新型双吡啶盐的合成及其作为硝酸根离子荧光增强型探针的性能研究  

New Bipyridinium Salt:Synthesis and Application as a Fluorescence Enhancement Probe of Nitrate Ion

作　　者：邹顺瑛 孙文豪[2] 贡卫涛[3] 

机构地区：[1]大连金州新区环境监测站,辽宁大连116600 [2]大连市环境监测中心,辽宁大连116000 [3]大连理工大学化工学院,辽宁大连116024

出　　处：《光谱学与光谱分析》2015年第6期1597-1600,共4页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(21206016)资助

摘　　要：阴离子普遍存在于生命体和环境中,在化学、生物学、医学和环境领域都具有重要的作用,而硝酸根是其中一种非常重要的无机阴离子,对环境和人体健康都具有极大危害。目前测定硝酸根离子的方法主要有电化学法、离子色谱法和离子选择性电极法等。虽然各方法各具优势,但也存在明显不足。电化学法重现性差,而离子色谱法和离子选择性电极法需要较为复杂、昂贵的仪器及较长的分析时间。荧光光谱由于具有较高的灵敏度和操作简便等优点,近年来成为阴离子识别和检测领域的研究热点。以吡喃盐为起始原料,设计合成了一种新型的双吡啶盐化合物,通过核磁共振1 H谱、13 C谱以及高分辨质谱确定了其分子结构。并研究了其与不同阴离子的荧光识别性能,显示出对硝酸根离子明显的特异性识别。在双吡啶盐溶液中滴加硝酸根离子后,荧光呈现显著增强,而其他竞争性阴离子则淬灭初始荧光。通过荧光滴定实验证实双吡啶盐探针与硝酸根离子形成稳定的1∶1超分子配合物,稳定常数lgK=5±0.02。通过计算机模拟计算以及变温核磁共振波谱表明硝酸根离子与双吡啶盐上活性氢形成稳定的氢键,并诱导整个双吡啶盐分子的共平面性增大,荧光强度增强,从而达到选择性识别的效果。Anions are ubiquitously distributed not only in biological systems but also in environment.Accordingly,anion recognition and sensing have attracted increasing attention due to the important roles anion plays in biological,chemical and environmental fields.Among various anionic species,NO-3is a very important inorganic anions which has a great harm to the environment and human health.At present,methods for the determination of NO-3mainly contained electrochemical method,ion chromatography and ion selective electrode method.Although all methods have their own advantages,but also has the obvious deficiency.Such as,the reproducibility of electrochemical method is not good,and ion chromatography and ion selective electrode method usually require expensive apparatus and lengthy analytical time.As a contrast,fluorescence spectroscopy become a hot research topic in anion recognition and detection because of its high sensitivity and easy operation and other advantages in recent years.New bipyridinium salt L was designed and synthesized using pyrylium as a starting material.The molecular structure was determined by 1 H NMR,13 C NMR,and high resolution mass spectrometry.The molecular recognition properties of L have been investigated through fluorescence titration experiments.The results indicate that L has sensitive and selective fluorescent response to NO-3among other different anions.Significant enhancements in the fluorescence intensity of L were observed when various concentrations of NO-3were added,while other competing anions have a quenching effect towards the initial fluorescence of solution.The fluorescence titration spectra shows that the bonding stoichiometry between receptor L and NO-3is 1∶1as a supramolecular complexes（lgK=5±0.02）.The chemosensing properties of L were evaluated through quantum chemical calculations and the variable temperature 1 H NMR titration.These results suggested that L has strong binding affinity towards NO-3with high selectivity,which may be ascribed to the specific hydrogen bond

关 键 词：双吡啶盐 硝酸根 荧光探针 超分子 阴离子 

分 类 号：O657.3[理学—分析化学]