Preparation of a Molecularly Imprinted Polymer Nanotubes Membrane and Its Application in the Determination of Catecholamines in Urine Samples†

doi:10.7503/cjcu20170568

Abstract

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

CLC Number:

O657

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2018, 39(4): 653.

Figures/Tables 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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