橙汁特征性理化品质分析与鉴伪方法研究
详细信息    本馆镜像全文|  推荐本文 |  |   获取CNKI官网全文
摘要
不同果汁的理化品质特征和所含芳香成分的类别和数量千差万别。本文对2006与2007两年度不同品种橙汁理化品质进行了研究,同时考察了市售不同品牌不同类型的橙汁和橙汁饮料的特征理化品质差异。并采用HS-SPME与GC-MS联用的方法,对实验室自制NFC橙汁以及市售100%NFC橙汁与RFC橙汁的芳香成分进行分析判别。还采用FOX 4000电子鼻对同一产地不同品种的橙汁和桔汁进行风味区分,并对掺假不同梯度的橙汁进行了定性和定量分析。此外还利用缓冲能力和电子鼻技术对不同品种橙汁的原橙汁含量进行了研究。研究结论如下:
     1.橙汁特征理化品质分析
     2006年度与2007年度的同一品种原橙汁的理化品质没有显著差异,理化品质较稳定。PCA分析结果表明:pH值、a~*值、b~*值、可溶性固形物含量、总酸含量、固/酸比值、蔗糖含量、葡萄糖/总糖比值、富马酸含量、VC含量、水溶性黄酮含量及矿物元素Cu、Fe、Mg、Mn、Zn的含量等在第一主成分上有较高的载荷,所以第一主成分是这16个指标的综合反映,而且这16个指标的系数相当,进而说明这16项指标用于评价不同品种原橙汁的理化品质都是必不可少的。果糖含量、葡萄糖含量、果糖/葡萄糖比值、氨基态氮含量以及矿物元素Cr的含量在第二主成分上有较高载荷。L~*值和Ca含量对第三主成分贡献较大。以上这三个主成分从三个方面刻画分析了不同品种原橙汁的理化品质情况具有98.3%的可靠性。
     考察了市售不同品牌不同类型的橙汁和橙汁饮料的特征理化品质,并对其进行判别分析后得到:有pH值、L~*值、a~*值、b~*值、可溶性固形物含量、总酸含量、固/酸比值、果糖和葡萄糖含量等9种理化指标值进入判别函数,并且所得判别模型既可以用判别函数对未知样品的类型进行判别,也可以用已知类型的样品对取得的函数进行判别效果检验。对原始数据进行回代检验后显示,取得的判别函数对原始数据的类型判别效果很好,正确率为100%。因此,利用这种理化品质的差异性对橙汁的类型进行科学的判别是可行的。
     2.利用芳香成分识别橙汁类型的初步研究
     采用峰面积归一化法对橙汁的芳香成分进行相对定量,参考中外文献报道,借助多元统计分析,以橙汁样品中18种芳香化合物的相对含量为自变量,对NFC和RFC两种类型橙汁进行判别分析后得到:从10个橙汁样品中共检测到烃类、醇类、酯类、醛类、酮类等共127种芳香化合物,相比于其他种类芳香成分,烃类和醇类化合物含量是其中的主要组成成分。以芳香化合物相对含量为自变量建立了2个Fisher线性判别函数,所得判别模型既可以用判别函数对未知样品的类型进行判别,也可以用己知类型的样品对取得的函数进行判别效果检验。并对原始数据进行回代检验,显示取得的判别函数对原始数据的类型判别效果很好,正确率为100%。因此,可以利用这种芳香成分的差异性对橙汁的类型进行识别分析。
     3.基于电子鼻对桔汁与橙汁的鉴别分析
     电子鼻可以有效地鉴别不同品种的橙汁与桔汁,并具有良好的灵敏度和重复性。因此,可以通过建立不同品种橙汁的特征指纹库,有效的进行品种橙汁的鉴别和保护。通过对掺假不同比例桔汁的橙汁样品进行检测,PCA分析结果显示,掺假不同比例桔汁的橙汁随着桔汁混合比例的提高,橙汁样品呈现良好的分别趋势,气味指纹呈一定趋势变化。对橙汁比例的PLS拟合分析,拟合效果良好,相关系数达0.9996,并对桔汁含量的拟合也取得了较好的效果。说明电子鼻不仅对定性检测橙汁掺假具备很好的灵敏度,而且对掺假比例的定量结果也有较高的准确性,且预测效果好。
     4.原橙汁含量的分析
     利用溶液缓冲能力测原橙汁含量的方法简便、快捷,对检测仪器要求不高,适合工厂企业等非专业检测机构检测使用。但对于不同品种的橙汁,其缓冲系数有一定的差别。该方法可能可以推广到更多的果汁含量的测定上。
     采用电子鼻技术对不同原橙汁含量的样品进行识别,在用电子鼻定量检测原橙汁的含量时,随着原橙汁含量的增大,电子鼻传感器响应信号逐渐增大,灵敏度较好,区分度较高。借助仪器内置的多元统计软件对不同原橙汁含量的样品进行了PLS拟合分析,拟合效果良好,相关系数达0.9996。说明用电子鼻定量检测原橙汁的含量具有可行性。
Different juices have different physical and chemical character and different aroma compositions. In this paper, physical and chemical character of several varieties of orange juice in 2006 and 2007 were researched, also analysed the different commercial brands of different types of orange juice and Orange beverage . Aroma components of not from concentrated orange juice and refrigerated orange juice from concentrated were analysed by integrated using HS-SPME-GC-MS, and then distinguished them by SPSS. FOX 4000 electronic nose was used to distinguish the different orange juice and mandarin orange juice which come from one region, and also used to analyze adulterated orange juice qualitatively and quantitatively. In addition, we calculated the contents of raw orange juice by measuring buffer capacity and by the electronic nose technology. The main results of this paper are as follows.
     1. Analysis of physical and chemical character
