有机化学 ›› 2019, Vol. 39 ›› Issue (4): 1013-1022.DOI: 10.6023/cjoc201809025 上一篇    下一篇

所属专题: 荧光探针-生物传感合辑 有机超分子化学合辑

研究论文

一种新型苯并咪唑-酰腙衍生物用于比色和荧光识别F和AcO

李英俊a, 赵月a, 靳焜b, 刘季红c, 周晓霞a, 杨凯栋a   

  1. a 辽宁师范大学化学化工学院 大连 116029;
    b 大连理工大学精细化工国家重点实验室 大连 116012;
    c 大连理工大学化学分析测试中心 大连 116023
  • 收稿日期:2018-09-20 修回日期:2018-12-03 出版日期:2019-04-25 发布日期:2018-12-21
  • 通讯作者: 李英俊 E-mail:chemlab.lnnu@163.com
  • 基金资助:

    辽宁省自然科学基金(No.20102126)资助项目.

A Novel Benzimidazole-Hydrazone Derivative for Colorimetric and Fluorescent Recognition of F and AcO

Li Yingjuna, Zhao Yuea, Jin Kunb, Liu Jihongc, Zhou Xiaoxiaa, Yang Kaidonga   

  1. a College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029;
    b State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012;
    c Chemistry Analysis and Inspection Center, Dalian University of Technology, Dalian 116023
  • Received:2018-09-20 Revised:2018-12-03 Online:2019-04-25 Published:2018-12-21
  • Contact: 10.6023/cjoc201809025 E-mail:chemlab.lnnu@163.com
  • Supported by:

    Project supported by the Natural Science Foundation of Liaoning Province (No.20102126).

合成出了1个新的苯并咪唑-酰腙衍生物,N'-(2-羟基-1-萘基)亚甲基-2-[2-(4-甲基苯磺酰基甲基)-1H-苯并咪唑-1-基]乙酰肼(L),并利用IR,1H NMR,13C NMR,HRMS和元素分析对其结构进行了表征.利用裸眼、紫外-可见与荧光光谱研究了L对阴离子的识别性能.研究结果表明,向化合物L的CH3CN溶液中加入F-,AcO-和H2PO合成出了1个新的苯并咪唑-酰腙衍生物,N'-(2-羟基-1-萘基)亚甲基-2-[2-(4-甲基苯磺酰基甲基)-1H-苯并咪唑-1-基]乙酰肼(L),并利用IR,1H NMR,13C NMR,HRMS和元素分析对其结构进行了表征.利用裸眼、紫外-可见与荧光光谱研究了L对阴离子的识别性能.研究结果表明,向化合物L的CH3CN溶液中加入F-,AcO-和H2PO4-后,溶液由无色变为亮黄色.在紫外灯下(λ=365 nm),加入F-和AcO-后,L的溶液发射出黄色荧光.表明化合物L可作为裸眼识别F-,AcO-和H2PO4-的探针.紫外和荧光光谱实验结果显示,探针L可高选择性和高灵敏性识别F-和AcO-.探针L与F-和AcO-的结合常数(Ka)分别为4.25×103和2.96×104 L·mol-1,检出限(DL)分别为3.63×10-7和8.51×10-8 mol·L-1.Job曲线和密度泛函理论(DFT)计算证明,探针L与F-/AcO-是1:1配位.通过1H NMR滴定确定了探针L与F-/AcO-的络合机理.实验结果表明,化合物L可作为检测F-和AcO-的比色和荧光探针.

关键词: 苯并咪唑-酰腙, 阴离子, 裸眼识别, 比色和荧光探针

A novel benzimidazole-hydrazone derivative,N'-(2-hydroxy-1-naphthyl)methylene-2-[2-(4-methylphenylsulfonyl-methyl)-1H-benzoimidazol-1-yl]acetohydrazide (L), was synthesized and characterized by IR, 1H NMR, 13C NMR, HRMS and elemental analysis. The recognition properties of L for anions were studied by naked eye, ultraviolet-vis and fluorescence spectroscopy. The results showed that the color of the solution changes from colorless to bright yellow upon addition of F-, AcO- and H2PO4- to the CH3CN solution of compound L. The solution of L emitted yellow fluorescence after the addition of F- and AcO- under the UV lamp (λ=365 nm). It indicated that compound L can be used as a probe for the naked eye to recognize F-, AcO- and H2PO4-. The experimental results of UV and fluorescence spectroscopy showed that the probe L can recognize F- and AcO- with high selectivity and sensitivity. The binding constants (Ka) of probe L to F- and AcO- were 4.25×103 and 2.96×104 L·mol-1, respectively. The detection limits (DL) were 3.63×10-7 and 8.51×10-8 mol·L-1, respectively. The stoichiometry of complexation between L and F-/AcO- was 1:1, which was supported by the Job's plot and density functional theory (DFT) calculations. The mechanism of binding of L with F-/AcO- was established by 1H NMR titration. The results showed that compound L can be used as a colorimetric and fluorescent probe for detecting F- and AcO-.

Key words: benzimidazole-hydrazone, anion, naked-eye recognition, colorimetric and fluorescent probe