Li Wanning, Cai Taimei, Tian Jianwen, Dong Yaru, Hu Fuqiang, Peng Hailong
School of Chemistry and Chemical Engineering, Nanchang University, Nanchang, 330031, China.
School of Life Science, Jiangxi Science and Technology Normal University, Nanchang, 330013, China.
Anal Chim Acta. 2025 Feb 1;1337:343566. doi: 10.1016/j.aca.2024.343566. Epub 2024 Dec 19.
Carbosulfan residues in environment is very harmful to human health. The rapid and high sensitive detection of carbosulfan residues is particularly important to guarantee human health and safety. The conventional chromatographic techniques and enzyme inhibition strategies cannot realize on-site and visual detection of carbosulfan. It is clear that a novel nanozyme-based method was need, which exhibited advantages in low-cost, rapidity, and portability with easy-to-use operation.
A medium entropy-derived flower-like FeCeCu nanozyme (FeCeCuzyme) were prepared via the metal-organic coordination method with "Ostwal ripening" growth process. FeCeCuzyme exhibited an excellent oxidase-like activity due to an abundant active sites in the flower-like structure. Carbosulfan can produce the sulfide compound by hydrolysis reaction under acidic condition, which could easily form sulfide-metal bonds with FeCeCuzyme, thereby significantly quenching their oxidase-like activity and hindering nanozyme-mediated chromogenic reaction. Given this phenomenon, the FeCeCuzyme were used as a colourimetric sensor for highly-specific carbosulfan detection without using acetylcholinesterase and HO. The FeCeCuzyme colourimetric sensor showed a wide linear range from 0.15 to 50.00 μM (R = 0.9970) with low detection limit of 0.13 μM. Meanwhile, FeCeCuzyme sensor was integrated with smartphone to design a portable detection platform, which realizes the on-site and rapid detection of carbosulfan with easy-to-operation. A low detection limit of 0.14 μM was obtained in the linear relation of 0.15-50.00 μM. The satisfactory recoveries (91.17%-108.00 %) from the spiking method were highly agreed with HPLC technique, and which further verified the feasibility of FeCeCuzyme-based strategies in real samples.
This work provides a pioneer new avenue for design of novel nanozymes, and offers an efficient alternative to the conventional methods for specifical, fast, and on-sites detection of carbosulfan in environment.
环境中的丁硫克百威残留对人类健康危害极大。快速、高灵敏地检测丁硫克百威残留对于保障人类健康与安全尤为重要。传统的色谱技术和酶抑制策略无法实现丁硫克百威的现场可视化检测。显然，需要一种新型的基于纳米酶的方法，该方法在低成本、快速性和便携性以及易于操作方面具有优势。
通过金属有机配位法并采用“奥斯特瓦尔德熟化”生长过程制备了一种中熵衍生的花状FeCeCu纳米酶（FeCeCuzyme）。由于花状结构中存在丰富的活性位点，FeCeCuzyme表现出优异的类氧化酶活性。丁硫克百威在酸性条件下通过水解反应可生成硫化物化合物，该化合物能与FeCeCuzyme轻松形成硫 - 金属键，从而显著淬灭其类氧化酶活性并阻碍纳米酶介导的显色反应。基于此现象，FeCeCuzyme被用作比色传感器用于高特异性检测丁硫克百威，无需使用乙酰胆碱酯酶和HO。FeCeCuzyme比色传感器的线性范围为0.15至50.00 μM（R = 0.9970），检测限低至0.13 μM。同时，将FeCeCuzyme传感器与智能手机集成设计了一个便携式检测平台，实现了丁硫克百威的现场快速检测且操作简便。在0.15 - 50.00 μM的线性关系中获得了0.14 μM的低检测限。加标法的回收率令人满意（91.17% - 108.00%），与高效液相色谱技术高度吻合，进一步验证了基于FeCeCuzyme策略在实际样品中的可行性。
这项工作为新型纳米酶的设计提供了一条开创性的新途径，并为环境中丁硫克百威的特异性、快速和现场检测提供了一种有效的替代传统方法的手段。
