Wu Di, Yu Zhichao, Qin Jiao, Li Meijin, Tang Dianping
Key Laboratory of Analytical Science for Food Safety and Biology (MOE & Fujian Province), Department of Chemistry, Fuzhou University, Fuzhou 350108, People's Republic of China.
Anal Chem. 2025 May 27;97(20):10947-10954. doi: 10.1021/acs.analchem.5c02358. Epub 2025 May 15.
This study presents a colorimetric sensor for cancer screening utilizing the bifunctional enzyme activity of NiCo Prussian blue analogue (PBA), a PBA material. By introducing oxygen vacancies and employing a dual-metal doping strategy, NiCo PBA overcomes the limitations in catalytic activity observed in single-metal-doped materials (such as Ni PBA and Co PBA), significantly enhancing both peroxidase-like (POD) and catalase-like (CAT) activities. Compared to single-metal-doped Ni PBA and Co PBA, NiCo PBA exhibited a 30.08-fold increase in POD activity and a 4.83-fold increase in CAT activity, demonstrating higher sensitivity in carcinoembryonic antigen (CEA) detection. By integrating NiCo PBA with a cascade catalytic reaction principle, we developed a highly efficient and sensitive CEA detection method. NiCo PBA was utilized as a catalytic material in this method. Under the action of glucose oxidase, the decomposition of hydrogen peroxide was catalyzed by NiCo PBA, and oxygen was generated. Furthermore, a blue flocculent substance was produced when NiCo PBA was reacted with a chromogenic substrate. Through mutual verification by these two methods, the quantitative determination of CEA in serum samples was achieved. The experimental results demonstrated that the POD-like activity detection range was 0.2-50 ng mL, with a limit of detection (LOD) of 0.061 ng mL, while the CAT-like activity detection range was 0.1-20 ng mL, with an LOD of 0.028 ng mL. The sensitivity of this method was substantially increased compared to monometallic materials. Furthermore, this strategy possesses good scalability and can be adapted for the detection of various analytes by replacing different recognition units, providing an efficient detection platform for early cancer screening.
本研究展示了一种用于癌症筛查的比色传感器，该传感器利用了一种普鲁士蓝类似物（PBA）材料——镍钴普鲁士蓝类似物的双功能酶活性。通过引入氧空位并采用双金属掺杂策略，镍钴普鲁士蓝克服了单金属掺杂材料（如镍普鲁士蓝和钴普鲁士蓝）中观察到的催化活性限制，显著提高了过氧化物酶样（POD）和过氧化氢酶样（CAT）活性。与单金属掺杂的镍普鲁士蓝和钴普鲁士蓝相比，镍钴普鲁士蓝的POD活性提高了30.08倍，CAT活性提高了4.83倍，在癌胚抗原（CEA）检测中表现出更高的灵敏度。通过将镍钴普鲁士蓝与级联催化反应原理相结合，我们开发了一种高效且灵敏的CEA检测方法。在该方法中，镍钴普鲁士蓝被用作催化材料。在葡萄糖氧化酶的作用下，镍钴普鲁士蓝催化过氧化氢分解并产生氧气。此外，当镍钴普鲁士蓝与显色底物反应时会产生蓝色絮状物质。通过这两种方法的相互验证，实现了血清样品中CEA的定量测定。实验结果表明，类POD活性检测范围为0.2 - 50 ng/mL，检测限（LOD）为0.061 ng/mL，而类CAT活性检测范围为0.1 - 20 ng/mL，LOD为0.028 ng/mL。与单金属材料相比，该方法的灵敏度大幅提高。此外，该策略具有良好的可扩展性，通过替换不同的识别单元可适用于各种分析物的检测，为早期癌症筛查提供了一个高效的检测平台。
