An Zhiquan, Jian Xiaoyu, Ma Jiateng, Li Minjie, Zhang Bihong, Guo Liang-Hong
College of Energy Environment and Safety Engineering & College of Carbon Metrology, China Jiliang University, Hangzhou 310018, Zhejiang, P. R. China.
College of Life Science, China Jiliang University, Hangzhou 310018, Zhejiang, P. R. China.
ACS Sens. 2025 Jun 27;10(6):4544-4555. doi: 10.1021/acssensors.5c00822. Epub 2025 May 16.
Photoelectrochemical-colorimetric (PEC-CL) dual-mode detection integrates PEC and CL advantages for bioanalysis but often faces low efficiency, complex conditions, and performance trade-offs due to different signal transduction materials. Here, BiOI was functionalized by Bi self-doping and morphology engineering, forming a 3D Bi-doped BiOI nanoflower with excellent PEC and CL properties. This material was innovatively developed as a single transduction material for self-powered PEC-CL dual-mode detection. The synergistic enhancement of photoelectric conversion and peroxidase (POD)-like activity was systematically investigated. Using γH2AX, a genotoxicity biomarker, as a model, a self-powered PEC sandwich immunosensor was constructed with ITO/Au as the photocathode, BiOI-Ab2 as the signal probe, and CdInS as the photoanode. Upon γH2AX recognition, BiOI was introduced on the photocathode via an immunoreaction. The well-matched energy levels between Au and BiOI, along with the dual-photoelectrode effect, enable a sensitive "signal-on" PEC analysis. Simultaneously, a sandwich immunoreaction involving the BiOI-labeled secondary antibody occurred in the microplate containing HO and 3,3',5,5'-tetramethylbenzidine (TMB), among which BiOI-catalyzed HO produced reactive oxygen species, which further oxidized TMB to produce color, thus achieving the high-throughput visual detection of γH2AX. The PEC-CL dual-mode sensor exhibited broad linear ranges (0.1 pg/mL to 1000 ng/mL for PEC, 1 pg/mL to 500 ng/mL for CL) with ultralow detection limits of 23.9 and 330 fg/mL, respectively. The sensitivity of PEC mode is 100-fold higher than the ELISA method. Moreover, the practicability of the PEC-CL immunosensor was verified in cell lysates exposed to known genotoxic compounds. This sensing platform is versatile, which allows the detection of other biomarkers by changing the recognition element.
光电化学比色（PEC-CL）双模式检测集成了PEC和CL在生物分析方面的优势，但由于信号转导材料不同，常常面临效率低、条件复杂和性能权衡等问题。在此，通过铋自掺杂和形貌工程对BiOI进行功能化，形成具有优异PEC和CL性能的三维铋掺杂BiOI纳米花。这种材料被创新性地开发为用于自供电PEC-CL双模式检测的单一转导材料。系统研究了光电转换和类过氧化物酶（POD）活性的协同增强。以遗传毒性生物标志物γH2AX为模型，构建了以ITO/Au为光阴极、BiOI-Ab2为信号探针、CdInS为光阳极的自供电PEC夹心免疫传感器。在识别γH2AX后，通过免疫反应将BiOI引入光阴极。Au和BiOI之间良好匹配的能级以及双光电极效应实现了灵敏的“信号开启”PEC分析。同时，在含有HO和3,3',5,5'-四甲基联苯胺（TMB）的微孔板中发生了涉及BiOI标记二抗的夹心免疫反应，其中BiOI催化HO产生活性氧，活性氧进一步氧化TMB产生颜色变化，从而实现γH2AX的高通量可视化检测。该PEC-CL双模式传感器表现出宽线性范围（PEC为0.1 pg/mL至1000 ng/mL，CL为1 pg/mL至500 ng/mL），检测限分别低至23.9和330 fg/mL。PEC模式的灵敏度比ELISA方法高百倍。此外，在暴露于已知遗传毒性化合物的细胞裂解物中验证了PEC-CL免疫传感器的实用性。这种传感平台具有通用性，通过改变识别元件可检测其他生物标志物。
