School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 401331, China.
State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese Medical Sciences, University of Macau, Macau, China.
Anal Chim Acta. 2024 Nov 22;1330:343298. doi: 10.1016/j.aca.2024.343298. Epub 2024 Oct 5.
Nanozymes have the advantages of cost effective, simple synthesis, high durability and stability, and have been widely used in various fields. However, only a few nanomaterials with multiple enzyme-like activity have been reported, and most of the currently developed nanozymes are usually used in colorimetric or fluorescence analysis depending on a single colorimetric or fluorescence signal output. In this study, a copper-based dual-ligand biomimetic nanoflower (Cu-MN) was constructed, which demonstrated potential multiple enzyme-like activity, and was applied to the multi-mode detection of 2,4-dichlorophenol (2,4-DP), epinephrine (EP), and HO.
The laccase-like activity of Cu-MN can catalyze the conversion of 2,4-DP and EP, resulting in the formation of red and yellow-brown oxidation products with distinct UV absorption peaks at 510 nm and 485 nm, respectively. Furthermore, the fluorescence emission peak at 426 nm of Cu-MN can be dynamic quenched during substrate oxidation due to the fluorescence internal filtration effect (IFE). Therefore, a dual-mode analysis method was constructed to detect 2,4-DP and EP by fluorescence and ultraviolet colorimetry, which was successfully applied in natural lake water and rabbit plasma analysis, respectively. Furthermore, a colorimetric sensing strategy based on the peroxidase-like activity of Cu-MN was developed and successfully applied to the monitoring of HO in hydrogen peroxide disinfectant. Additionally, the visualization analysis method was also established by RGB reading of the smartphone.
In brief, inspired by the fluorescence characteristics of 2-aminoterephthallc acid and the imidazole group of 2-methylimidazole, a novel copper-based dual-ligand biomimetic nanoflower (Cu-MN) was prepared and used to establish multi-mode method for the detection of 2,4-DP, EP, and HO, which opens up new avenues for its applications in bioanalysis and environmental monitoring.
纳米酶具有成本效益高、合成简单、耐久性和稳定性好等优点，已广泛应用于各个领域。然而，目前报道的具有多种酶样活性的纳米材料很少，大多数目前开发的纳米酶通常依赖于单一比色或荧光信号输出，用于比色或荧光分析。在这项研究中，构建了一种具有潜在的多种酶样活性的铜基双配体仿生纳米花（Cu-MN），并将其应用于 2,4-二氯苯酚（2,4-DP）、肾上腺素（EP）和 HO 的多模式检测。
Cu-MN 的漆酶样活性可以催化 2,4-DP 和 EP 的转化，导致形成具有明显紫外吸收峰的红色和黄棕色氧化产物，分别为 510nm 和 485nm。此外，由于荧光内滤效应（IFE），Cu-MN 的荧光发射峰在 426nm 处可以在底物氧化过程中被动态猝灭。因此，构建了一种通过荧光和紫外比色法检测 2,4-DP 和 EP 的双模式分析方法，分别成功应用于天然湖水和兔血浆分析。此外，基于 Cu-MN 的过氧化物酶样活性，开发了一种比色传感策略，并成功应用于过氧化氢消毒剂中 HO 的监测。此外，还通过智能手机的 RGB 读数建立了可视化分析方法。
简而言之，受 2-氨基对苯二甲酸的荧光特性和 2-甲基咪唑的咪唑基团的启发，制备了一种新型的铜基双配体仿生纳米花（Cu-MN），并用于建立用于检测 2,4-DP、EP 和 HO 的多模式方法，为其在生物分析和环境监测中的应用开辟了新途径。
