基于Au^(3+)和I-构建的单-(6-二乙烯三胺-6-去氧)-β-环糊精超分子荧光开关  

Mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin Supramolecular Fluorescent Switch Constructed Based on Au^(3+)and I^(-)

作　　者：鲁佳佳 杨俊丽 古捷 杨举 高振杰 苏丽娇 陶欣 袁明伟 杨丽娟 Lu Jiajia;Yang Junli;Gu Jie;Yang Ju;Gao Zhenjie;Su Lijiao;Tao Xin;Yuan Mingwei;Yang Lijuan(Key Laboratory of Intelligent Supramolecular Chemistry at the University of Yunnan Province,National and Local Joint Engineering Research Center for Green Preparation Technology of Biobased Materials,School of Chemistry&Environment,Yunnan Minzu University,Kunming 650500)

机构地区：[1]云南民族大学化学与环境学院云南省高校智能超分子化学重点实验室生物基材料绿色制备技术国家地方联合工程中心,昆明650500

出　　处：《有机化学》2022年第5期1474-1482,共9页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21762051);云南省高校有机功能分子及材料科技创新团队;云南省教育厅科学研究基金资助项目。

摘　　要：选用绿色高效的方法合成了具有较好水溶性的单-(6-二乙烯三胺-6-去氧)-β-环糊精(3N-β-CD),通过核磁共振氢谱(1H NMR)和高分辨质谱(HRMS)对其结构进行表征.用合成的3N-β-CD作为荧光探针对水溶液中的27种离子进行检测,发现Au^(3+)和I-能使3N-β-CD的荧光猝灭.进一步通过荧光滴定、Job曲线、核磁共振、红外光谱、离子干扰、时间响应对3N-β-CD检测Au^(3+)和I-的性能进行了研究.结果表明,Au^(3+)的最低检测限为2.73×10^(-6) mol/L,与3N-β-CD络合的化学计量比为1∶1;I-的最低检测限为1.44×10^(-6) mol/L,与3N-β-CD络合的化学计量比为2∶1;表明该探针可以灵敏地检测Au^(3+)和I-.此外,当I-加入3N-β-CD与Au^(3+)的混合溶液中,3N-β-CD的荧光强度会逐渐恢复;有趣的是,当Au^(3+)加入3N-β-CD与I-的混合溶液中,3N-β-CD的荧光强度也会逐渐恢复.表明Au^(3+)与I-可作为荧光“开-关”来控制3N-β-CD的荧光发光行为,从而使Au^(3+)和I-实现互相检测.并在此基础上设计了控制3N-β-CD荧光开-关的逻辑门.该研究为3N-β-CD作为荧光“开-关”传感器的研究与应用提供了新的实验思路.Mono-(6-diethylenetriamine-6-deoxy)-β-cyclodextrin(3N-β-CD)with the good water solubility was synthesized by a green and efficient method,and its structure was characterized by 1H NMR and HRMS.3N-β-CD was used as a fluorescent probe to detect 27 kinds of ions in aqueous solution.The results showed that the fluorescence of 3N-β-CD was quenched by Au^(3+)and I^(-).The performance of 3N-β-CD for detecting Au^(3+)and I-was further explored by fluorescence titration,Job curve,nuclear magnetic resonance,infrared spectroscopy,ion interference and time response.The results diplayed that the minimum detection limit of 3N-β-CD for Au^(3+)was 2.73×10^(-6) mol/L and the binding stoichiometry ratios of 3N-β-CD with Au^(3+)was 1∶1,while the minimum detection limit of 3N-β-CD for I-was 1.44×10^(-6) mol/L and the binding stoichiometry ratios of 3N-β-CD with I-was 2∶1.In addition,the fluorescence intensity of 3N-β-CD gradually recovered when I^(-)was added into the mixed solution of 3N-β-CD and Au^(3+).Interestingly,the fluorescence intensity of 3N-β-CD also gradually recovered when Au^(3+)was added into the mixed solution of 3N-β-CD and I^(-).The results exhibited that Au^(3+)and I-could be used as fluorescence“on-off-on”to control the fluorescence behavior of 3N-β-CD,and thus enabled Au^(3+)and I-to detect each other.On this basis,the logic gate controlling 3N-β-CD fluorescence switch was designed.This work provides a new apporach for the research and application of 3N-β-CD as a fluorescence“on-off-on”sensor.

关 键 词：单-(6-二乙烯三胺-6-去氧)-β-环糊精 金离子 碘离子 荧光开-关 逻辑门 

分 类 号：O657.3[理学—分析化学]