7 11 Vol. 7 No. 11 2016 11 Journal of Food Safety and Quality Nov., 2016 刘 威 1, 刘伟丽 1,2, 魏晓晓 1, 李琴梅 1, 张梅 1,2* (1., 100089; 2., 100089) 摘要 :, ( ) ( ),,, 关键词 : ; ; Application of nuclear magnetic resonance spectroscopy in the detection of food adulteration LIU Wei 1, LIU Wei-Li 1,2, WEI Xiao-Xiao 1, LI Qin-Mei 1, ZHANG Mei 1,2* (1. Beijing Centre for Physical and Chemical Analysis, Beijing Key Laboratory of Organic Materials Testing Technology & Quality Evaluation, Beijing 100089, China; 2. Beijing Academy of Science and Technology Key Laboratory of Analysis and Testing Technology, Beijing 100089, China) ABSTRACT: With the advantages of rapid non-destructive detection, easy operation and excellent repeatability, nuclear magnetic resonance (NMR) technology is widely applied in the detection of food adulteration. NMR technology, such as low-field NMR, quantitative NMR, and miscellaneous nuclear NMR, can be applied to detect adulterated milk mixed with the additional materials (water, salt, urea, soybean milk, reconstituted milk, etc.), adulterated olive oil with low value oils (soybean oil, corn oil, etc.), adulterated valuable rice, honey and wine. Combined with statistical analysis methods, such as principal component analysis (PCA), partial least squares-discriminant analysis (PLS-DA), and soft independent modeling of class analogy (SIMCA), NMR technology can distinguish many adulterated foods. This review summarized the application of NMR technology in the detection of food adulteration, which can promote the further application of NMR technology in detection of food quality and safety, and provide new ideas and methods for the identification of adulteration in other fields. KEY WORDS: nuclear magnetic resonance; food; adulteration detection 基金项目 : (PXM2016_178305_000010) Fund: Supported by Specific Financial Funds of Beijing Academy of Science and Technology (PXM2016_178305_000010) * 通讯作者 :,, E-mail: zhmei@scbg.ac.cn *Corresponding author: ZHANG Mei, Associate Researcher, Beijing Centre for Physical and Chemical Analysis, Beijing 100089, China. E-mail: zhmei@scbg.ac.cn
11, : 4359 1 引言,,, [1-3] [4] [5] - - [6-8] [9-13],, ;, ;,,,, ;, 2 核磁共振技术的特点 (nuclear magnetic resonance, NMR),,,,,,, 2, NMR,,, NMR; NMR,, NMR, NMR,,,,, 1 H NMR,, [14] ( ) ( ) (T1) (T2) (D)3,, T1, ( ), T1, T1 T2, D, NMR, NMR, NMR, NMR,, 3 核磁共振技术在食品掺假鉴别中的应用, T2,,, T2,, T2 [15], [16-31], 3.1 乳制品,,,,,,,, ( ), [16]
4360 7 (principal component analysis, PCA) ( ), Carr-Purcell-Meiboom- Gill(CPMG, ),,, [17],,,,,, (partial least squares discriminant analysis, PLS-DA) (linear discriminant analysis, LDA), 100%, 83.3% 100%, 73.3% 76.67%, PCA PLS-DA LDA, LDA Santos [18] ( 1 H TD-NMR),, T2, T2 (soft independent modeling of class analogy, SIMCA) k (k-nearest neighbor, knn), 2, 0.66 1.00, 1 H TD-NMR, ( ),,, 3.2 粮油,,,,,,,,, ( ) ( ),,,,,,,, [19] ( ), PCA PLSR Carr-Purcell-Meiboom- Gill (CPMG),,, ; PLSR CPMG, [20], 3 ( ),,, Vlahov [21], (distortionless enhancement by polarization transfer, DEPT),,, DEPT, Vigli [22], 13 192, DA, 128, 64, DA, 100%, 5% ( ),, Mannina [23], (artificial neural network, ANN),, 2%~20% 100%, 8%,
