Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, China.
Institute of Biomedical Sciences, School of Life Sciences, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China; Institute of Integrative Biosciences, CECOS University of IT and Emerging Sciences, Peshawar, KPK, Pakistan.
Talanta. 2017 Mar 1;164:307-313. doi: 10.1016/j.talanta.2016.10.085. Epub 2016 Oct 27.
Salicylaldehyde based hydrazones 2-((2-methyl-2-(pyridin-2-yl)hydrazono)methyl)phenol (SMPH), 4-methyl-2-((2-methyl-2-(pyridin-2-yl)hydrazono)methyl)phenol (MSMPH) and 4-fluoro-2-((2-methyl-2-(pyridin-2-yl)hydrazono)methyl)phenol (FSMPH) were prepared and structurally characterized. These hydrazones exhibited fluorescence "turn on" response toward Al in dimethyl formamide/water (DMF/HO) (1: 1) mixture. SMPH showed enhanced emission (70 folds) as compared to MSMPH (46 folds) and FSMPH (28 folds) upon the addition of 3 equivalents of Al. Similarly a red shift was observed in the emission wavelength of hydrazone/Al mixture from non-substituted (SMPH) to fluoro-substituted (FSMPH) and in turn to methyl-substituted (MSMPH). They also showed high selectivity towards Al over the other common metal ions. Among the tested metal ions only copper interfered and quenched the fluorescence completely. Further SMPH was investigated spectroscopically in details for Al detection. The binding phenomenon of SMPH was analyzed by H NMR and HR-ESI-MS. Mass analysis showed a 1: 1 complex formation of SMPH with Al. Job's plot also confirmed their 1: 1 interaction. SMPH showed a good tolerance for Al detection in acidic to neutral pH, ranges 3-8. The limit of detection (LOD) for Al was observed to be 1.5×10M. Moreover SMPH and MSMPH were studied for living cells imaging in MCF-7 (Michigan Cancer Foundation-7) cells. These analyses also revealed the importance of these hydrazones in monitoring Al in living cells.
基于水杨醛的腙 2-((2-甲基-2-(吡啶-2-基)腙基)甲基)苯酚（SMPH）、4-甲基-2-((2-甲基-2-(吡啶-2-基)腙基)甲基)苯酚（MSMPH）和 4-氟-2-((2-甲基-2-(吡啶-2-基)腙基)甲基)苯酚（FSMPH）被制备并进行了结构表征。这些腙在二甲基甲酰胺/水（DMF/HO）（1:1）混合物中对 Al 表现出荧光“开启”响应。与 MSMPH（46 倍）和 FSMPH（28 倍）相比，SMPH 的发射增强（70 倍）在加入 3 当量的 Al 后。同样，在腙/Al 混合物中，从未取代的（SMPH）到氟取代的（FSMPH），然后到甲基取代的（MSMPH），观察到发射波长的红移。它们还对 Al 表现出相对于其他常见金属离子的高选择性。在测试的金属离子中，只有铜干扰并完全猝灭荧光。进一步详细研究了 SMPH 对 Al 检测的光谱性质。通过 1H NMR 和 HR-ESI-MS 分析了 SMPH 的结合现象。质谱分析表明 SMPH 与 Al 形成 1:1 的络合物。Job 图也证实了它们的 1:1 相互作用。SMPH 在酸性到中性 pH 范围内（3-8）对 Al 检测具有良好的耐受性。Al 的检测限（LOD）观察到为 1.5×10M。此外，还研究了 SMPH 和 MSMPH 在 MCF-7（密歇根癌症基金会-7）细胞中的活细胞成像。这些分析还揭示了这些腙在监测活细胞中 Al 方面的重要性。
