Rapid analysis of sulfamethoxazole residue in milk based on fluorescence spectroscopy coupled with chemometrics
-
摘要: 食品中抗生素的残留威胁着消费者的健康。目前用于食品中抗生素残留的检测方法通常经过复杂的预处理、耗时繁琐,而荧光检测具有快速、灵敏度高的特点。本文旨在利用荧光-化学计量学方法建立牛奶中磺胺类抗生素残留的快速检测方法,应用所建立的校正模型对6个品牌共14种商业巴氏奶和UHT奶(包括全脂奶、脱脂奶、半脱脂、高钙)的未知样品进行预测,结果表明,偏最小二乘-判别法(PLS-DA)模型能准确地区分磺胺甲基异恶唑最大残留量上下的样品,假阴性的概率为3.12%,远小于欧盟规定的5%。偏最小二乘法(PLS)法对样品进行定量测定时,在0~210μg/L范围内有良好的线性关系,相关系数为0.9992,样品的回收率可达到87.9%~131.6%,方法的检测限(CCα)为2.54μg/L,定量限(CCβ)为5.07μg/L,平均相对标准偏差为3.24%。该方法可应用于液态乳中磺胺甲基异恶唑残留的快速检测。Abstract: Antibiotic residues in animal tissues and products could bring risks to the health of consumers.The commonly employed methods for detecting antibiotic residues often involve time consuming protocols, whereas the fluorescence method was characterized as rapid and sensitive.In this study, a method had been developed for rapid screening of sulfamethoxazole residues in milk with fluorescence spectroscopy and the chemometrics tools.The established model was applied to 6 brands of commercial milk including pasteurized and UHT milk (whole, skimmed, semi-skimmed, high calcium) .The results showed a significant discrimination by partial least squares discriminant analysis (PLS-DA) between the negative and positive milk samples with a 3.12% of false negative probability, which was below 5% required by the European Union.And quantification could be acquired by further analysis with partial least squares (PLS) with a recovery between 87.9%~131.6%.The correlation coefficient was 0.9992 in the linear range of 0~210μg/kg, and the detection capability (CCβ) and detection limit (CCα) were 2.54μg/L and 5.07μg/L, respectively.The average relative standard error of the prediction model was 3.24%.This method showed potential in rapid screening and analysis of sulfamethoxazole residues in milk.
-
Keywords:
- fluorescence;chemometrics;sulfonamide;milk; /
-
[1] Molina MP, Althaus RL, Molina A, et al.Antimicrobial agent detection in ewes’milk by the microbial inhibitor test brilliant black reduction test-BRT AiM (R) [J].International Dairy Journal, 2003, 13 (10) :821-826.
[2] 中华人民共和国农业部.中华人民共和国农业部公告第235号[Z].2002. [3] Perez N, Gutierrez R, Noa M, et al.Liquid chromatographic determination of multiple sulfonamides, nitrofurans, and chloramphenicol residues in pasteurized milk[J].Journal of Aoac International, 2002, 85 (1) :20-24.
[4] Wen Y, Zhang M, Zhao Q, et al.Monitoring of five sulfonamide antibacterial residues in milk by in-tube solid-phase microextraction coupled to high-performance liquid chromatography[J].Journal of Agricultural and Food Chemistry, 2005, 53 (22) :8468-8473.
[5] Jacobsen AM, Halling-Sorensen B, Ingerslev F, et al.Simultaneous extraction of tetracycline, macrolide and sulfonamide antibiotics from agricultural soils using pressurised liquid extraction, followed by solid-phase extraction and liquid chromatography-tandem mass spectrometry[J].Journal of Chromatography A, 2004, 1038 (1-2) :157-170.
[6] Lindsey ME, Meyer M, Thurman EM.Analysis of trace levels of sulfonamide and tetracycline antimicrobials, in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry[J].Analytical Chemistry, 2001, 73 (19) :4640-4646.
[7] Reeves VB.Confirmation of multiple sulfonamide residues inbovine milk by gas chromatography-positive chemical ionization mass spectrometry[J].J Chromatogr B, 1999, 723 (1-2) :127-137.
[8] Cheng YJ, Huang SH, Singco B, et al.Analyses of sulfonamide antibiotics in meat samples by on-line concentration capillary electrochromatography-mass spectrometry[J].J Chromatogr A, 2011, 1218 (42) :7640-7647.
[9] Blanco CC, Carretero SA, Peinado FS, et al.Determination of the antibacterial drug sulfamethoxazole in pharmaceutical preparations containing trimethoprim by spectrofluorimetry after derivatization with fluorescamine[J].Fresenius J Anal Chem, 1999, 365 (5) :444-447.
[10] 吴海龙, 俞汝勤.化学多维校正的若干新进展[J].化学通报, 2011, 74 (9) :771-782. [11] 中华人民共和国卫生部中国国家标准化管理委员会.GB/T22966-2008.牛奶和奶粉中16种磺胺类药物残留量的测定 (液相色谱-串联质谱法) [S].北京:中国标准出版社, 2008. [12] Espinosa-Mansilla A, De la Pena AM, Salinas F, et al.Partial least squares multicomponent fluorimetric determination of fluoroquinolones in human urine samples[J].Talanta, 2004, 62 (4) :853-860.
[13] Diez R, Sarabia L, Ortiz MC.Rapid determination of sulfonamides in milk samples using fluorescence spectroscopy and class modeling with n-way partial least squares[J].Analytica Chimica Acta, 2007, 585 (2) :350-360.
[14] Barker M, Rayens W.Partial least squares for discrimination[J].Journal of Chemometrics, 2003, 17 (3) :166-173.
[15] Lutz U, Lutz RW, Lutz WK.Metabolic profiling of glucuronides in human urine by LC-MS/MS and partial least-squares discriminant analysis for classification and prediction of gender[J].Analytical Chemistry, 2006, 78 (13) :4564-4571.
[16] Udenfriend S, Stein S, Bohlen P.Fluorescamine:A Reagent for Assay of Amino Acids, Peptides, Proteins, and Primary Amines in the Picomole Range[J].Science, 1972, 178 (4063) :871-872.
[17] Liu XM, Metzger LE.Application of fluorescence spectroscopy for monitoring changes in nonfat dry milk during storage[J].Journal of Dairy Science, 2007, 90 (1) :24-37.
[18] Dufour E, Riaublanc A.Potentiality of spectroscopic methods for the characterisation of dairy products I Front-face fluorescence study of raw, heated and homogenised milks[J].Lait, 1997, 77 (6) :657-670.
[19] Council Regulation (EEC) .No2377/90of26June1990laying down a Community procedure for the establishment of maximum residue limits of veterinary medicinal products in foodstuffs of animal origin[S].Off J L, 1990:224.
[20] Rodriguez N, Real BD, Ortiz MC, et al.Usefulness of parallel factor analysis to handle the matrix effect in the fluorescence determination of tetracycline in whey milk[J].Analytica Chimica Acta, 2009, 632 (1) :42-51.
计量
- 文章访问数: 125
- HTML全文浏览量: 13
- PDF下载量: 251