Abstract

Simultaneous quantitative analysis of catecholamines (CAs) and their respective acid metabolites in biological fluids can become a powerful tool for diagnosis and treatment of various diseases. However, selective sample preparation procedure is necessary to isolate the aforementioned analytes from the matrix. Therefore, we propose a synthetic strategy for the preparation of a molecularly imprinted sorbent with binding sites for both CAs and their respective acid metabolites. The synthesis combines noncovalent and semicovalent imprinting methods. Methylenebisacrylamide, 4-vynilbenzyl-N,N,N-trimethylammonium (3,4-dimethoxyphenyl)acetate, and 3-phenylpropylacrylate were used as the cross-linker, functional monomer 1/“dummy” template 1, and functional monomer 2/“dummy” template 2 under precipitation polymerization conditions, respectively. The polymer was characterized using Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy. The binding properties were studied by constructing adsorption isotherms and conducting competitive binding tests. The performance of the molecularly imprinted polymers (MIPs) toward CAs and the acids was described by good imprinting factors (3.1–5.6), fast-binding equilibrium, and the ability to differentiate nonmethylated CAs from methylated ones. The MIP was used to simultaneously isolate the analytes from human plasma under dispersive solid-phase extraction conditions with subsequent detection using optimized UHPLC/MS/MS procedure. As a result, no major interferences were detected which suggests that the impurities were well separated from the analytes.

摘要

同时定量分析生物液体中的儿茶酚胺（CA）及其各自的酸代谢产物可以成为诊断和治疗各种疾病的有力工具。但是，必须有选择性的样品制备程序才能从基质中分离出上述分析物。因此，我们提出了一种合成策略，用于制备具有两个CA及其各自酸代谢物结合位点的分子印迹吸附剂。该合成结合了非共价和半共价印迹方法。亚甲基双丙烯酰胺，4-季戊基苄基-N，N，N-三甲基铵（3,4-二甲氧基苯基）乙酸酯和丙烯酸3-苯丙酯用作交联剂，功能单体1 /“虚拟”模板1，和功能单体2 /“分别在沉淀聚合条件下的“虚拟”模板2。使用傅立叶变换红外光谱和扫描电子显微镜对聚合物进行表征。通过构建吸附等温线并进行竞争性结合试验研究了结合性能。分子印迹聚合物（MIP）对CA和酸的性能由良好的印迹因子（3.1-5.6），快速结合平衡以及区分非甲基化CA与甲基化CA的能力来描述。MIP用于在分散固相萃取条件下从人血浆中同时分离分析物，并随后使用优化的UHPLC / MS / MS程序进行检测。结果，未检测到主要干扰，这表明杂质已与分析物充分分离。