11, : 4361 Mannina [24], (International Standardization Organization, ISO), 600 MHz, 10%, (500 MHz 400 MHz) Šmejkalová [25],, 10%, 30%,,, Agiomyrgianaki [26],, (canonical discriminant analysis, CDA) (corpus-based translation studies, CBTs) 2 5% [27] NMR,, 10% [28], 1 H NMR,, 1 H NMR 20, 1 H NMR 83.5%, 20 70.1%,,,,,,,, 3.3 其它食品,,,, Musharraf [29], 5.39, 2, 0.1%~1%, Ribeiro [30], (0%~100%), ph, 2 T2, T2, Ferrari [31],,, 95% 4 展望,,, 参考文献 [1] Scotter CNG. Non-destructive spectroscopic techniques for the measurement of food quality [J]. Trends Food Sci Technol, 1997, 8(9): 285 292. [2] Butz P, Hofmann C, Tauscher B. Recent developments in noninvasive technologies for fresh fruit and vegetable internal quality analysis [J]. J Food Sci, 2005, 70(9): 131 141. [3] Zheng C, Sun DW, Zheng L. Recent developments and applications of image features for food quality evaluation and inspection-a review [J]. Trends Food Sci Technol, 2006, 17(12): 642 655. [4],,. / [J]., 2009, 29(1): 122 126. Sun T, Xu HR, Ying YB. Progress in application of near infrared spectroscopy to nondestructive on-line detection of products/food quality
4362 7 [J]. Spectrosc Spect Anal, 2009, 29(1): 122 126. [5]. (ACE) [D]. :, 2010. Hong W. Angiotensin I converting enzyme(ace) inhibitory peptides derived from casein [D]. Wuhu: Anhui Polytechnic University, 2010. [6]. ACE [D]. :, 2011. Wei CY. Preparation of ACE inhibitory peptides by coupling of enzymatic hydrolysis and membrane separation from casein non-phosphopeptides [D]. Wuxi: Jiangnan University, 2011. [7],,,. [J]., 2011, 32(6): 188 191. Cui J, Kong XZ, Zhou HM, et al. Study on the pretreatment of wheat gluten and continuous enzymatic membrane reaction [J]. Sci Technol Food Ind, 2011, 32(6): 188 191. [8],,,. [J]., 2010, 35(1): 88 92. Xiong ZQ, Xu ZH, Wei ZC, et al. Study progress on the process of protein hydrolysis by enzyme membrane reactor [J]. Food Sci Technol, 2010, 35(1): 88 92. [9] Van der Weerd L, Melnikov SM, Vergeldt FJ, et al. Modelling of self-diffusion and relaxation time NMR in multicompartment systems with cyclindrical geometry [J]. J Magn Reson Imaging, 2002, 156(2): 213 221. [10],,. [J]., 2008, 24(6): 117 120. Qi YX, Cheng J, Wang Q. Application of nuclear magnetic reaonance technology in food detection [J]. Food Mach, 2008, 24(6): 117 120. [11],,. [J]., 2011, 32(1): 325 29. Zhou N, Liu BL, Wang X. Application of nuclear magnetic resonance technology in food analysis and detection [J]. Sci Technol Food Ind, 2011, 32(1): 325 329. [12],. [J]., 2013, 34(23): 374 376. Du MH, Sun YJ. Application of low-field nuclear magnetic resonance technique in food safety analysis and detection [J]. Sci Technol Food Ind, 2013, 34(23): 374 376. [13],,,. [J]., 2016, (1): 57 60. Li QQ, Zhu D, Pang XM, et al. Application of high-field nuclear magnetic resonance technology in food quality detection [J]. Qual Saf Agro-Prod, 2016, (1): 57 60. [14],,,. [M]. :, 2009. Yuan RS, Lin XY, Zhang JS, et al. Application of nuclear magnetic resonance in food and biological system [M]. Beijing: China Light Industry Press, 2009. [15]. [D]. :, 2008. Han JZ. Study on quality evaluation and improvement of fresh pork [D]. Hangzhou: Zhejiang Gongshang University, 2008. [16],,,. [J]., 2010, 26(9): 340 344. Jiang C, Han JZ, Fan JL, et al. Rapid detection of adulterated milk by low field-nuclear magnetic resonance