New Fluorescent Chemosensors for Cationic Guests: 1,8-Bis(azacrown)anthracenes

New macrocyclic ditopic anthracenyl receptors display largechelation-enhanced fluorescence (CHEF) effects upon the addition of linear dications⁺NH₃(CH₂)_nNH₃ ⁺. The amplitude of the effect, which is dependent on the chain length,was at a maximum for propylenediammonium cation. This 1,8-bisazacrown anthracene displaysdifferent binding affinities toward metal ions compared to those of 9-azacrown anthracene.     

两种新型F-荧光化学传感器的合成及其性质研究

本文设计合成了N⁶-对甲苯磺酰胺腺嘌呤(I)和邻苯二对甲苯磺酰胺(Ⅱ)两种主体化合物.通过对其与阴离子物种之间相互作用的研究发现,它们在乙腈溶液中和Cl^-、Br^-、NO₃^-、NO₂^-、HSO₄^-、Ac^-、F^-几种阴离子相互作用时,仅对F^-具有专一的选择性识别作用.F^-离子可使I和Ⅱ主体的荧光吸收猝灭并发生红移.通过试验证明,F^-离子和I、Ⅱ主体的识别作用机理是因形成了激基缔合物.     

新型氮杂18-冠-6衍生物的合成及其与阳离子的配位性能

通过1,10-二氧-4,7,13,16-四氮杂18-冠-6 (1)与2-羟基-5-硝基苄基溴反应合成了一个四硝基酚取代的氮杂18-冠-6衍生物(2). 采用UV-Vis光谱法研究了混合溶剂中冠醚2对H^＋, Mg^2＋, Ca^2＋, Sr^2＋, Ba^2＋和Pb^2＋的光谱响应及配位性能. 结果表明, 随溶液pH值的增大, 冠醚2的最大吸收峰由319 nm逐渐红移到426 nm, 并伴随着强度的增大; 其与几种阳离子形成配合物的稳定常数随阳离子半径的增加而增大, 从而展示了对Ba^2＋和Pb^2＋高的配位能力.     

Bile Acids-Selective Chemosensors Based on NBD-amine-Modified Cyclodextrins

A new type of fluorescent chemosensor, based on modified cyclodextrins bearing the fluorophore unit NBD-amine, was prepared. One of these new chemosensors, NC0γCD is very sensitive to bile acids, but is not sensitive to other guests (e.g. adamantane and borneol derivatives). The response of the new type of chemosensor to a guest was an increase in the fluorescence intensity and the sensitivity parameter (ΔI/I ₀ ) dose not correlate to the binding affinity of NC0γCD.     

基于酰胺的荧光双冠醚阴离子受体的合成和识别性能研究

合成了一种带有荧光基团蒽的酰胺型双冠醚阴离子受体3. 用荧光光谱、紫外-可见吸收光谱及核磁共振氢谱研究了其与F^－, Cl^－, Br^－, I^－, H₂PO₄^－, AcO^－离子的相互作用, 结果表明3只对F^－具有很好的选择性识别能力, 并形成配合比为1∶2的络合物, 通过荧光发射强度计算出主体3与F^－间的相互作用时的结合常数.     

对称萘酚亚胺化合物的pH荧光效应及对阴离子的识别作用

合成了一种含萘酚结构的对称亚胺主体化合物。通过对其与阴离子物种之间相互作用的研究,观察到在水溶液中,随着体系pH值的升高,主体荧光强度增强并且最大发射波长红移。其荧光性能与pH存在着强烈的依赖关系,具有明显的pH荧光"开-关"作用。同时,在乙腈溶液中,该结构对F-有较强的荧光选择响应,对Ac-响应稍弱,而对其它阴离子的选择响应较差。结合所观察到的实验现象,对实验结果进行了分析和讨论,并初步探讨了该化合物对H 、OH-、F-、Ac-的识别机理。     

