Zamani Ali, Tajbakhsh Mahmood, Sarrafi Yaghoub
Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran.
J Fluoresc. 2025 Sep 2. doi: 10.1007/s10895-025-04473-x.
A novel fluorescent and colorimetric probe (L3), based on 2,6-pyridinedicarbohydrazide, was rationally designed and synthesized for the highly selective and reversible detection of Cu²⁺ ions. The structural and optical properties of the probe were comprehensively characterized by FT-IR, ¹H NMR, UV-Vis spectroscopy, fluorescence analysis, ESI⁺-MS, and elemental analysis. The probe L3 displayed a high selectivity, high sensitivity and quick response to Cu ions in the presence of other competing cations including Ba, K, Pb, Hg, Al, Zn, Fe, Tl, Mg, Ni, Nd, Fe, Ag, Ca, Cs, Co, Cd, Sr, and Mn ions). Upon interaction with Cu²⁺, probe L3 exhibited distinct optical responses, including significant fluorescence quenching, a notable redshift in the UV-Vis spectrum, and a rapid, visible color change from colorless to greenish-yellow under aqueous conditions and across a broad pH range. The detection limit was calculated to be as low as 2.28 × 10⁻⁹ M, with an association constant (Ka) of 2.2 × 10¹¹ M⁻², indicating strong binding affinity. Job's plot and ¹H NMR titration confirmed a 1:2 stoichiometric complex formation between L3 and Cu²⁺ ions. The probe also exhibited excellent reversibility, as confirmed by fluorescence recovery upon adding Na₂EDTA, suggesting its suitability for real-time and reusable sensing applications. Furthermore, the practical utility of L3 was demonstrated using test strips for Cu²⁺ detection in aqueous environments, and its effectiveness was further validated in real water samples, including tap water, drinking water, and seawater, achieving recovery rates up to 99.2%. These findings suggest that L3 is promising for the sensitive, rapid, and cost-effective monitoring of copper ions in environmental and drinking water systems.
基于2,6-吡啶二甲酰肼,合理设计并合成了一种新型荧光比色探针(L3),用于高选择性、可逆地检测Cu²⁺离子。通过傅里叶变换红外光谱(FT-IR)、¹H核磁共振(¹H NMR)、紫外可见光谱、荧光分析、电喷雾电离正离子质谱(ESI⁺-MS)和元素分析对该探针的结构和光学性质进行了全面表征。在存在包括Ba、K、Pb、Hg、Al、Zn、Fe、Tl、Mg、Ni、Nd、Fe、Ag、Ca、Cs、Co、Cd、Sr和Mn离子在内的其他竞争性阳离子的情况下,探针L3对Cu离子表现出高选择性、高灵敏度和快速响应。与Cu²⁺相互作用时,探针L3表现出明显的光学响应,包括显著的荧光猝灭、紫外可见光谱中明显的红移,以及在水性条件下和较宽的pH范围内从无色迅速变为黄绿色的可见颜色变化。计算得出检测限低至2.28×10⁻⁹ M,缔合常数(Ka)为2.2×10¹¹ M⁻²,表明具有很强的结合亲和力。Job曲线和¹H NMR滴定证实L3与Cu²⁺离子之间形成了1:2的化学计量比配合物。加入Na₂EDTA后荧光恢复证实该探针还具有优异的可逆性,表明其适用于实时和可重复使用的传感应用。此外,使用测试条在水环境中检测Cu²⁺证明了L3的实际应用价值,其有效性在包括自来水、饮用水和海水在内的实际水样中得到进一步验证,回收率高达99.2%。这些发现表明L3有望用于环境和饮用水系统中铜离子的灵敏、快速且经济高效的监测。