     There was no significant difference in physical and chemical character of same species of orange juice between 2006 and 2007. PCA result showed that: pH, a~*, b~* , solid/acid ratio, glucose/total sugar ratio and content of soluble solids, total acid, sucrose, fumaric acid, VC, flavones, Cu, Fe, Mg, Mn, Zn have a higher load in the first principal component, and the first principal component is the comprehensive reflection of 16 indicators, and it is essential. The content of fructose, glucose, amino nitrogen, Cr and fructose/glucose ratio were remarkable higher in the second principal component. L~*and the content of Ca were remarkable higher in the third principal component. Over the three principal components accounted for physical and chemical character of orange juice for about 98.3% reliability.
     LDA result showed that: there were 9 kinds of physical and chemical parameters entered the gained discriminant functions, such as pH, L~*, a~* , b~* , solid/acid ratio and content of soluble solids, total acid, fructose, glucose. The gained discriminant functions can not only determine the unknown samples, but also can be determined from the known samples. The discriminant functions with 100% accuracy were constructed. Therefore, it was practical to make use of physical and chemical character to establish a scientific judgment of orange juice identification.
     2. Preliminary research on the identification of orange juice types by the use of aroma compositions
     The quantitative results showed that there were 127 aroma components in the 10 juice samples, and hydrocarbons, esters, alcohols, ketones, and aldehydes were the major constituents. With Chinese and foreign literature, 18 of which mainly contributed to orange juice aroma were analyzed by LDA, and established two Fisher linear discriminant function according to aroma compounds which quantified relatively. The gained discriminant functions can not only determine the unknown samples, but also can be determined from the known samples. The discriminant functions with 100% accuracy were constructed. Therefore, it was practical to make use of aroma compounds to identify the type of orange juice.
     3. Distinguish of orange juice and mandarin orange juice by electronic nose
     Electronic nose can identify different species of orange juice and mandarin orange juice effectively, and has a good sensitivity and repeatability. Therefore, we can establish the characteristics fingerprint of different varieties of orange juice to identify and protect varieties of orange juice effectively. Meanwhile, through detecting the different adulterated orange juice samples, PCA result showed that the trend of aroma fingerprint changed along with the proportion of mandarin orange juice to orange juice. PLS result is good, and the correlation coefficient is 0.9996. Therefore, electronic nose can detect adulterated orange juice qualitatively and quantitatively.
     4. Analysis of content of raw orange juice
     Calculating the contents of raw orange juice by measuring buffer capacity is simple and rapid, and be appropriate for other non-professional testing organizations. But different orange juice maybe have different buffer capacity coefficient. This method may be extended to calculate the contents of other juice.
