利用石墨烯及中空结构的金纳米笼构建了无标记型电化学免疫传感器,并用于微囊藻毒素的检测。利用多元醇还原法合成制备了导电性好、催化性强、生物相容性好的金纳米笼;再利用高分散的石墨烯将其固定于玻碳电极表面,进一步吸附固定微囊藻毒素抗体。在无微囊藻毒素存在时,电化学探针[Fe(CN)6]3-/4-在传感器界面上能获得较高的电流响应信号。当培育了微囊藻毒素后,抗体与微囊藻毒素形成免疫结合物,增加了电极表面的电荷密度和传质阻力,阻碍[Fe(CN)6]3-/4-扩散到电极表面,导致[Fe(CN)6]3-/4-的电流响应信号明显降低,电流减小的程度间接地与微囊藻毒素的浓度成比例,可实现对微囊藻毒素的检测。实验考察了抗原培育时间,抗体浓度等条件对该传感器响应性能的影响。结果表明,此传感器对微囊藻毒素的线性响应范围为0.05~1000μg/L,检出限为0.017μg/L,优于文献报道。此传感器操作简单,并且具有良好的稳定性,将其用于实际水样中微囊藻毒素的检测,平均加标回收率为94.1%。
A label-free electrochemical immunosensor using hollow structure nanomaterials based on its ordered porous and big surface area was designed. Au nanocage, with good conductivity, catalysis, and biocompatibility, was prepared and modified on the surface of glassy carbon electrode with graphene to immobilize antibody of microcystin directly. In the absence of microcystin, biosensor can obtain high current response signal of electrochemical probe ( [ Fe( CN) 6 ] 3-/4-. When microcystin was combined with its antibody specifically, the charge density and mass transfer resistance on the surface of electrode increased, resulting in a decrease of the corresponding peak current of [ Fe ( CN ) 6 ] 3-/4-. This change was in proportion to the concentration of microcystin indirectly. Experiment conditions such as cultivation time of antigen and concentration of antibody were optimized. The results showed wide linear range of 0. 05 μg/L-1. 0 mg/L and the detection limit of 0. 017 ng/mL. This sensor has good stability and simple production procedure. This sensor provides a new and simple means for the ultrasensitive determination of microcystins in real water samples.