Synthesis and Crystal Structure of a New N-alkylated Azacrown Ligand

1mTRODUCTIONAzamacrocyclicligandsandtheirmacrocyclicderivativeswithincorporatingpendantarmsgroupshavereceivedmuchattentionfortheirusesiniontransportandasmodelsinbiomimicresearchc1-51.Recentlymuchattentionisespeciallyfocusedonstudyingtransitionmetalcomplexesofmacrocycles"-".Conversely,onlyafewre-Portsareaboutcomplexesofmixedoxygen-nitrogendonormacrocyclesincorporatingtwoPendantarms,mostofwhicharecarboxylicacidgroups.Theymaybeappliedinionidentification,iontransportandionseparation"-"'aswell…     

Macrocyclic anthracene-anchored calix[4]arene as a sensitive and selective fluorescent chemosensor for ytterbium ions

ABSTRACT

A novel anthracene anchored cone calix[4]arene pyridine amide receptor C4PA was synthesized and characterized by combination of spectroscopic and spectrophotometric techniques. Ion binding properties of C4PA towards a series of metal cations were investigated by UV and fluorescence spectra. A remarkable increase for receptor C4PA in fluorescence intensity in the presence of trace amounts of Yb³⁺ was observed. C4PA showed “turn on” type fluorescence response toward Yb³⁺ with high selectivity and C4PA also retained its selectivity toward Yb³⁺ in the presence of most competing metal ions.     

阴离子荧光受体研究进展

本文总结了近年来阴离子荧光受体的研究进展和荧光化学传感的主要机理,主要 介绍以下3类受体的设计合成及其在阴离子识别中的应用:(1)以氢键或静电作用键合阴 离子的受体(包括酰胺、脲及硫脲、胍盐和硫脲盐、五员杂环);(2)含金属和路易斯酸的受体;(3)以竞争键合机制识别阴离子的"化学传感体系".     

Cation Recognition by Picolyl-Armed Calix[4]crown-5-azacrown-5s

A series of N-pivot calix[4]crown-5-azacrown-5 ethers substituted by 2-picolyl, 3-picolyl and benzyl groups respectively were synthesized. The nitrogen atom of the 2-picolyl group is found to participate in the silver ion complexation through three dimensional encapsulation.     

核苷磷酸盐对含双芘侧链荧光敏感器化合物的荧光猝灭与分子识别

合成了一种在水溶液中对核苷磷酸盐ATP,ADP,AMP阴离子具有识别能力的荧光化学敏感器分子---化合物1。通过检测化合物1在水溶液中芘激基缔合物荧光发射强度随核苷磷酸盐、腺嘌呤等的加入而引起的变化,求出不同核苷磷酸盐及腺嘌呤对芘激基缔合物荧光发射的猝灭常数,并进行了比较研究。利用荧光发射强度随不同核苷磷酸盐引入而发生的变化计算出化合物1对不同核苷磷酸盐进行配位的配位稳定常数。结果表明所合成的化合物1对ATP有着良好的识别力选择功能。此外,还利用分子力学的计算方法对化合物1及其与核苷磷酸盐形成配合物后的分子构象及几何尺寸作了计算,并结合实验结果进行了初步讨论。     

1,8-萘酰亚胺为发色团的Zn2+荧光探针的合成及性能研究

合成了以1,8-萘酰亚胺为发色团,以联吡啶为离子受体的Zn²⁺荧光探针,并进行了表征及离子识别性能的研究。研究表明该化合物对Zn²⁺具有良好的识别性能,同时相对于Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Ni²⁺, Pb²⁺等金属离子具有良好的选择性。     

基于蒽-苯并咪唑鎓的荧光传感器对H2PO4-的高选择性识别

设计合成了基于蒽-苯并咪唑鎓的受体分子1和2,通过荧光发射光谱研究了受体分子1和2对F^-、Cl^-、Br^-、I^-、AcO^-、HSO₄^-、H₂PO₄^-、NO₃^-、ClO₄^-等阴离子的识别性能。 研究发现,在受体分子1和2的乙腈溶液(5.0×10^-6 mol/L)中加入10倍化学计量的H₂PO₄^-时,受体分子1的荧光猝灭百分数为13%,受体分子2的荧光猝灭百分数高达94%,表明受体分子2在构型上与H₂PO₄^-更匹配,可作为H₂PO₄^-的荧光关闭型(turn-off)探针。 受体分子2与H₂PO₄^-的结合比为1:1,结合常数为(3.70±0.16)×10⁴ L/mol,检出限为3.77×10^-6 mol/L。     