     Using electronic nose technology to detect samples which had different content of the raw orange juice, the result showed that the electronic nose sensor response signal increased along with the content of raw orange juice, and the sensitivity is good. With the built-in multivariate statistical analysis, the samples which had different content of the raw orange juice were analyzed by PLS. PLS result is good, and the correlation coefficient is 0.9996. It illuminated that using electronic nose to detect the content of the raw orange juice quantitatively was feasible.
引文
1.陈晓明,李景明,李艳霞,等.人工神经网络在饮料工业中的应用研究进展.饮料工业.2005,8(1):8-12
    2.程绍南.美国甜橙汁贸易和FCOJ、NFCOJ的竞争态势.柑桔与亚热带果树信.2002,18(3):8-9
    3.程绍南.世界柑桔加工业升起的新星--非浓缩橙汁.柑桔与亚热带果树信.2000,16(9):10
    4.杜锋,雷鸣.电子鼻及其在食品工业中的应用.食品科学.2003,24(5):161-163
    5.方建生,方国桢,周长江.真伪果汁的判别与检测方法.中国乳品工业.1997,125(16):28-31
    6.高海燕,周晓慧,吴继红,等.利用缓冲容量检测梨汁饮料中果汁含量.食品与发酵工业.2005,31(11):101-104
    7.海铮,王俊.电子鼻信号特征提取与传感器优化的研究.传感器技术学报.2006,19(3):206-210
    8.胡博然,李华.不同年份干红葡萄酒香气物质分析研究.食品科学,2006,27(10):488-492
    9.胡耀星,袁三喜,李静娜,等.荧光法鉴定柑桔汁饮料掺假.食品工业科技.2005(5):166-168
    10.贾宗艳,任发政,郑丽敏.电子鼻技术及在乳制品中的应用研究进展.中国乳品工业.2006,34(4):35-38.
    11.林震岩.多变量分析--SPSS的操作与应用.北京:北京大学出版社.2007
    12.刘世民,刘岩.水溶性黄酮类物质比色测定的研究.粮食加工.2004(5):58-60
    13.刘学铭,肖更生,陈卫东,等.果汁鉴伪技术研究进展.食品与发酵工业.2006,32(6):87-91
    14.刘志东,郭本恒,王荫愉,等.电子鼻在乳品工业中的应用.食品与发酵工业.2007,33(2):102-107
    15.马耀宏,史建国,杨俊慧,等.果汁饮料中还原糖快速测定技术的研究.食品与发酵工业.2006,32(6)::104-106.
    16.聂雪梅,刘仲明,张水华,等.电子鼻在食品领域的应用.传感技术.2004,23(10):1-3
    17.沈夏艳,陈颖,黄文胜,等.果汁鉴伪技术及其研究进展.检验检疫科.2007,17(4):63-66
    18.王俊,胡桂仙.电子鼻与电子舌在食品检测中的应用研究进展.农业工程学报.2004,20(2):292-295.
    19.王丽霞,钟海雁,崔涛,等.橙汁饮料香气组分的初步分析.食品与机械.2006,22(3):86-89.
    20.王元军.基于判别分析的泥鳅和大鳞副泥鳅识别.安徽农业科学.2008,36(2):564-568
    21.吴厚玖.中国汁用甜橙的生产和橙汁加工业的发展前景.中国南方果树.2005,34(6):27-28
    22.吴继军,肖更生,等.利用缓冲能力检测桑果汁饮料中果汁含量的方法研究.食品科学.2003,(6):100-102.
