Key Laboratory of Optic-Electric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao, 266042, People's Republic of China.
Mikrochim Acta. 2023 Mar 13;190(4):131. doi: 10.1007/s00604-023-05701-6.
An "on-off-on"-type electrochemiluminescence (ECL) aptamer sensor based on Ru@Zn-oxalate metal-organic framework (MOF) composites is constructed for sensitive detection of sulfadimethoxine (SDM). The prepared Ru@Zn-oxalate MOF composites with the three-dimensional structure provide good ECL performance for the "signal-on." The MOF structure with a large surface area enables the material to fix more Ru(bpy). Moreover, the Zn-oxalate MOF with three-dimensional chromophore connectivity provides a medium which can accelerate excited-state energy transfer migration among Ru(bpy) units, and greatly reduces the influence of solvent on chromophore, achieving a high-energy Ru emission efficiency. The aptamer chain modified with ferrocene at the end can hybridize with the capture chain DNA1 fixed on the surface of the modified electrode through base complementary pairing, which can significantly quench the ECL signal of Ru@Zn-oxalate MOF. SDM specifically binds to its aptamer to separate ferrocene from the electrode surface, resulting in a "signal-on" ECL signal. The use of the aptamer chain further improves the selectivity of the sensor. Thus, high-sensitivity detection of SDM specificity is realized through the specific affinity between SDM and its aptamer. This proposed ECL aptamer sensor has good analytical performance for SDM with low detection limit (27.3 fM) and wide detection range (100 fM-500 nM). The sensor also shows excellent stability, selectivity, and reproducibility, which proved its analytical performance. The relative standard deviation (RSD) of SDM detected by the sensor is between 2.39 and 5.32%, and the recovery is in the range 97.23 to 107.5%. The sensor shows satisfactory results in the analysis of actual seawater samples, which is expected to play a role in the exploration of marine environmental pollution.
一种基于 Ru@Zn-草酸盐金属有机骨架(MOF)复合材料的“开-关-开”型电化学发光(ECL)适体传感器被构建用于灵敏检测磺胺二甲氧嘧啶(SDM)。所制备的具有三维结构的 Ru@Zn-草酸盐 MOF 复合材料为“信号开启”提供了良好的 ECL 性能。具有大表面积的 MOF 结构使材料能够固定更多的 Ru(bpy)。此外,具有三维发色团连接性的 Zn-草酸盐 MOF 提供了一种可以加速 Ru(bpy)单元之间激发态能量转移迁移的介质,并且大大降低了溶剂对发色团的影响,实现了高能 Ru 发射效率。末端修饰有二茂铁的适体链可以通过碱基互补配对与固定在修饰电极表面的捕获链 DNA1 杂交,这可以显著猝灭 Ru@Zn-草酸盐 MOF 的 ECL 信号。SDM 特异性地与其适体结合,将二茂铁从电极表面分离出来,从而产生“信号开启”的 ECL 信号。适体链的使用进一步提高了传感器的选择性。因此,通过 SDM 与其适体之间的特异性亲和力实现了对 SDM 的高灵敏度检测特异性。该提出的 ECL 适体传感器对 SDM 具有低检测限(27.3 fM)和宽检测范围(100 fM-500 nM)的良好分析性能。传感器还表现出出色的稳定性、选择性和重现性,证明了其分析性能。传感器检测到的 SDM 的相对标准偏差(RSD)在 2.39%至 5.32%之间,回收率在 97.23%至 107.5%范围内。该传感器在实际海水样品分析中表现出令人满意的结果,有望在海洋环境污染探测中发挥作用。