Tianjin Key Laboratory on Technologies Enabling Development of Clinical Therapeutics and Diagnostics, School of Pharmacy, Tianjin Medical University, Building B, 22 Qixiangtai Road, Heping District, Tianjin, 300072, China.
School of Chemistry and Chemical Engineering, Shandong Provincial Key Laboratory/Collaborative Innovation Center of Chemical Energy Storage & Novel Cell Technology, Liaocheng University, Liaocheng, 252000, China.
Anal Bioanal Chem. 2022 Sep;414(22):6557-6570. doi: 10.1007/s00216-022-04213-1. Epub 2022 Jul 12.
Molecularly imprinted polymers (MIPs) can exhibit antibody-level affinity for target molecules. However, the nonspecific adsorption of non-imprinted regions for non-target molecules limits the application range of MIPs. Herein, we fabricated PEGylated boronate-affinity-oriented ellagic acid-imprinting magnetic nanoparticles (PBEMN), which first integrated boronate-affinity-oriented surface imprinting and sequential PEGylation for small molecule-imprinted MIPs. The resultant PBEMN possess higher adsorption capacity and faster adsorption rate for template ellagic acid (EA) molecules than the non-PEGylated control. To prove the excellent performance, the PBEMN were linked with hydrophilic boronic acid-modified/fluorescein isothiocyanate-loaded graphene oxide (BFGO), because BFGO could selectively label cis-diol-containing substances by boronate-affinity and output ultrasensitive fluorescent signals. Based on a dual boronate-affinity synergy, the PBEMN first selectively captured EA molecules by boronate-affinity-oriented molecular imprinted recognition, and then the EA molecules were further labeled with BFGO through boronate-affinity. The PBEMN linked BFGO (PBPF) strategy provided ultrahigh sensitivity for EA molecules with a limit of detection of 39.1 fg mL, resulting from the low nonspecific adsorption of PBEMN and the ultrasensitive fluorescence signal of BFGO. Lastly, the PBPF strategy was successfully employed in the determination of EA concentration in a spiked beverage sample with recovery and relative standard deviation in the range of 96.5 to 104.2% and 3.8 to 5.1%, respectively. This work demonstrates that the integration of boronate-affinity-oriented surface imprinting and sequential PEGylation may be a universal tool for improving the performance of MIPs.
分子印迹聚合物（MIPs）可以对目标分子表现出抗体水平的亲和力。然而，非印迹区域对非目标分子的非特异性吸附限制了 MIPs 的应用范围。在此，我们制备了聚乙二醇化硼酸亲和定向鞣花酸印迹磁性纳米粒子（PBEMN），它首先集成了硼酸亲和定向表面印迹和小分子印迹 MIPs 的顺序聚乙二醇化。与非聚乙二醇化对照相比，所得的 PBEMN 对模板鞣花酸（EA）分子具有更高的吸附容量和更快的吸附速率。为了证明其优异的性能，将 PBEMN 与亲水性硼酸改性/荧光素异硫氰酸酯负载氧化石墨烯（BFGO）相连，因为 BFGO 可以通过硼酸亲和选择性标记含有顺二醇的物质，并输出超灵敏的荧光信号。基于双重硼酸亲和协同作用，PBEMN 首先通过硼酸亲和定向分子印迹识别选择性捕获 EA 分子，然后 EA 分子通过硼酸亲和进一步与 BFGO 标记。PBEMN 连接 BFGO（PBPF）策略为 EA 分子提供了超高的灵敏度，检测限低至 39.1 fg mL，这归因于 PBEMN 的低非特异性吸附和 BFGO 的超灵敏荧光信号。最后，该 PBPF 策略成功用于测定加标饮料样品中的 EA 浓度，回收率和相对标准偏差分别在 96.5%至 104.2%和 3.8%至 5.1%的范围内。这项工作表明，硼酸亲和定向表面印迹和顺序聚乙二醇化的集成可能是提高 MIPs 性能的通用工具。