    23.吴丽莉,林炳芳.果汁饮料中原果汁含量的检测鉴定.中国畜产与食品.1997,4(6):274-275
    24.吴守一,邹小波.电子鼻在食品行业中的应用研究进展.江苏理工大学学报(自然科学版).2000,21(6):13-17
    25.徐清渠.《橙、柑、桔汁及其饮料中果汁含量的测定》国家标准概况.饮料工业.2002,5(B03):16-18
    26.徐亚丹,王俊,赵国军.基于电子鼻的对掺假的”伊利”牛奶的检测.中国食品学报.2006,6(5):111-118
    27.徐亚丹,王俊,赵国军.检测掺假牛奶的电子鼻传感器阵列的优化.传感技术学报.2006,19(4):957-962
    28.许长卿.期盼非浓缩还原型橙汁能撑起我国橙汁类型饮料发展的蓝天.饮料工业.2005,8(1):13-15
    29.于丽薇,蒋丽萍.果汁饮料真假的鉴别方法.哈尔滨学院学报.2002,23(8):66-67
    30.余亚白.世界橙汁加工业现状及我国发展对策.中国果业信息.2006,123(12):4-5
    31.张玉.中国柑橘产业可持续发展制约因素与对策.中国热带农业.2007(5):10-11
    32.张爱玉,张秋明,张展薇,等.利用氨基氮含量及缓冲能力检测两番莲果汁饮料中果 汁含量的研究.食品科学.2004,25(11):49-51
    33.郑元桂,林国信.柑桔类果汁饮料的真实度鉴定.软饮料工业.1996(3):38-40
    34.Ahmed E M,Dennison R A,Shaw P E.Effect of selected oil and essence volatile components on flavor quality of pumpout orange juice.J Agric Food Chem.1978,26:368-372
    35.Antolovich M,Li X,Robards K.Detection of adulteration in Austrlain orange juices by Stable Carbon Isotope Ratio Analysis(SCIRA).J Agric Food Chem.2001,49(7):2623-2626
    36.Bicchi C E Panero O M,Pellegrino G M,Vanni A C.Characterization of roasted coffee and coffee beverages by solid phase microextraction-gas chromatography and principal component analysis.J Agric Food Chem.1997,45(12):4680-4686
    37.Brause A R,Raterman J M,Petrus D R,Doner L W.Verification of authenticity of orange juice.Journal of the Association of Official Analytical Chemists.1984,67(3):535-539
    38.Brause A R,Raterman J M.Verification of authenticity of apple juice.Journal of the Association of Official Analytical Chemists.1982,65(4):846-849
    39.Buettner A,Schieberle P.Characterization of the most odor-active volatiles in fresh,hand-squeezed juice of grapefruit(Citrus paradisi Macfadyen).J Agric Food Chem.1999,47:5189-5193
    40.Camara M,Diez C,Tori ja E.Chemical characterization of pineapple juices and nectars Principal components analysis.Food Chem.1999,54:93-100
    41.Chang-Chai Ng,Chen-Chin Chang,et al..Rapid molecular identification of freshly squeezed and reconstituted orange juice.International Journal of Food Science Technology.2006,41:646-651 Sass Kiss A,Sass M.Distribution of various peptides in citrus fruits (grapefruit,lemon,and orange).J Agric Food Chem.2002,50(7):2117-2120
    42.Christophe Steine,Fre' de' ric Beaucousin,et al..Potential of Semiconductor Sensor Arrays for the Origin Authentication of Pure Valencia Orange Juices.J Agric Food Chem.2001,49:3151-3160
    43.Christophe Cordelia,Issam Moussa,et al..Recent Developments in Food Characterization and Adulteration Detection:Technique-Oriented Perspectives.J Agric Food Chem.2002, 50: 1751-1764
    44. Coleman W M, Lawson S N. Solid-phase microextraction-gas chromatogramphic-mass selective detection analysis of selected sources of menthol. J Chromatogr Sci. 1998, 36: 401-405
    45. De La Calle Garcia D, Reichenbacher M, Danzer K, et al.. Analysis of wine bouquet components using Headspace SPME-Capillary Gas Chromatography. J High Res Chromatogr. 1998, 21(7): 368-373
    46. Dutta R, Hines E L, Gardner J W, et al.. Tea quality prediction using a tin oxidebased electronic nose: an artificial intelligence approach. Sensors and Actuators B. 2003, 94: 228-237
    47. Eisele T A. Determination of D-malic acid in apple juice by liquid chromatography: collaborative study. Journal of the Association of Official Analytical Chemists. 1996, 79(1): 50-54
    48. Elmore J S, Erbahadir M A, Mottram D S. Comparison of Dynamic Headspace Concentration on Tenax with Solid Phase Microextraction for the Analysis of Aroma Volatiles. J Agric Food Chem. 1997,45: 2638-2641
    49. Eric Jamin, Rea Gis Guea Rin, et al.. Improved Detection of Added Water in Orange Juice by Simultaneous Determination of the Oxygen-18/Oxygen-16 Isotope Ratios of Water and Ethanol Derived from Sugars. J Agric Food Chem. 2003, 51: 5202-5206
    50. Fabio C, Umberto S, Claudio R, et al. Optimization of the determination of organic acids and sugars of fruit juices by ion-exclusion liquid chromatography. Journal of Food Composition and Analysis. 2005, 18: 121-130
    51. Febe G W, David H, Donald S M, et al.. Detection of fruit juice authenticity using pyrolysis mass spectroscopy. Food Chemistry. 2000(69): 215-220
    52. Fellers P J. Citrus fruits: processed and derived products of oranges. In Encyclopedia of Food Science. Food Technology and Nutrition. Vol II. Ed by MacRae R, Robinson R K. Sadler.
