Determination of Illegal Drugs in Urine Using Excitation-emission Matrix Fluorescence Coupled with Second-order Calibration†

doi:10.7503/cjcu20150228

Abstract

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

CLC Number:

O657.3

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(9): 1667.

Figures/Tables 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

References 28

[1]	Guo L., Lin Z. B., Huang Z. B., Liang H., Jiang Y., Ye Y. H., Wu Z. P., Zhang R. S., Zhang Y. R., Rao Y. L., Forensic Toxicol., 2015, 33(1), 104—111
[2]	Campora P., Bermejo A. M., Tabernero M. J., Fernandez P., Rapid Commun. Mass Sp., 2006, 20(8), 1288—1292
[3]	Zhang L., Wang Z.H., Li H., Liu Y., Zhao M., Jiang Y., Zhao W. S.,J. Chromatogr. B, 2014, 955, 10—19
[4]	Wei W.L., J Chinese People’s Public Security Univ., 2012, (3), 32—36
	(魏万里. 中国人民公安大学学报, 2012, (3), 32—36)
[5]	Luo F., Crim. Tech., 2011, (1), 16—18(罗芳. 刑事技术, 2011, (1), 16—18)
[6]	Jia J. Y., Zhang Y. R., Wan J., Liu G. Y. Yu C., Chin. J. Drug. Depend, 2008, 17(1), 36—38
	(贾晶莹, 张玉荣, 万钧, 刘罡一, 余琛. 中国药物依赖性杂志, 2008, 17(1), 36—38)
[7]	Katainen E., Elomaa M., Laakkonen U. M., Sippola E., Niemela P., Suhonen J., Jarvinen K., J. Forensic. Sci., 2007, 52(1), 88—92
[8]	Wang J. F., Yu J., Sun X. L., Wang D. F., J. Light Scatt., 2012, 24, 312—315
	(王继芬, 余静, 孙兴龙, 王定方. 光散射学报, 2012, 24, 312—315)
[9]	Cai H., Guo X. J., He T., Pan R., Xiong W., Shen J. L., Chin. J. Optics & Applied Optics, 2010, 3(3), 209—222
	(蔡禾, 郭雪娇, 和挺, 潘锐, 熊伟, 沈京玲. 中国光学与应用光学, 2010, 3(3), 209—222)
[10]	Xu P., Cao Z.N., Shi H. X., Zheng H., Qian Z. H.,Crim. Tech., 2011, (4), 47—50
	(徐鹏, 曹珍年, 石慧霞, 郑珲, 钱振华. 刑事技术, 2011, (4), 47—50)
[11]	Qu D., Wang Y. Y., Jiao Y., Hua L., Liu C. W., Liu J. H., Chen A. Y., Chin. J. Health Lab. Tech., 2009, 19(11), 2558—2559
	(曲典, 王燕燕, 焦义, 华琳, 刘春伟, 刘敬华, 陈安宇. 中国卫生检验杂志, 2009, 19(11), 2558—2559)
[12]	Wang L., Guo S. X., Dai Y. Z., Yang L. B., Liu G. K., Chin. J. Anal. Chem., 2015, 43(1), 33—39
	(王磊, 郭淑霞, 戴吟臻, 杨良保, 刘国坤. 分析化学, 2015, 43(1), 33—39)
[13]	de Bairros A. V., Lanaro R., de Almeida R. M., Yonamine M., Forensic Sci. Int., 2014, 243, 47—54
[14]	Lin H. R., Choi K. I., Lin T. C., Hu A. R., J. Chromatogr. B, 2013, 929, 133—141
[15]	Markechova D., Majek P., Kleinova A., Sadecka J., Anal. Methods-UK, 2014, 6(2), 379—386
[16]	Feudjio W. M., Ghalila H., Nsangou M., Kongbonga Y. G. M., Majdi Y., Talanta, 2014, 130, 148—154
[17]	Ferretto N., Tedetti M., Guigue C., Mounier S., Redon R., Goutx M., Chemosphere, 2014, 107, 344—353
[18]	Kang C., Wu H. L., Xiang S. X., Xie L. X., Liu Y. J., Yu Y. J., Sun J. J., Yu R. Q., Anal. Methods-UK, 2014, 6(16), 6358—6368
[19]	Nie J. F., Wu H. L., Zhu S. H., Han Q. J., Fu H. Y., Li S. F., Yu R. Q., Talanta, 2008, 75(5), 1260—1269
[20]	Sun Y. M., Wu H. L., Wang J. Y., Yu R. Q., Chem. J. Chinese Universities, 2013, 34(5), 1084—1091
	(孙艳梅, 吴海龙, 王建瑶, 俞汝勤. 高等学校化学学报, 2013, 34(5), 1084—1091)
[21]	Poryvkina L., Aleksejev V., Babichenko S.M., Ivkina T.,Optical Pattern Recognition ⅩⅫ, 2011, 8055
[22]	Mazina J., Aleksejev V., Ivkina T., Kaljurand M., Poryvkina L., J. Chemometr., 2012, 26(8/9), 442—455
[23]	Harshman R. A., UCLA Working Papers in Phonetics, 1970, 16(1), 1—84
[24]	Wu H. L., Shibukawa M., Oguma K., J. Chemometr., 1998, 12(1), 1—26
[25]	Chen Z. P., Wu H. L., Yu R. Q., J. Chemometr., 2001, 15(5), 439—453
[26]	Olivieri A. C., J. Chemometr., 2004, 18(7/8), 363—371
[27]	Olivieri A. C., Anal. Chem., 2005, 77(15), 4936—4946
[28]	Bro R., Kiers H. A. L., J. Chemometr., 2003, 17(5), 274—286