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

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.

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

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.