基于稀土离子介导石墨烯量子点荧光开关的凝血酶生物传感器

摘要

A label-free method for sensitive and selective detection of thrombin ( Tb) was constructed based on rare earth ion mediated fluorescence switch of graphene quantum dots ( GQDs) . Rare earth ion ( Er3+) can assemble onto the surface of GQDs through the coordination interaction between Er3+ ions and the carboxylate groups located on the surface or edge of the GQDs, resulting in the aggregation of the GQDs and thereby decrease of the fluorescence of the GQDs. In the presence of Tb, the oxygen and nitrogen-donor atoms in Tb can coordinate with Er3+ ions and compete with the carboxylate groups on GQDs to coordinate Er3+ ions, thus the interaction between GQDs and Er3+ ions is reduced, which lead to the restoration of the GQDs fluorescence. In this study, the sensing mechanism was demonstrated by transmission electron microscopy, atomic force microscope, Fourier transform infrared spectroscopy, UV-Vis absorption and fluorescence spectroscopy. The limit of detection for Tb assay was as low as 0. 049 nmol/L. Moreover, this assay was successfully applied to the selective determination of Tb in real samples.%稀土离子(Er3+)可与荧光石墨烯量子点(GQDs)表面的含氧基团发生配位,在Er3+介导下形成高配位数的GQDs/Er3+配合物,引起GQDs聚集而使其荧光减弱.凝血酶(Tb)中的氮和氧等原子可与Er3+发生配位作用,从而与GQDs竞争结合Er3+,减弱了GQDs与Er3+的作用而使其荧光恢复.通过检测GQDs的荧光即可实现对Tb活性的高灵敏分析,构建了基于Er3+介导GQDs荧光开关的Tb传感方法,采用透射电镜、原子力显微镜、红外吸收光谱以及荧光光谱等对传感机理进行了研究.本方法对Tb的检出限低至0.049 nmol/L,其它蛋白质对Tb检测无明显干扰,实际样品中Tb加标回收率为98.0%~105.3%,相对标准偏差为0.6%~4.2%.