CAS Key Laboratory of Coastal Environmental Processes and Ecological Remediation, Yantai Institute of Coastal Zone Research (YIC), Chinese Academy of Sciences (CAS); Shandong Key Laboratory of Coastal Environmental Processes, YICCAS, Yantai, Shandong 264003, P. R. China.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
Anal Chem. 2020 Mar 17;92(6):4284-4291. doi: 10.1021/acs.analchem.9b04911. Epub 2020 Mar 6.
Nowadays, polymeric membrane potentiometric sensors based on the molecularly imprinted polymers (MIPs) have been successfully developed for detection of various organic and biological species. However, it is difficult for these sensors to perform reversible detection of the targets due to the high affinities of the MIPs toward the targets. In this work, we propose a novel method for fully reversible potentiometric detection of neutral phenols based on the stimulus-responsive MIP as the selective receptor. Since such smart receptor can switch its recognition abilities according to the external environmental stimuli, the MIP binding sites in the polymeric membrane can be regenerated via the stimulus after each measurement. Thus, potentiometric reversible detection of the target can be achieved. As a proof of concept, the pH-responsive MIP is used as the selective receptor, which can be synthesized by using 4-vinylphenylboronic acid as the functional monomer. The boronate-affinity MIP can covalently bind with a -diol containing compound to form a five- or six-membered cyclic ester in a weakly alkaline aqueous solution, while the produced ester dissociates when the surrounding pH is changed to acidic. By using catechol as a model, the proposed smart sensor exhibits a significantly improved reversibility compared to the conventional MIP-based sensor. We believed that the stimulus-responsive MIP-based sensing strategy could provide an appealing way to design reversible MIP-based electrochemical and optical sensors.
如今,基于分子印迹聚合物 (MIP) 的聚合物膜电位传感器已成功开发用于检测各种有机和生物物种。然而,由于 MIP 对目标物具有高亲和力,这些传感器很难进行目标物的可逆检测。在这项工作中,我们提出了一种基于刺激响应 MIP 作为选择性受体的新型方法,用于对中性酚进行完全可逆的电位检测。由于这种智能受体可以根据外部环境刺激改变其识别能力,因此可以在每次测量后通过刺激来再生聚合物膜中的 MIP 结合位点。因此,可以实现对目标物的电位可逆检测。作为概念验证,使用 pH 响应 MIP 作为选择性受体,其可以通过使用 4-乙烯基苯硼酸作为功能单体来合成。硼酸亲和 MIP 可以在弱碱性水溶液中与含有 -二醇的化合物共价结合形成五元或六元环酯,而当周围 pH 变为酸性时,生成的酯会解离。以儿茶酚为例,与传统的基于 MIP 的传感器相比,所提出的智能传感器表现出显著提高的可逆性。我们相信,基于刺激响应 MIP 的传感策略可以为设计可逆 MIP 基电化学和光学传感器提供一种有吸引力的方法。