Use of modern nuclear magnetic resonance spectroscopyin wine analysis:determination of minor compounds[J].Analytica Chimica Acta,2002,458:77～84
[117]Carvalho M.L.,Barreiros M.A.,Costa M.M.,et al.Study of heavy metals in Madeira wine by total reflection X-ray fluorescence analysis[J].X-ray Spectrom,1996,25:29～32
[118]Anjos M.J.,Lopes R.T.,Jesus E.F.O.,et al.Trace elements in red and white wines using total-reflection X-ray fluorescence[J].Spectrochim Acta Part B,2003,58:2227～2332.
[119]Gruber X.,Kregsamer P.,Wobrauschek P.,et al.Total-reflection X-ray fluorescence analysis of Austrian wine[J].Spectrochimica Acta Part B,2006,61:1214～1218
[120]张仲平，孙英，牛超等．香椿多酚类化合物的提取、分离和薄层研究[J]．中国野生植物资源，2002，21(4)：52～53
[121]魏泱，丁明玉．茶多酚的色谱分析法[J]．色谱，2000，18(1)：35～38
[122]栾天罡，李攻科，张展霞．相微萃取-衍生化法与气相色谱-质谱联用分析葡萄酒中多酚类化合物[J]．中山大学学报(自然科学版)，2001，40(1)：54～57
[123]Serapinas P.,Venskutonis P.R.,Aninkevicius V.,et al.Step by step approach to multi-element data analysis in testing the provenance of wines[J].Food Chemistry,2008,107(4):1652～1660
[124]常建华，董绮功．波谱原理及解析[M]．北京：科学出版社，2001
[125]许金钩，王尊本主编．荧光分析法(第三版)[M]．北京：科学出版社，2006
[126]田广军．基于三维荧光谱参数化及模式识别的水中油类鉴别与测定[D]．燕山大学博士学位论文，2005
[127]Kazuyuki Horie,Hideharu Vshiki,Francoise M.Winnik.张镇西等编译.Molecular Photonics Fundamentals and Practical Aspects[M].北京：科学出版社,2004:8～69
[128]Kasap S.O.Optoelectronics and Photonics[M].Beijing:Publishing House of Electronics Industry,2003:1～27
[129]陈国珍．荧光分析法[M]．北京：科学出版社，1990
[130]李润卿．有机结构波谱分析[M]．天津：天津大学出版社，2002
[131]杨茹，邱法林，刘翔．分光光度学[M]．北京：机械工业出版社，1998
[132]Pilar Vinas,Carmen L(?)pez-Erroz,Juan Jos(?)Mar(?)n-Hern(?)ndez,et al.Determination of phenols in wines by liquid chromatography with photodiode array and fluorescence detection[J].Journal of Chromatography A,2000,871:85～93
[133]Sergio G(?)mez-Alonso,Esteban Garc(?)a-Romero,Isidro Hermos(?)n-Guti(?)rrez.HPLC analysis of diverse grape and wine phenolics using direct injection and multidetection by DAD and fluorescence[J].Journal of Food Composition and Analysis,2007,20:618～626
[134]Vitrac X.,Monti J.,Vercauteren J.,et al.Direct liquid chromatographic analysis of resveratrol derivatives and flavanonols in wines with absorbance and fluorescence detection[J].Anal.Chim.Acta,2002,458:103～110
[135]Dufour(?).,Letort A.,Laguet A.,et al.Investigation of variety,typicality and vintage of French and German wines using front-face fluorescence spectroscopy[J].Analyfica Chimica Acta,2006,563:292～299
[136]Sikorska,E.,G(?)recki,T.,Khmelinskii,I.V.,et al.Fluorescence Spectroscopy for Characterization and Differentiation of Beers.Journal of the Institute of Brewing,2004,110:267～275
[137]Vlasov Yu.G,Legin A.,Runditskaya A.,et al.Nonspecific sensor arrays(electronic tongue)for chemical analysis of liquids[J].Pure and Applied Chemistry,2005,77(11):1965～1983
[138]田师一，邓少平，2006：多频脉冲电子舌对酒类品种的区分与辨识[J]．，酿酒科技，11：24-26
[139]丁耐克．食品风味化学[M]．北京：中国轻工出版社，1996，12～19
[140]王平．人工嗅觉与人工味觉[M]．北京科技出版社，2000，1～20
[141]Hayashi H.,Yamanaka M.,Toko K.,et al.Multichannel taste sensor using lipid membranes,Sensors and Acfualors E,1990,2:205～213
[142]Hayashi K.,Toko K.,Yamanaka M.,et al.Electronic characteristics of lipid-modified monolayer membranes for taste sensors[J].Sensors and Actuators B,1995,23:55～61