Synthesis and characterization of M(II) (M = Cd,Hg and Pb) complexes with naphthodiaza-crown macrocyclic ligand and study of metal ion recognition by fluorescence, 1H NMR spectroscopy,and DFT calculation

To find metal ion recognition by L (L = O₂N₂-donor naphthodiaza-crown macrocyclic ligand), the complexes [ML]²⁺ (M = Cd, Hg and Pb) were synthesized and characterized by IR, ¹H, ¹³C NMR, and mass spectrometry, as well as elemental microanalysis. Hg(II) showed perceptible enhancement of the fluorescence of L in which ultra-low limit of detection for Hg(II) by L was determined as 1 nM in ethanol and DMSO. L reserved selectivity of Hg(II) in its binary mixtures with metal cations in solution. A 1 : 1 stoichiometry was found for the interaction of Hg(II) with L while Benesi–Hildebrand method was applied to calculate its complexation binding constant (K_BH) employing fluorescence spectrophotometry. The monitoring of the chemical shifts in ¹H NMR spectra of these complexes demonstrated that the central macrocycle of L was tailored for the size of Hg(II). Density functional theory calculations using B₃LYP/6–31G* basis set demonstrated that the macrocycle cavity of L was properly fitted for complex formation with Hg(II) cation, while both Cd(II) and Pb(II) cations did not form strong bonds with L from inadequate cation size. The present study shows detection method of Hg(II) and also possible application of naphthodiaza as an appropriate fluorophore macrocyclic ligand for detecting other metal ions.     

两种臂式荧光氮杂冠醚化学传感器

合成了萘基臂式苯并氮杂15-冠-5 (3)和5-氯喹啉基臂式苯并氮杂15-冠-5 (4)两种荧光化学传感器, 由元素分析、NMR等进行了结构表征|在乙醇溶剂中采用紫外光谱和荧光光谱法分别研究了冠醚3和4对金属离子K^＋, Ca^2＋, Mg^2＋, Pb^2＋, Co^2＋, Ni^2＋, Mn^2＋, Cu^2＋, Zn^2＋, Cd^2＋和Hg^2＋的选择性传感性能. 结果表明, 冠醚3仅对Cu^2＋离子有显著的传感作用, 是一种典型的辐射能量转移过程. 冠醚4对Ni^2＋, Co^2＋, Cu^2＋和Mn^2＋离子有特殊的敏感性, 金属离子浓度逐渐增大使冠醚4产生先增强后猝灭的荧光现象, 荧光增强归因于阻断了从冠环氮原子到喹啉荧光体的弱光诱导电子转移(PET)过程, 而选择性猝灭源于冠醚环与喹啉基团对金属离子协同螯合的机制. 冠醚3和4的构性关系表明, 发光体基团对传感器的选择性能够产生重要的影响.     

可用于连续识别Cu^2+和阴离子、中性分子荧光探针的研究进展

铜(Cu)含量的高低直接影响着生命体的正常运转和自然体系的平衡.检测铜离子的方法多种多样,其中具有较高敏感度和选择性的荧光化学传感器应用更加广泛.综述了以Cu^2+为基的荧光化学传感器通过替换法实现了对阴离子S^2-, CN^-, H2PO4^-, PPi和I^-以及中性分子ATP、ADP和生物硫醇等的连续识别的研究进展.     

Fluorescence turn-on chemosensor for Hg<Superscript>2+</Superscript> based on a rhodamine derivative and its application in bioimaging

A fluorescence turn-on chemosensor based on rhodamine B derivative (FD10) has been developed as a highly sensitive chemosensor for Hg²⁺. A prominent fluorescence enhancement was measured in the presence of Hg²⁺, which was in agreement with the changes in the absorption spectrum. Furthermore, by means of laser scanning fluorescence microscopy experiments, it was demonstrated that FD10 was cell-permeable and could be used as a fluorescent probe for monitoring Hg²⁺ in living cells. Supported by the National Natural Science Foundation of China (Grant No. 20801015) and Shanghai Leading Academic Discipline Project (Grant No. B108)