    53. Goiffon J P, Mouley P P, Gaydou E M. Anthocyanic pigment determination in red fruit juices, concentrated juices and syrups using liquid chromatography. Analytica Chimica Acta. 1999,382:39-50
    54. Golaszewski R, Sims C A, O'Keefe S F, et al.. Sensory Attributes and. Volatile Components of Stored Strawberry Juice. J Food Sci. 1998, 63(4): 734-738
    55. Haleva-Toledo E, Nairn M, Zehavi U, Rouseff R L. Formation of a-terpineol in citrus juices, model and buffer solutions. J Food Sci. 1999, 64: 838-841
    56. Jack T W, E Vogels, Loes Terwel, et al. Detection of Adulteration in Orange Juices by a New Screening Method Using Proton NMR Spectroscopy in Combination with Pattern Recognition Techniques. J Agric Food Chem. 1996, 44: 175-180
    57. Jordan M J, Tillman T N, Mucci B, et al.. Using HS-SPME to determine the effects of reducing insoluble solids on aromatic composition of orange juice. Food Science and Technology. 2001, 34 (4): 244-250
    58. Juraj Jezek, Milan Suhaj. Application of capillary isotachophoresis for fruit juice authentication. Journal of Chromatography A. 2001(916): 185-189
    59. Kyriakidis N B. Use of pectinesterase for detection of hydrocolloids addition in natural orange juice. Food Hydrocolloids. 1999, 19:497-500
    60. Lay-Keow Ng, Michel Hupe. Analysis of Sterols: a Novel Approach for Detecting Juices of Pineapple, Passion fruit, Orange and Grapefruit in Compounded Beverages. J Sci Food Agric. 1998,76:617-627
    61. Leon L, Kelly J D, Downey G.Detection of apple juice adulteration using near-infrared transflectance spectroscopy. Appl Spectrosc. 2005, 59(5): 593-599
    62. Maccarone E, Campisi S, Fallico B. et al.. Flavor components of Italian orange juices. Journal of Agricultural and Food Chemistry. 1998, 46: 2293-2298
    63. Manuela O Connell, Giabriela Valdora, Gustavo Peltzer. A practical approach for fish freshness determinations using a portable electronic nose. Sensors and Actuators B. 2001. 80: 149-154
    64. Marialuisa Ruiz Del Castillo, MariaM Caja, et al.. Use of the Enantiomeric Composition for the Assessment of the Authenticity of Fruit Beverages. J Agric Food Chem. 2003, 51: 1284-1288
    65. Miller K G, Poole C F, Pawlowski T M P. Classification of the botanical origin of cinnamon by solid-phase microextraction and gas chromatography Chromatographia. 1996, 42: 639-646
    66. Mims W, Wysocki A, Weldon R. Understanding NFC and RECON orange juice demand [DB/OL]. Florda State, USA: Institute of Food and Agricultural Sciences, University of Florida. 20051106, http: //edis.ifas.ufl.edu/pdffiles/FE/FE 17500.pdf.