[143]Iiyama S.,Ezaki S.,Toko K.,et al.Study of astringency and pungency with multichannel taste sensor made of lipid membranes[J].Sensors and Actuators B,1995,24～25:75～79
[144]Toko K.Taste sensor with global selectivity[J].Material Science and Engineering C,1996,4:69～82
[145]Oohira K.,Toko K.Theory of electric characteristic of the lipid/PVC/DOPP membrane and PVC/DOPP membrane in response to taste stimuli[J].Biophysical Chemistry,1996,61:29～35
[146]Iiyama S.,Suzuki Y.,Ezaki S.,et al.Objective scaling of taste of sake using taste sensor and glucose sensor[J].Materials Science and Engineering C,1996,4:45～49
[147]Iiyama S.,Kuga H.,Ezak S.,et al.Peculiar change in membrane potential of taste sensor caused by umami substances[J].Sensors and Actuators B,2003,91:191～194
[148]Ju M.J.,Hayama K.,Hayashi K.,et al.Discrimination of pungent-tasting substances using surface-polarity controlled sensor with indirect in situ modification[J].Sensors and Actuators B,2003,89:150～157
[149]Habara M.,Ikezaki H.,Toko K,Study of sweet taste evaluation using taste sensor with lipid/polymer membranes [J]. Biosensors and Bioelectronics, 2004, 19: 1559-1563
[150] Toko K., Murata T., Matsuno T, et al. Taste map of beer by a multichannel taste sensor [J]. Sensors Mafer, 1992, 4: 145-151
[151] Yamada H., Mizota Y, Toko K., et al. Highly sensitive discrimination of taste of milk with homogenization treatment using a taste sensor [J]. Materials Science and Engineering C, 1997, 5: 41-45
[152] Sakai H., Iiyama S., Toko K. Evaluation of water quality and pollution using multichannel sensors [J]. Sensors and Actuators B, 2000, 66: 251-255
[153] Imamura T, Toko K., Yanagisawa S., et al. Monitoring of fermentation process of miso (soybean paste) using multichannel taste sensor [J]. Sensor and Actuators B, 1996, 37: 179-185
[154] Iiyama S., Yahiro M., Toko K. Measurements of soy sauce using taste sensor [J]. Sensors and Actuators B, 2000, 66: 205-206
[155] Legin A., Bychkov E.A., Vlasov Y.G. Analytical applications of chalcogenide glass chemical sensors in environmental monitoring and process control [J]. Sensors and Actuators B, 1995, 24: 309-311
[156] Legin A., Vlasov Y.G., Rudnitskaya A.M. et al. Cross-sensitivity of chalcogenide glass sensors in solutions of heavy metal ions [J]. Sensors and Actuators B, 1996, 34: 456-461
[157] Natale C.D., Davide F., Brunink J.A.J., et al. Multicomponent analysis of heavy metal cations and inorganic anions in liquids by a non-selsective chalcogenide glass sensor array [J]. Sensors and Actuators B, 1996, 34: 539-542
[158] Rudnitskaya A., Ehlert A., Legin A., et al. Multisensor system on the basis of an array of non-specific chemical sensors and artificial neural networks for determination of inorganic pollutants in a model[J]. Talanta, 2001, 55: 425-431
[159] Mourzina Y.G., Schubert J., Zander W., et al. Development of multisensor systems based on chalcogenide thin film chemical sensors for the simultaneous multicomponent analysis of metal ions in complex solutions [J]. Electrochimica Acta, 2001, 47: 251-258
