有机化学 ›› 2021, Vol. 41 ›› Issue (7): 2839-2847.DOI: 10.6023/cjoc202102013 上一篇    下一篇

研究论文

高选择性快速检测Cu2+的水杨酰腙型探针的合成及在逻辑门和吸附中的应用

何佳伟a, 解正峰a,b,*(), 薛松松a, 刘宇程a,b, 石伟a, 陈鑫c,*()   

  1. a 西南石油大学化学化工学院 油气田应用化学四川省重点实验室 成都 610500
    b 西南石油大学工业危废处置与资源化利用研究院 成都 610500
    c 西南石油大学化学化工学院 计算化学与分子模拟中心 成都 610500
  • 收稿日期:2021-02-02 修回日期:2021-03-10 发布日期:2021-03-25
  • 通讯作者: 解正峰, 陈鑫
  • 基金资助:
    四川省青年科技创新研究团队(2020JDTD0018)

Synthesis of Salicylhydrazone Probe with High Selectivity and Rapid Detection Cu2+ and Its Application in Logic Gate and Adsorption

Jiawei Hea, Zhengfeng Xiea,b(), Songsong Xuea, Yucheng Liua,b, Wei Shia, Xin Chenc()   

  1. a Oil & Gas Field Applied Chemistry Key Laboratory of Sichuan Province, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500
    b Research Institute of Industrial Hazardous Waste Disposal and Resource Utilization, Southwest Petroleum University, Chengdu 610500
    c Center for Computational Chemistry and Molecular Simulation, College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500
  • Received:2021-02-02 Revised:2021-03-10 Published:2021-03-25
  • Contact: Zhengfeng Xie, Xin Chen
  • Supported by:
    Sichuan Youth Science and Technology Innovation Research Team Project(2020JDTD0018)

以4-溴代三苯胺、5-甲醛基呋喃-2-硼酸和水杨酰肼为原料, 设计合成了一种新型的可快速识别Cu2+的席夫碱类荧光探针分子(HJW-2), 并通过1H NMR,13C NMR和HR-MS对其结构进行了表征. 基于分子内电荷转移机理(ICT),HJW-2展现出优异的溶剂效应, 对Cu2+具有快速识别、高选择性和专一性, 检测限低至9.8×10–8 mol•L–1, 响应时间仅需10 s, 通过1H NMR滴定实验和HRMS以及密度泛函理论计算, 对其可能的响应机理进行了探究. HJW-2已成功用于分析不同水样中的Cu2+浓度, 并且利用HJW-2在乙二胺四乙酸(EDTA)存在时的可逆性, 以Cu2+和EDTA为化学输入, 构建了分子逻辑门. 在实际应用中, 通过聚丙烯酰胺(PAM)掺杂HJW-2 (PAM-HJW-2)能实现对Cu2+的高效吸附, 去除率达到99.94%, 并通过扫描电子显微镜(SEM)和X光微区分析(EDS)对PAM-HJW-2吸附前后的微观形貌和元素变化进行了对比.

关键词: 荧光探针, 铜离子, 分子逻辑门, 吸附, 分子内电荷转移机理(ICT)

A novel Schiff base fluorescent probe (HJW-2) was designed and synthesized from 3-bromo-N,N-diphenylaniline, 5-formaldehyde-furan-2-boric acid and 2-hydroxybenzohydrazide. The structure of the probe molecule was confirmed by1H NMR,13C NMR and HRMS. Based on the mechanism of intra-molecular charge transfer (ICT),HJW-2 shows excellent solvent effect.HJW-2 displayed efficiency, high selectivity, and specificity in the detection of Cu2+. The detection limit of HJW-2 on Cu2+ is as low as 9.8×10–8 mol•L–1, and the response time is only 10 s. The possible mechanism was studied by1H NMR, HRMS and density functional theory (DFT) calculations.HJW-2 has been successfully used to analyze the content of Cu2+ in different water samples. Further, by utilizing the reversibility of HJW-2 in the presence of ethylene diamine tetraaccetic acid, the molecular logic gate is constructed with Cu2+ and EDTA as chemical inputs. Then, polyacrylamide (PAM) doping with HJW-2 (PAM-HJW-2) had high adsorption for Cu2+ and the removal rate was 99.94%. The micro-morphology of PAM-HJW-2 before and after adsorption was observed by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS)

Key words: fluorescent probe, copper ions, molecular logic gate, adsorption, intra-molecular charge transfer (ICT)