    67. Moshonas M G, Shaw P E, Buslig B S. Retention of Fresh Orange Juice Flavor and Aroma in an Aqueous Distillate from Valencia Orange Juice. Journal of Food Quality. 1993, 16 (6): 101-108
    68. Moshonas M G., Shaw P E. Dynamic headspace gas chromatography combined with multivariate analysis to classify fresh and processed orange juices. J Essent Oil Res. 1997, 9: 133-139
    69. Moshonas M G., Shaw P E. Quantitation of Volatile Constituents in Mandarin Juices and Its Use for Comparison with Orange Juices by Multivariate Analysis. J. Agric. Food Chem. 1997,45:3968-3972
    70. Nisperos-Carriedo M O, Shaw P E. Comparison of volatile flavor components in fresh and processed orange juices. J Agric Food Chem. 1990, 38: 1048-1052
    71. Ooghe W et al.. Amino acid norms applied for detection of dilutions and adulterations of fruit juices. Fluess Obst. 1982,49: 618
    72. Pan G G, Kilmartin P A, Smith B G, et al.. Detection of orange juice adulteration by tangelo juice using multivariate analysis of polymethoxy lated flavones and carotenoids. J Sci Food Agric. 2002, 82:421-427.
    73. Petrus D R, Attaway J A. Spectral characteristics of Florida orange juice and orange pulpwash Collaborative study. Journal of the Association of Offical Analytical Chemists. 1985,68(6): 1202-1206
    74. R Goodacre, D Hammond, et al.. Quantitative analysis of the adulteration of orange juice with sucrose using pyrolysis mass spectrometry and chemometrics. Journal of Analytical and Applied Pyrolysis. 1997(40-41): 135-158
    75. Roussel S, Bellon Maurel V, Roger J M, et al.. Authenticating white grape must variety with classification models based on aroma sensors, FT-IR and UV spectrometry. J Food Engineer. 2003, 60: 407-419
    76. Saavedra L, Garcia A, Barbas C. Development and validation of a capillary electrophoresis method for direct measurement of isocitric, citric , tartaric and malic acids as adulteration markers in orange juice. J Chromatography A. 2000, 881(1-2): 395-401
    77. Saavedra L, Ruperez F J, et al.. Capillary Electrophoresis for Evaluating Orange Juice Authenticity: a Study on Spanish Oranges. J Agric Food Chem. 2001,49: 9-13
    78. Schieber A, Keller P, Carle R. Determination of phenolic acids and flavonoids of apple and pear by high performance liquid chromatography. J Chromatography A. 2001, 910: 265-273
    79. Shaw P E, Moshonas M G. Quantitation of volatile constituents in orange juice drinks and its use for comparison with pure juices by multivariate analysis. Lebensm Wiss Technol. 1997, in press.
    80. Shaw P E, et al. Discriminant and principal component analyses to classify commercial orange juices based on relative amounts of volatile juice constituents. J Sci Food Agric. 1999,79: 1949-1953
    81. Shui G H, Leong L P. Separation and determination of organic acids and phenolic compounds in fruit juices and drinks by high performance liquid chromatography. Journal of Chromatography A. 2002, 977: 89-96
    82. Simpkins W A, Louie H, Wu M, et al.. Trace elements in Australian orange juice and other products. Food Chem. 2000, 71: 423-433
    83. Sinclair W B. The Biochemistry and Physiology of the Lemon and Other Citrus Fruits. University of California, Oakland, CA. 1984, 152-156
    84. Swallow K W, Low N H, Petrus D R. Detection of orange juice adulteration with beet medium invert sugar using anion-exchange liquid chromatography with pulsed amperometric detection. J Assoc Off Anal Chem. 1991, 74(2): 341-345
    85. Tonder D, Petersen M A, Poll L, et al. Discrimination between freshly made and stored reconstituted orange juice using GC odor profiling and aroma values. Food Chem. 1998, 61(1):223-229
    86. Zidkova J, Chmelik J. Determination of saccharides in fruit juices by capillary electrophoresis and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. J Mass Spectrom. 2001, 36: 417-421

© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号

地址:北京市海淀区学院路29号 邮编:100083

电话:办公室:(+86 10)66554848;文献借阅、咨询服务、科技查新:66554700