[160] Ipatov A., Ivanov M., Makarychev-Mikhailov S., et al. Determination of cyanide using flow-injection multisensor system [J]. Talanta, 2002, 58: 1071-1076
[161] Legin A., Rudnitskaya A., Lvova L., et al. Evaluation of Italian wine by the electronic tongue: recognition, quantitative analysis and correlation with human sensory perception [J]. Analytica ChimicaActa, 2003, 484: 33-44
[162] Rudnitskaya A., Delgadillo I., Legin A., et al. Prediction of the Port wine age using an electronic tongue [J]. Chemometrics and Intelligent Laboratory Systems, 2007, 88 (1): 125-131
[163] Legin A., Rudnitskaya A., Seleznev B., et al. Electronic tongue for quality assessment of ethanol, vodka and eau-de-vie [J]. Analytica Chimica Acta, 2005, 534: 129-135
[164] Rudnitskaya A., Kirsanov D., Legin A., et al. Analysis of apples varieties - comparison of electronic tongue with different analytical techniques [J]. Sensors and Actuators B, 2006, 116: 23-28
[165] Turner C, Rudnitskaya A., Legin A. Monitoring batch fermentations with an electronic tongue [J]. Journal of Biotechnology, 2003, 103: 87-91
[166] Legin A., Kirsanov D., Rudnitskaya A., et al. Multicomponent analysis of fermentation growth media using the electronic tongue (ET) [J]. Talanta, 2004, 64: 766-772
[167] Soderstrom C, Rudnitskaya A., Legin A., et al. Differentiation of four Aspergillus species and one Zygosaccharomyces with two electronic tongues based on different measurement techniques[J].Journal of Biotechnology,2005,119:300～308
[168]Winquist F.,Wide P.,Lundstr(o|¨)m I.,et al.An electronic tongue based on voltammetry[J].Analytica ChimicaActa,1997,357:21～31
[169]Ivarsson P.,Kikkawa Y.,Winquist F.,et al.Comparison of a voltammetric electronic tongue and a lipid membrane taste sensor[J].Analytica Chimica Acta,2001,449:59～68
[170]Winquist F.,Bjorklund R.,Krantz-Rülcker C.,et al.An electronic tongue in the dairy industry[J].Sensors and Actuators B,2005,111～112:299～304
[171]Ivarsson P.,Johansson M.,H(o|¨)jer N.E.,et al.Supervision of rinses in a washing machine by a voltammetric electronic tongue.Sensors and Actuators B,2005,108:851～857
[172]Gut(?)s A.,Cespedes F.,Valle M.D.,et al.A flow injection voltammetric electronic tongue applied to paper mill industrial waters[J].Sensors and Actuators B,2006,115:390～395
[173]Riul A.,Mattoso L.H.C.,Telles G.D.,et al.Characterization of Langmuir-Blodgett films of parent polyaniline[J].Thin Solid Fills,1996,284～285:177～180
[174]Riul A.,Dhanabalan A.,Mattoso L.H.C.,et al.Characterization of 16-mer polyaniline composite Langmuir-Blodgett films[J].Thin Solid Films,1998,329:576～580
[175]Riul A.,Dhanabalan A.,Cotta M.A.,et al.AFM studies of composite 16-mer polyaniline Langmuir-Blodgett(LB)Films[J].Synthetic Metals,1999,101:830～831
[176]Riul A.,Taylor D.M.,Mills C.A.,et al.Langmuir and Langmuir-Blodgett(LB)films of 4-dicyanom ethylene,4Hcyclopenta[2,1-b,3,4-b']dithiophene[J].Thin Solid Film,2000,366:249-254
[177]Riul A.,Gallardo Soto A.M.,Mello S.V.,et al.An electronic tongue using polypyrrole and polyaniline[J].Synthetic Metals,2003,132:109～116
[178]Riul A.,Mallegrim R.R.,Fonseca F.J.,et al.An artificial taste sensor based on conducting polymers[J].Biosensors and Bioelectronics,2003,18:1365～1369.
