Hebei Province Key Laboratory of Measurement Technology and Instrument , Institute of Electric Engineering, Yanshan University, Qinhuangdao, Hebei 066004, China
Abstract：Three kinds of quinolones (fluoroquinoline, enrofloxacin and levofloxacin) in honey were analyzed by three-dimensional fluorescence spectroscopy. The spectra were pretreated to eliminate the second-order Rayleigh scattering and Raman scattering, and the spectral noise was eliminated by wavelet optimization set ensemble empirical mode decomposition (EEMD). The bilinear least square/residual bilinear (BLLS/RBL) algorithm was used to detect the samples before and after pretreatment. The results show that after pretreatment, the spectrum of each component in the sample can be accurately resolved, and it has a high similarity with the original spectrum. In the quantitative analysis, the predicted average recovery (RA) of fluoroquinoline, enrofloxacin and levofloxacin is 94.99%, 100.20%, 103.20% respectively, the root mean square error (RMSE) is 4.03, 0.21, 0.29μg/L respectively, the sensitivity (SL) is 3.2×103, 3.5×104, 3.3×104μg/L, respectively; and the detection lower limit (Lout) is 2.08, 0.18, 0.19μg/L respectively, which are superior to the results without pretreatment.
［1］杨微微. 动物源性食品蜂蜜中六种氟喹诺酮药物残留检测方法研究［D］. 贵阳: 贵阳医学院, 2015.
［2］陈卫平, 彭程伟, 杨阳, 等. 北京市地下水中典型抗生素分布特征与潜在风险［J］. 环境科学, 2017, 38(12): 5074-5080.
Chen W P, Peng C W, Yang Y, et al. Distribution Characteristics and Risk Analysis of Antibiotic in the Groundwater in Beijing［J］. Environmental Science, 2017, 38(12): 5074-5080.
［3］林春瑶, 刘功良, 白卫东, 等. 蜂产品抗生素残留检测的研究进展［J］. 农产品加工, 2019 (5): 78-81.
Lin C Y, Liu G L, Bai W D, et al. Advances in the Detection of Antibiotic Residues in Bee Products［J］. Roducts Rocessing, 2019 (5): 78-81.
［4］李总领, 李凌光, 陈沅, 等. 探讨兽药残留的种类及危害［J］. 中兽医学杂志, 2019(5): 83.
Li Z L, Li L G, Chen Y, et al. Discussion on the types and harm of veterinary drug residues［J］. Chinese Journal of Traditional Veterinary Science, 2019(5): 83.
［5］夏环, 王妍, 荆涛, 等. 分子印迹固相萃取-高效液相色谱法测定蜂蜜中三种氟喹诺酮类抗生素残留［J］. 分析科学学报, 2012, 28(3): 297-302.
Xia H, Wang Y, Jing T, et al. Determination of Three Fluoroquinolones Antibiotics residue in Honey Using Molecularly Imprinted Solid phase Extraction Coupled with high Performance Liquid Chromatography［J］. Journal of Analytical Science, 2012, 28(3): 297-302.
［6］徐宜宏, 李晓东, 姜玲玲, 等. 超高效液相色谱串联质谱法同时检测蜂蜜中多种抗生素残留的研究［J］. 畜牧与饲料科学, 2018, 39(12): 17-22.
Xu Y H, Li X D, Jiang L L, et al. Simultaneous Determination of Multiple Antibiotics in Honey by UPLC-MS/MS［J］. Animal Husbandry and Feed Science, 2018, 39(12): 17-22.
［7］王书涛, 朱彩云, 刘洺辛, 等. 基于CS-SVM的山梨酸钾的荧光光谱检测法研究［J］. 计量学报, 2018, 39(5): 747-752.
Wang S T, Zhu C Y, Liu M X, et al. Study on Fluorescence Spectrometric Detection of Potassium Sorbate Based on CS-SVM［J］. Acta Metrologica Sinica, 2018, 39(5): 747-752.
［8］Ntakatsane M, Chen P, Liu J S, et al. Multi-dimensional fluorescence spectroscopy coupled with chemometrics in rapid antibiotic detection and discrimination ［J］. Journal of food measurement & characterization, 2020, 14(4): 1892-1900.
［9］尹春玲, 张秋霞, 胡乐乾. 三维荧光结合二阶校正用于牛奶中3种喹诺酮类药物的同时定量测定［J］. 河南工业大学学报(自然科学版), 2009, 30(4): 49-53.
Yin C L, Zhang Q X, Hu L Q. Imultaneous Quantitative of Three Dimensional Fluorescence Spectrum with Second-order Calibration Algorithm ［J］. Henan University of Technology, 2009, 30(4): 49-53.
［10］Osorio A, Toledo-Neira C, Bravo M. Critical evaluation of third-order advantage with highly overlapped spectral signals. Determination of fluoroquinolones in fish-farming waters by fluorescence spectroscopy coupled to multivariate calibration ［J］. Talanta, 2019, 204: 438-445.
［11］Wang S T, Liu S Y, Che X G, et al. Recognition of polycyclic aromatic hydrocarbons using fluorescence spectrometry combined with bird swarm algorithm optimization support vector machine ［J］. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2020, 224: 117404.
［12］张立国, 张淑清, 李莎莎, 等. 电能质量扰动识别的不同时频分析方法研究［J］. 计量学报, 2017, 38(3): 345-350.
Zhang L G, Zhang S Q, Li S S, et al. Study on the Detection and Classification of Power Quality Disturbances Using Difference Time-frequency Methods［J］. Acta Metrologica Sinica, 2017, 38(3): 345-350.
［13］王书涛, 车先阁, 王志芳, 等. 基于小波优化EEMD的甲烷浓度检测信号研究［J］. 光学技术, 45(3): 269-274.
Wang S T, Che X G, Wang Z F, et al. Research on methane concentration detection signal based on wavelet optimization EEMD ［J］. Optical Technique, 45(3): 269-274.
［14］Asadpour-Zeynali K, Maryam Sajjadi S, Taherzadeh F, et al. Analysis of variation matrix array by bilinear least squares-residual bilinearization (BLLS-RBL) for resolving and quantifying of foodstuff dyes in a candy sample［J］. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2014, 123: 273-281.
［15］Damiani P C, Nepote A J, Bearzotti M, et al. A Test Field for the Second-Order Advantage in Bilinear Least-Squares and Parallel Factor Analyses: Fluorescence Determination of Ciprofloxacin in Human Urine［J］. Analytical Chemistry, 2004, 76(10): 2798-2806.
［16］Yuan Y, Wang S, Cheng Q, et al. Simultaneous determination of carbendazim and chlorothalonil pesticide residues in peanut oil using excitation-emission matrix fluorescence coupled with three-way calibration method［J］. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2019, 220: 117088.
2021, Vol. 42 
