Gautam Siddharth, Singh Nitish Kumar, Gupta Nancy, Hoque Md Najbul
Department of Chemistry, Netaji Subhas University of Technology, Dwarka Sector-3, Dwarka, Delhi, 110078, India.
Department of Chemistry, Indian Institute of Technology, Roorkee, Uttarakhand, 247667, India.
J Fluoresc. 2025 Sep 5. doi: 10.1007/s10895-025-04521-6.
This study reports the synthesis, characterization, and multifunctional sensing capabilities of a novel quinoline-based Schiff base ligand (L), designed for selective and sensitive detection of Ni, Cu, Zn ions, and CO⁻ anions. L exhibits distinct colorimetric responses visible to the naked eye-pale yellow to amber red for Ni, caramel brown for Cu, and canary yellow for Zn-enabling efficient and straightforward detection. Fluorescence studies reveal a selective green fluorescence "turn-on" response for Zn, complemented by fluorescence quenching in the presence of CO⁻, demonstrating the ligand's reusability and robustness. Moreover, the fluorescent quenching of L-Zn by CO⁻ enabled the detection of CO⁻ using the Stern-Volmer plot, with a limit of detection (LOD), the limit of quantification (LOQ), and rate constant (K) for CO⁻ calculated to be 3.594 µM, 10.891 µM, and 0.64 molL, respectively. Furthermore, a Job's plot experiment was conducted to determine the precise stoichiometric ratio of complex formation, revealing a 1:2 (ML) adduct between M and L, which was further confirmed by ESI-MS spectra and DFT calculation. Comprehensive analyses, including FTIR, ESI-MS, H and C NMR, UV-Visible, fluorescence spectroscopy, and DFT calculations, elucidate the electronic properties, binding, and sensing mechanism of L. NBO, MEP mapping and HOMO-LUMO analysis further highlight nucleophilic and electrophilic reactive sites, confirming the L's suitability for selective coordination with metal ions. Compared to existing sensing systems, L offers competitive or superior detection limits, high selectivity, and visual responsiveness, making it a potential candidate for practical applications in metal ion sensing.
本研究报告了一种新型喹啉基席夫碱配体(L)的合成、表征及多功能传感能力,该配体设计用于选择性和灵敏地检测镍、铜、锌离子以及一氧化碳阴离子(CO⁻)。L对镍呈现出肉眼可见的明显比色响应——从浅黄色变为琥珀红色,对铜为焦糖棕色,对锌为亮黄色,从而实现高效且直观的检测。荧光研究表明,L对锌有选择性的绿色荧光“开启”响应,且在存在CO⁻时会发生荧光猝灭,这证明了该配体的可重复使用性和稳定性。此外,CO⁻对L-Zn的荧光猝灭使得能够使用斯特恩-沃尔默图检测CO⁻,计算得出CO⁻的检测限(LOD)、定量限(LOQ)和速率常数(K)分别为3.594 μM、10.891 μM和0.64 molL。此外,进行了乔布氏图实验以确定配合物形成的精确化学计量比,结果表明M与L之间形成了1:2(ML)加合物,电喷雾电离质谱(ESI-MS)光谱和密度泛函理论(DFT)计算进一步证实了这一点。包括傅里叶变换红外光谱(FTIR)、ESI-MS、氢和碳核磁共振(H和C NMR)、紫外可见光谱、荧光光谱以及DFT计算在内的综合分析阐明了L的电子性质、结合情况和传感机制。自然键轨道(NBO)、分子静电势(MEP)映射和最高占据分子轨道-最低未占据分子轨道(HOMO-LUMO)分析进一步突出了亲核和亲电反应位点,证实了L与金属离子选择性配位的适用性。与现有的传感系统相比,L具有竞争力或更优的检测限、高选择性和视觉响应性,使其成为金属离子传感实际应用的潜在候选者。