三维荧光光谱结合二阶校正算法用于尿液中常见毒品的检测

doi:10.7503/cjcu20150228

摘要/Abstract

摘要：

利用三维荧光光谱技术结合二阶校正算法对尿液中冰毒、 3,4-亚甲基二氧基甲基苯丙胺、可卡因和吗啡4种毒品进行快速定量分析. 结果表明, 平行因子(PARAFAC)、交替三线性分解(ATLD)和自加权交替三线性分解(SWATLD)算法均能很好地分辨出待测组分, 且通过PARAFAC与SWATLD算法解析三维光谱数据获得的尿液背景干扰下4种毒品的平均回收率为92.8%~106.1%, 相对误差低于8%. 三维荧光光谱结合二阶校正算法可用于常见毒品滥用者的快速检测, 为缉毒禁毒工作提供新的检测手段.

关键词: 三维荧光光谱, 二阶校正, 尿液, 毒品

Abstract:

A novel method was developed for the determination of methamphetamine, 3,4-methylenedioxymethamphetamine(MDMA), cocaine and morphine in urine by excitation-emission matrix fluorescence coupled with second-order calibration algorithm. The results showed that the excitation and emission spectra of the four illegal drugs can be resolved accurately based on parallel factor analysis(PARAFAC), self-weighted alternating trilinear decomposition(SWATLD) and alternating trilinear decomposition(ATLD). Additionally, the average spike recoveries are 92.8%—106.1%, and the relative errors are below 8% for all the illegal drugs in the presence of interference of urine by PARAFAC and SWATLD algorithms. The satisfactory results obtained in this work indicate that the excitation-emission matrix fluorescence coupled with second-order calibration is an effective and fast method for screening illegal drug abuses, and it provides a new detection technique for narcotics department.

Key words: Excitation-emission matrix fluorescence, Second-order calibration, Urine, Illegal drug

中图分类号:

O657.3

TrendMD:

徐布一, 叶懿, 阮若云, 颜有仪, 廖林川. 三维荧光光谱结合二阶校正算法用于尿液中常见毒品的检测. 高等学校化学学报, 2015, 36(9): 1667.

XU Buyi, YE Yi, RUAN Ruoyun, YAN Youyi, LIAO Linchuan. Determination of Illegal Drugs in Urine Using Excitation-emission Matrix Fluorescence Coupled with Second-order Calibration^†. Chem. J. Chinese Universities, 2015, 36(9): 1667.

图/表 7

Table 1 Concentrations of four illegal drugs in the calibration(1#—10#) and prediction(11#—16#) samples

No.	Concentration/(mg·L^-1)				No.	Concentration/(mg·L^-1)
No.	MA		MDMA	COC	MOR	MA	MDMA	COC	MOR
1^#	2.0	0.03	0.4	2.5	9^#	18.0	0.05	0.3	0.5
2^#	4.0	0.06	0.8	5.0	10^#	20.0	0.08	0.7	3.0
3^#	6.0	0.09	0.1	2.0	11^#	4.0	0.03	0.4	4.0
4^#	8.0	0.01	0.5	4.5	12^#	6.0	0.06	0.8	3.5
5^#	10.0	0.04	0.9	1.5	13^#	8.0	0.08	0.3	3.0
6^#	12.0	0.07	0.2	4.0	14^#	12.0	0.02	0.7	2.0
7^#	14.0	0.1	0.6	1.0	15^#	14.0	0.04	0.2	1.5
8^#	16.0	0.02	1.0	3.5	16^#	16.0	0.07	0.6	1.0

Fig.1 Three-dimensional fluorescence spectra(A) and contour spectra(B) of MA, MDMA, COC and MOR mixtures, and the overlying contour spectra of four pure illegal drugs with urine(C)

Fig.2 Core consistency values as a function of the number of component

Fig.3 Resolved and actual excitation spectra(A1—A3) and emission spectra(B1—B3) of 4 illegal drugs resolved by PARAFAC(A1, B1), SWATLD(A2, B2) and ATLD(A3, B3) with N=5

Fig.4 Resolved and actual excitation spectra(A) and emission spectra(B) of 4 illegal drugs resolved by ATLD with N=6

Fig.5 Actual concentrations and concentration loadings of MA(A), MDMA(B), COC(C) and MOR(D) resolved by PARAFAC, SWATLD and ATLD algorithms

Table 2 Figures of merit for determination of MA, MDMA, COC and MOR obtained from PARAFAC and SWATLD algorithms

Drug	Algorithm	R	AR(%)	REP(%)	RMSEP/(mg·L^-1)	SEN/(L·mg^-1)	SEL	LOD/(mg·L^-1)
MA	PARAFAC	0.999	103.1	3.10	0.395	601	0.43	0.245
	SWATLD	0.999	101.0	1.85	0.275	575	0.41	0.356
MDMA	PARAFAC	0.999	95.7	4.63	0.002	7349	0.019	0.0003
	SWATLD	0.994	92.8	7.34	0.003	6969	0.018	0.0004
COC	PARAFAC	0.993	106.1	6.98	0.0358	1154	0.030	0.0339
	SWATLD	0.992	103.3	6.99	0.0352	1260	0.032	0.0410
MOR	PARAFAC	0.999	97.1	2.87	0.0666	373	0.028	0.0868
	SWATLD	0.998	100.6	3.37	0.0704	428	0.034	0.0125

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