分子印迹纳米管膜的制备及对人体尿液中儿茶酚胺类药物的检测

doi:10.7503/cjcu20170568

摘要/Abstract

摘要：

以多巴胺(DA)为模板, 多孔阳极氧化铝膜(AAO)为反应载体, 合成了多巴胺分子印迹聚合物纳米管膜(AAO@MIP). 利用扫描电子显微镜对分子印迹纳米管膜的形貌进行了表征, 并用高效液相色谱(HPLC)研究了其对儿茶酚胺类(CLs)药物的吸附性能. 实验结果表明, 在最优萃取条件下, AAO@MIP 纳米管膜对多巴胺、肾上腺素和去甲肾上腺素具有较高的选择性, 3种儿茶酚胺类药物在0.50~300 μmol/L浓度范围内呈良好的线性关系(r²>0.9970); 检出限(S/N=3)分别为15.5, 12.6和22.5 ng/L. AAO@MIP纳米管膜对多巴胺的最大吸附容量可达82.1 μmol/g; 6次吸附-解吸附重复利用后, 吸附容量仅降低3.3%. 将AAO@MIP 纳米管膜应用于萃取人体尿液中3种儿茶酚胺, 样品加标回收率为74.0%~100.4%, 相对标准偏差(RSD)为3.6%~6.8%. 该方法简便、快速、选择性高, 适用于检测人体尿液中的儿茶酚胺类药物的含量.

关键词: 多孔阳极氧化铝膜, 分子印迹纳米管膜, 儿茶酚胺, 高效液相色谱

Abstract:

A molecularly imprinted nanotubes membrane(AAO@MIP) was prepared using dopamine(DA) as template, porous anodic alumina(AAO) as reactor. The morphology of AAO@MIP was characterized by means of scanning electron microscopy(SEM). The specific adsorption performance of AAO@MIP to catecholamines(CLs) was investigated by high performance liquid chromatography(HPLC). Results of adsorption experiments revealed that the AAO@MIP has good extraction capacity and selectivity to dopamine, epinephrine and norepinephrine. A good linearity was achieved for CLs over the range of 0.50-300 μmol/L and the limit of detection(S/N=3) was found to be as low as 15.5, 12.6 and 22.5 ng/L for dopamine, epinephrine and norepinephrine, respectively. The maximum adsorption capacity of AAO@MIP to dopamine can reach 82.1 μmol/g. And the adsorption capacity is only reduced by 3.3% after six times adsorption-desorption. The proposed method was applied to the determination of CLs in human urine samples. The average recoveries ranged from 74.0% to 100.4% with the relative standard deviation(RSD) of 3.6%-6.8%. The developed method is rapid, selective and sensitive, and could be adapted to the analysis of CLs in urine samples.

Key words: Porous anodic alumina(AAO), Molecularly imprinted nanotubes membrane, Catecholamine, High performance liquid chromatography

中图分类号:

O657

TrendMD:

丘秀珍, 华永标, 郭会时, 卢文贯. 分子印迹纳米管膜的制备及对人体尿液中儿茶酚胺类药物的检测. 高等学校化学学报, 2018, 39(4): 653.

QIU Xiuzhen, HUA Yongbiao, GUO Huishi, LU Wenguan. Preparation of a Molecularly Imprinted Polymer Nanotubes Membrane and Its Application in the Determination of Catecholamines in Urine Samples^†. Chem. J. Chinese Universities, 2018, 39(4): 653.

图/表 9

Scheme 1 Schematic diagram of the grafting dopamine MIP within nanopores of AAO membrane

Fig.1 FTIR spectra of 4-VPBA(a) and 4-VPBA ester(b)

Fig.2 SEM images of AAO(A) and AAO@MIP(B) nanotubes membrane

Fig.3 Adsorption kinetic curves of AAO@MIP(a), AAO@NIP(b) and AAO(c) nanotubes membrane(A) and the static adsorption curve of AAO@MIP nanotubes membrane(B)

Fig.4 Chemical structures of dopamine and its structural analogues(A) and extraction amount of dopamine, its structural analogues and reference compounds with AAO@MIP and AAO@NIP membrane(B)

Fig.5 Repeatability of AAO@MIP for DA

Table 1 Linear range, limit of detection(LOD) and RSD of AAO@MIP coupled with HPLC for the detection of dopamine and its structural analogues

Analyte	Linearity range/(μmol·L^-1)	Linearity equation	R²	LOD/(ng·L^-1)	RSD(%)(n=5)
Normetanephrine	0.50-300	y=123756x-17993	0.9975	22.5	4.7
Epinephrine	0.50-300	y=12922x+149.95	0.9998	12.6	6.1
Dopamine	0.50-300	y=44142x+1175.7	0.9990	15.5	5.2

Table 2 Recovery results obtained for CLs after spiking human urine samples at different concentration levels

Compound	Sample/(μmol·L^-1)	Added/(μmol·L^-1)	Found/(μmol·L^-1)	Recovery(%)	RSD
Dopamine	0.97	1.0	1.8	83.0	6.5
		10.0	10.5	95.3	4.7
		50.0	51.2	100.4	4.9
EP	ND^*	1.0	0.86	86.0	5.4
		10.0	9.1	91.0	3.6
		50.0	47.4	94.8	3.9
NEP	0.46	1.0	1.2	74.0	6.8
		10.0	9.9	94.4	5.9
		50.0	46.8	92.7	4.0

Fig.6 Chromatograms of human urine sample solution(a), spiked sample solution(b) and spiked sample solution after extraction by AAO@MIP(c)Peak 1: Norepinephrine; peak 2: epinephrine;peak 3: dopamine.

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