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基于简单吡啶水杨醛亚胺的荧光“开启”传感器,用于在混合水相介质中对 Zn2+、Al3+ 和 OH- 离子的独特检测。

Simple pyridyl-salicylimine-based fluorescence "turn-on" sensors for distinct detections of Zn2+, Al3+ and OH- ions in mixed aqueous media.

机构信息

Department of Materials Science and Engineering, National Chiao Tung University, Hsinchu 30049, Taiwan (ROC).

出版信息

Analyst. 2013 May 21;138(10):2931-42. doi: 10.1039/c3an36840h.

Abstract

Simple pyridyl-salicylimine derivatives (F1, F2 and F3) are reported for the first time as fluorescence "turn-on" sensors for distinct detections of Zn(2+), Al(3+) and OH(-) ions in mixed-aqueous media CH3CN/H2O with volume ratios of 6/4 and 3/7 (at pH = 7 and 25 °C) via internal charge transfer (ICT), chelation enhanced fluorescence (CHEF), and deprotonation mechanisms. F1 and F2 show diverse turn-on sensing applications to Zn(2+), Al(3+) and OH(-) ions, but F3 exhibited the fluorescence turn-on sensing to Al(3+) and OH(-) ions in CH3CN/H2O (6/4; vol/vol). F1+Zn(2+) and F2+Zn(2+) complexes revealed the reversibilities and ratiometric displacements of Zn(2+) with ethylene diamine tetra acetic acid (EDTA) and Al(3+) ions, respectively, in CH3CN/H2O (6/4; vol/vol). On the other hand, F1, F2 and F3 in CH3CN/H2O (3/7; vol/vol) showed sensitivities only to Al(3+) ions but negligible selectivities to OH(-) ions. Stoichiometry of all sensor complexes were calculated as 1 : 1 by job's plots based on UV/Vis and PL titrations. The complex formation and binding sites of all sensor materials were well characterized by (1)H, (13)C NMR, and mass (FAB) spectral analysis. Detection limits were calculated from standard deviations and linear fitting calculations. The association constant (log K(a)) values of sensor complexes were evaluated from the fluorescence binding isotherms. The fluorescence decay constant (τ) values were estimated from time resolved fluorescence studies. Time, temperature, pH and solvent concentration effects towards sensor responses were fully investigated in this report.

摘要

首次报道了简单的吡啶基水杨醛亚胺衍生物(F1、F2 和 F3)作为荧光“开启”传感器,可在混合水相 CH3CN/H2O 中通过内部电荷转移(ICT)、螯合增强荧光(CHEF)和去质子化机制,在体积比为 6/4 和 3/7 的混合介质中(在 pH = 7 和 25°C 下)分别对 Zn(2+)、Al(3+)和 OH(-)离子进行独特的检测。F1 和 F2 对 Zn(2+)、Al(3+)和 OH(-)离子表现出不同的开启传感应用,但 F3 在 CH3CN/H2O(6/4;体积/体积)中对 Al(3+)和 OH(-)离子表现出荧光开启传感。F1+Zn(2+)和 F2+Zn(2+)配合物分别在 CH3CN/H2O(6/4;体积/体积)中显示了 Zn(2+)与乙二胺四乙酸(EDTA)和 Al(3+)离子的可逆性和比率置换。另一方面,F1、F2 和 F3 在 CH3CN/H2O(3/7;体积/体积)中仅对 Al(3+)离子表现出敏感性,但对 OH(-)离子几乎没有选择性。根据紫外/可见和 PL 滴定的 Job's 图计算,所有传感器配合物的化学计量比均为 1:1。通过 (1)H、(13)C NMR 和质量(FAB)光谱分析对所有传感器材料的配合物形成和结合位点进行了很好的表征。根据标准偏差和线性拟合计算得出检测限。从荧光结合等温线评估了传感器配合物的结合常数(log K(a))值。通过时间分辨荧光研究估算了荧光衰减常数(τ)值。本报告全面研究了传感器响应的时间、温度、pH 和溶剂浓度效应。

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