Ankara University, Faculty of Pharmacy, Department of Pharmaceutical Botany, Ankara, Turkey; Ankara University, Graduate School of Health Sciences, Ankara, Turkey.
Ankara University, Faculty of Pharmacy, Department of Pharmaceutical Botany, Ankara, Turkey.
Talanta. 2025 Jan 1;281:126895. doi: 10.1016/j.talanta.2024.126895. Epub 2024 Sep 16.
This study is the first successful application of a nanomaterial-supported molecularly imprinted polymer (MIP)-based electrochemical sensor for the sensitive and selective determination of apigenin (API), which is a naturally occurring product of the flavone class that is an aglycone of several glycosides. Secondary metabolites are biologically active substances produced by plants in response to various environmental factors. The levels of these compounds can vary depending on factors such as climate, soil conditions and the season in which the plants are grown. Therefore, the analysis of these compounds is essential to properly understand the biological effects of plant extracts and to ensure their safe use. To increase the glassy carbon electrode (GCE) surface's active surface area and porosity, zinc oxide nanoparticles (ZnO NPs) were integrated into the MIP-based electrochemical sensor design. Tryptophan methacrylate (TrpMA) was selected as the functional monomer along with other MIP components such as 2-hydroxyethyl methacrylate (HEMA, basic monomer), 2-hydroxy-2-methylpropiophenone (initiator), and ethylene glycol dimethacrylate (EGDMA, crosslinking agent). The morphological and electrochemical characterizations of the developed API/ZnO NPs/TrpMA@MIP-GCE sensor were performed with scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The indirect measurement approach via 5.0 mM [Fe(CN)] solution was utilized to determine API in the linear range of 1.0x10 M - 1.0x10 M. The limit of detection (LOD) and limit of quantification (LOQ) for standard solutions were found to be 2.47x10 and 8.23x10 M, respectively. In addition, the extraction processes were carried out using ultrasound-assisted extraction (UAE) and maceration (MCR) procedures. For Apium graveolens L., Petroselinum crispum (Mill.) Fuss and herbal supplement, the API recoveries varied from 98.79 % to 102.71 %, with average relative standard deviations (RSD) less than 2.25 % in all three cases. The sensor's successful performance in the presence of components with chemical structures similar to the API was also demonstrated, revealing its unique selectivity.
这项研究首次成功应用了一种基于纳米材料支撑的分子印迹聚合物（MIP）的电化学传感器，用于灵敏和选择性地测定芹菜素（API），API 是类黄酮类的天然产物，是几种糖苷的苷元。次生代谢物是植物在应对各种环境因素时产生的具有生物活性的物质。这些化合物的水平可能因气候、土壤条件和植物生长的季节等因素而有所不同。因此，分析这些化合物对于正确理解植物提取物的生物效应并确保其安全使用至关重要。为了增加玻碳电极（GCE）表面的活性表面积和孔隙率，将氧化锌纳米粒子（ZnO NPs）整合到基于 MIP 的电化学传感器设计中。色氨酸甲基丙烯酸酯（TrpMA）被选为功能单体，同时还有其他 MIP 成分，如 2-羟乙基甲基丙烯酸酯（HEMA，碱性单体）、2-羟基-2-甲基丙基苯甲酮（引发剂）和乙二醇二甲基丙烯酸酯（EGDMA，交联剂）。通过扫描电子显微镜（SEM）、能量色散 X 射线分析（EDX）、循环伏安法（CV）和电化学阻抗谱（EIS）对开发的 API/ZnO NPs/TrpMA@MIP-GCE 传感器进行了形态和电化学表征。通过 5.0mM [Fe(CN)]溶液的间接测量方法，在 1.0x10 M-1.0x10 M 的线性范围内测定 API。标准溶液的检测限（LOD）和定量限（LOQ）分别为 2.47x10 和 8.23x10 M。此外，提取过程分别采用超声辅助提取（UAE）和浸渍提取（MCR）程序进行。对于水芹、皱叶欧芹和草药补充剂，API 的回收率在 98.79%至 102.71%之间，在所有三种情况下，平均相对标准偏差（RSD）均小于 2.25%。该传感器在具有与 API 化学结构相似的成分存在下的成功表现也证明了其独特的选择性。
