Abstract：
A novel and robust electrochemical sensing tool for the determination of vismodegib (VIS), an anticancer drug, has been developed by integrating the selective recognition capabilities of molecularly imprinted polymer (MIP) and the sensitivity enhancement capability of metal-organic framework (MOF). Prior to this step, the electrochemical behavior of VIS was investigated using a bare glassy carbon electrode (GCE). It was observed that in 0.5 M H2SO4 solution as electrolyte, VIS has an oxidation peak around 1.3 V and the oxidation mechanism is diffusion controlled. The determination of VIS in a standard solution using a bare GCE showed a linear response in the concentration range from 2.5 μM to 100 μM, with a limit of detection (LOD) of 0.75 μM. Since sufficient sensitivity and selectivity could not be achieved with bare GCE, a MIP sensor was developed in the next step of the study. For this purpose, the GCE surface was first modified by drop casting with as-synthesized Co-MOF. Subsequently, a MIP network was synthesized via a thermal polymerization approach using 2-acrylamido-2-methylpropanesulfonic acid (AMPS) as monomer and VIS as template. MOFs are ideal electrode materials due to their controllable and diverse morphologies and modifiable surface properties. These characteristics enable the development of MIPs with more homogeneous binding sites and high affinity for target molecules. Integrating MOFs could help the performance of sensors with the desired stability and reproducibility. Electrochemical analysis revealed an observable enhancement of the output signal by the incorporation of MOF molecules, which is consistent with the sensitivity-enhancing role of MOF by providing more anchoring sites for the attachment of the polymer texture to the electrode surface. This MOF-MIP sensor exhibited impressive linear dynamic ranges ranging from 0.1 to 1.0 pM for VIS, with detection limits in the low picomolar range. In addition, the MOF-MIP sensor offers high accuracy, selectivity and precision for the determination of VIS, with no interference observed from complex media of serum samples. Additionally, in this study, Analytical GREEnness metric (AGREE), Analytical GREEnness preparation (AGREEprep) and Blue Applicability Grade Index (BAGI) were used to calculate the green profile score.
摘要：
一种新颖而强大的电化学传感工具，用于测定粘滞剂（VIS），一种抗癌药物，通过整合分子印迹聚合物（MIP）的选择性识别能力和金属有机骨架（MOF）的灵敏度增强能力来开发。在这一步之前，使用裸玻碳电极（GCE）研究了VIS的电化学行为。据观察，在0.5MH2SO4溶液作为电解质，VIS具有约1.3V的氧化峰,并且氧化机制是扩散控制的。使用裸GCE测定标准溶液中的VIS在2.5μM至100μM的浓度范围内显示出线性响应，检测限(LOD)为0.75μM。由于裸露的GCE无法实现足够的灵敏度和选择性，在研究的下一步中开发了MIP传感器。为此,首先用合成的Co-MOF通过滴铸对GCE表面进行改性。随后，以2-丙烯酰胺基-2-甲基丙磺酸（AMPS）为单体，VIS为模板，通过热聚合方法合成了MIP网络。MOF是理想的电极材料，因为它们具有可控和多样的形态和可修饰的表面性质。这些特征使得能够开发具有更均匀的结合位点和对靶分子的高亲和力的MIP。集成MOF可以帮助传感器的性能与期望的稳定性和再现性。电化学分析表明，通过掺入MOF分子，可以观察到输出信号的增强，这与MOF的灵敏度增强作用是一致的,其通过提供更多的锚定位点用于将聚合物纹理附着到电极表面。这MOF-MIP传感器表现出令人印象深刻的线性动态范围从0.1到1.0pM的VIS，检测限在低皮摩尔范围内。此外,MOF-MIP传感器提供高精度，测定VIS的选择性和精密度，从血清样品的复合培养基中没有观察到干扰。此外,在这项研究中，分析绿色度量(AGREE)，分析绿色准备(AGREEprep)和蓝色适用性等级指数(BAGI)用于计算绿色轮廓得分。
