基于杯[4]冠醚的1,3,4-噁二唑荧光探针的合成及对金属离子的识别  

Calix[4] crown-based 1,3,4-Oxadiazoles as Fluorescent Chemosensors:Synthesis and Ion Recognition

作　　者：谢迪欢 孙春[1] 王晓静[1] 韩杰[1] XIE Dihuan SUN Chun WANG Xiaojing HAN Jie(College of Chemistry, Nankai University, Tianjin 300071, China)

机构地区：[1]南开大学化学学院,天津300071

出　　处：《高等学校化学学报》2016年第11期1966-1971,2125-2128,共6页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21272130)资助~~

摘　　要：分别以2-苯基-5-(2-吡啶基)-1,3,4-噁二唑及2,5-二苯基-1,3,4-噁二唑为荧光基团,设计合成了基于杯[4]冠醚结构的荧光探针分子1a和1b;利用核磁共振氢谱(~1H NMR)、碳谱(^(13)C NMR)及高分辨质谱(HRMS)表征了其结构.采用紫外-可见光谱及荧光光谱考察了探针分子1a和1b对碱金属离子(Na^+,K^+,Cs^+)、碱土金属离子(Mg^(2+),Ca^(2+))及过渡金属离子(Mn^(2+),Co^(2+),Ni^(2+),Cu^(2+),Zn^(2+),Cd^(2+),Ag^+)的识别作用.结果表明,Na^+可使探针分子1a的二氯甲烷溶液荧光强度显著增强,K+和Cs^+对探针分子1a的荧光强度几乎无影响,而Ca^(2+)及所有过渡金属离子均可有效猝灭探针分子1a的荧光.探针分子1b对于碱金属离子的识别作用与探针分子1a相似,但其与过渡金属离子的络合作用弱于探针分子1a.根据核磁共振表征结果讨论了金属离子与荧光探针的络合位点.Two fluorescent chemosensors,1a and 1b,were synthesized by appending 2-phenyl-5-（ 2-pyridyl）-1,3,4-oxadiazole or 2,5-diphenyl-1,3,4-oxadiazole moieties on a calix[4]crown skeleton,respectively. Their molecular structures were characterized by proton and carbon nuclear magnetic resonance spectroscopy（1H NMR and 13C NMR） and high resolution mass spectroscopy（ HRMS）. The recognition behaviors of probes1 a and 1b in CH2Cl2 solution to alkali metal ions（ Na＋,K＋,Cs＋）,alkaline earth metal ions（ Mg2＋,Ca2＋）and transition metal ions（ Mn2＋,Co2＋,Ni2＋,Cu2＋,Zn2＋,Cd2＋,Ag＋） were investigated by UV-Vis spectrum and fluorescence spectrum. The results showed that Na＋enhanced the fluorescence intensity of probe 1a significantly,while K＋and Cs＋only resulted in negligible changes in the fluorescence. In contrast,Ca2＋and all the transition metal ions may quench the fluorescence greatly due to the photo-induced electron transfer mechanism. The recognition behaviors of probe 1b to alkali metal ions are similar to those of probe 1a,and complexation between probe 1b and the transition metal ions is weaker than that of probe 1a and the transition metal ions. The complexation has been investigated by means of ~1H NMR titration.

关 键 词：杯[4]冠醚 1 3 4-噁二唑 荧光探针 金属离子 

分 类 号：O626.27[理学—有机化学]