coupled with PCA method [J]. Trans CSAE, 2010, 26(9): 340 344. [17],,,. [J]., 2016, 32(7): 51 55. Chen YB, Liu MH, Wang SL, et al. Rapid detection of adulterated milk by low-field nuclear magnetic resonance combined with chemometric method [J]. Food Mach, 2016, 32(7): 51 55. [18] Santos PM, Pereira-Filho ER, Colnago LA. Detection and quantification of milk adulteration using time domain nuclear magnetic resonance(td-nmr) [J]. Microchem J, 2016, 124: 15 19. [19],,. [J]., 2015, 34(7): 789 794. Wang XL, Wu J, Tan MQ. Rapid detection of adulterated walnut oil by low field-nuclear magnetic resonance combined with chemometric method [J]. J Instrum Anal, 2015, 34(7): 789 794. [20],,. [J]., 2014, 35(20): 110 113. Shao XL, Zhang LY, Feng SL. Application of LF-NMR for detection of sesame oil adulteration [J]. Food Sci, 2014, 35(20): 110 113. [21] Vlahov G. Quantitative 13 C NMR method using the DEPT pulse sequence for the detection of olive oil adulteration with soybean oil [J]. Magn Reson Chem, 1997, 35(13): S8 S12. [22] Vigli G, Philippidis A, Spyors A, et al. Classification of edible oils by employing 31 P and 1 H NMR spectroscopy in combination with multivariate statistical analysis. A proposal for the detection of seed oil adulteration in virgin olive oils [J]. J Agric Food Chem, 2003, 51(19): 5715 5722. [23] Mannina L, Segre AL, Aparicio R. Using 1 H and 13 C NMR techniques and artificial neural networks to detect the adulteration of olive oil with hazelnut oil [J]. Eur Food Res Technol, 2004, 219(5): 545 548. [24] Mannina L, D Imperio M, Capitani D, et al. 1 H NMR-based protocol for the detection of adulteration of refined olive oil with refined hazelnut oil [J]. J Agric Food Chem, 2009, 57(24): 11550 11556. [25] Šmejkalová D, Piccolo A. High-power gradient diffusion NMR spectroscopy for the rapid assessment of extra-virgin olive oil adulteration [J]. Food Chem, 2010, 118(1): 153 158. [26] Agiomyrgiannaki A, Petrakis PV, Dais P. Detection of refined olive oil adulteration with refined hazelnut oil by employing NMR spectroscopy and multivariate statistical analysis [J]. Talanta, 2010, 80(5): 2165 2171. [27] Zhang X, Morris RH, Bencsik M, et al. Detection of virgin olive oil adulteration using low field unilateral NMR [J]. Sensors, 2014, 14(2): 2028 2035. [28],,,. 1 H-NMR [J]., 2016, 37(12): 80 84. He Y, Zheng YJ, Deng LL, et al. 1 H-NMR Spectroscopy and authenticity identification for Wuchang Daohuaxiang rice [J]. Sci Technol Food Ind, 2016, 37(12): 80 84.
11, : 4363 [29] Musharraf SG, Fatima SA, Siddiqui AJ, et al. 1 H-NMR fingerprinting of brown rice syrup as a common adulterant in honey [J]. Anal Methods, 2016, 8(34): 6444 6451. [30] Ribeiro ROR, Mársico ET, Carneiro CS, et al. Detection of honey adulteration of high fructose corn by low field nuclear magnetic resonance(lf 1 H NMR) [J]. J Food Eng, 2014, 135(2014): 39 43. [31] Ferrari E, Foca G, Vignali M, et al. Adulteration of the anthocyanin content of red wines: Perspectives for authentication by fourier transform-near infrared and 1 H NMR spectroscopies [J]. Anal Chim Acta, 2011, 701(2): 139 151. ( 责任编辑 : 刘丹 ) 作者简介 刘威, 博士, 助理研究员, 主要研究方向为核磁共振波谱分析 E-mail: liuwei@beijinglab.com.cn 张梅, 博士, 副研究员, 主要研究方向为分析化学 E-mail: zhmei@scbg.ac.cn