[179]Riul A.,Sousa H.C.,Malmegrim R.R.et al.Wine classification by taste sensors made from ultra-thin films and using neural networks[J].Sensors and Actuators B,2004,98:77～82
[180]Ferreira M.,Constantino C.J.L.,Riul A.,et al.Preparation,characterization and taste sensing properties of Langmuir-Blodgett Films from mixtures of polyaniline and a ruthenium complex[J].Polymer,2003,44:4205～4211
[181]Arrieta A.,Rodriguez-M(?)ndez M.L.,de Saja J.A.Langmuir-Blodgett film and carbon paste electrodes based on phthalocyanines as sensing units for taste[J].Sensors and Actuators B,2003,95:357～365
[182]Apetrei C.,Rodr(?)guez-M(?)ndez M.L.,Parra V.,et al.Array of voltammetric sensors for the discrimination of bitter solutions[J].Sensors and Actuators B,2004,103:145～152
[183]Arrieta A.A.,Apetrei C.,Rodr(?)guez-M(?)ndez M.L.,et al.Voltammetric sensor array based on conducting polymer-modified electrodes for the discrimination of liquids[J].Electrochimica Acta,2004,49:4543～4551
[184]Apetrei C.,Apetrei I.M.,Nevares I.,et al.Using an e-tongue based on voltammetric electrodes to discriminate among red wines aged in oak barrels or aged using alternative methods Correlation between electrochemical signals and analytical parameters[J].Electrochimica Acta,2006,in press
[185]Parra V.,Hernando T.,Rodr(?)guez-M(?)ndez M.L.,et al.Electrochemical sensor array made from bisphthalocyanine modified carbon paste electrodes for discrimination of red wines[J].Electrochimica Acta,2004,49:5177～5185
[186]刘大龙，方昉，门洪等．用于环境检测的电子舌研究[J]．传感器技术学报，2004，1：1～6
[187]Men H.,Zou S.F.,Li Y.,et al.A novel electronic tongue combined MLAPS with stripping voltammetry for environmental detection[J].Sensors and Actuators B,2005,110:350～357
[188]郭希山，潘敏，李光等．基于凝胶与纳米碳管复合体化学传感器的研究及人工味觉应用[J]．传感器技术学报，2003，16(4)：447～451
[189]郭希山，童基均，杨祥龙等．高聚物礅黑复合体化学传感器的研究及其在电子舌中的应用[J]．传感器技术学报，2006，19(3)：569～572
[190]滕炯华，王磊，袁朝辉．基于电子舌技术的果汁饮料识别[J]．测控技术，2004，23(11)：4～5
[191]吴坚，刘军，傅敏等．一种基于电子舌技术的绿茶分类方法[J]．2006，19(4)：963～965
[192]Tian Shi-Yi,Deng Shao-Ping,Ding Chun-Hui,et al.Discrimination of Red Wines Age by a Voltammetric Electronic Tongue Based on Multifrequency Large Amplitude Voltammetry and Pattern Recognition Method[J],Sensors and Materials,2007,19:287～298
[193]田师一，邓少平．多频脉冲电子舌对酒类品种的区分与辨识[J]．酿酒科技，2006，11：24～26
[194]牛海霞．电子舌在现代食品科学技术中的应用[J]．食品科技，2007，8：26～30