芘修饰杯芳烃对钠离子的高选择性荧光传感

经六步反应合成了新型杯[4]芳烃衍生物,其中杯[4]芳烃上缘的芘基作为荧光团,下缘的四个乙酯基作为离子载体,该化合物的结构经核磁和质谱鉴定.通过荧光光谱研究了主体化合物对碱、碱土金属离子的键合行为.结果表明主体化合物能够高选择性的识别钠离子,稳定常数为2190L·mol^-1.当加入钠离子时,芘基的excimer峰下降,同时monomer峰逐渐上升,而其它碱、碱土金属离子的加入没有导致主体化合物荧光光谱的变化.因此,该新型的杯[4]芳烃衍生物可以作为钠离子的荧光传感器.     

基于萘酰亚胺的Hg~(2+)和Cu~(2+)荧光探针

通过衍生化4-氨基-1,8-萘二甲酰亚胺合成了一个含有酰胺基和磺酰胺基配位点、可以选择性识别汞离子和铜离子的荧光探针(NAS)。在乙醇/4-羟乙基哌嗪乙磺酸(HEPES)缓冲溶液中,NAS显示淡黄色弱荧光,加入汞离子后变为蓝色强荧光,而铜离子能引起NAS荧光猝灭。常见金属离子对这两种离子的检测都没有影响,但铜离子会影响NAS对汞离子的荧光增强响应。通过质谱分析,并参考有关4-酰胺基萘二甲酰亚胺类荧光探针的研究文献,提出了NAS分别与汞离子及铜离子的配位结构。     

镝(Ⅲ)离子比色/荧光传感器:杯芳席夫碱的设计与合成

合成了一种新型含杯[4]芳烃的席夫碱类化合物,镝(III)离子的加入使得其溶液的颜色由无色变为黄色,荧光强度降低.而不含杯芳烃空腔的模型化合物加入硝酸镝后溶液颜色没有明显变化.这说明合成的含杯[4]芳烃的席夫碱化合物能够选择性的识别镝(III)离子,可用作分析化学中镝离子的检测.     

硫杂杯[4]芳烃酰胺基硫脲衍生物的合成

硫杂杯[4]芳烃四乙酸乙酯衍生物与水合肼反应生成硫杂杯[4]芳烃四酰肼衍生物(3),3与异硫氰酸苯酯反应得到新型硫杂杯[4]芳烃酰胺基硫脲衍生物,总产率61%。     

新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能

杯[4]-1,3-二乙酸乙酯衍生物(1)与水合肼反应生成杯[4]芳烃酰肼衍生物(2),化合物(2)与异硫氰酸苯酯反应得到含酰胺和硫脲单元的新型杯[4]芳烃衍生物(3).总产率达70%.系列氨基酸萃取实验表明化合物(3)对异亮氨酸有较好的选择性萃取能力.     

多重氮杂杯[4]芳烃和双杯[4]芳烃的合成与阳离子萃取性能

合成了含有偶氮基、胺基、酰胺基和席夫碱基新型杯[4]芳烃多重氮杂衍生物3和4以及双杯[4]芳烃5,产率分别为87%、89%和84%。它们的结构经1H NMR、ESI-MS和元素分析表征确证。液液两相萃取实验表明,它们对阳离子有较好的萃取能力,比仅含酰胺基和席夫碱基的类似杯芳烃衍生物有明显提高。     

含硫脲基的多重氮杂杯[4]芳烃衍生物的合成与有机染料配合性能

以杯[4]芳烃为平台,构筑结构与识别性能独特的杯[4]芳烃衍生物是有机超分子化学的重要研究领域.本文中,杯[4]二芳胺基衍生物3与异硫氰酸苯酯反应得到开链的二硫脲基杯[4]衍生物4,产率为95%.化合物3与等物质的量对二异硫氰酸苯酯反应得到二硫脲基桥连杯[4]衍生物5,产率为80%.与过量的对二异硫氰酸苯酯反应则以产率为82%得到化合物6.化合物6进一步与水杨酰肼反应得到含硫脲基的多重氮杂杯[4]衍生物7,产率为75%.紫外光谱配合实验表明新主体分子4~7对测试的4种有机染料分子(橙黄Ⅰ、茜绿素、维多利亚蓝和亚甲基蓝)均显示出较强的配合能力,配合常数的数量级达10~5,配合比为1∶1.开链结构与多重胺基和芳基结构更有利于配位包合能力的提高.     

硫杂杯芳烃冠醚的合成及其与氨基酸配合性能的研究

在普通杯芳烃骨架中引入硫原子可以改善普通杯芳烃的配合性能。文中首先合成了硫杂杯[4]芳烃四酰肼衍生物3,在弱酸的催化下继续与化合物4反应,高产率地合成了同时含酰胺和席夫碱单元的硫杂杯[4]芳烃冠醚衍生物5,新化合物的结构经1H NMR、元素分析、ESI-MS等表征证实。同时探讨了新型硫杂杯[4]芳烃衍生物5与系列-α氨基酸的配合性能。     

含酰胺和席夫碱单元的杯[4]芳烃衍生物的合成与配合性能

杯[4]-1,3-二乙酸乙酯衍生物1与水合肼反应生成杯[4]芳烃酰肼衍生物2, 然后进一步与相应的芳醛反应, 高产率地合成了三个新型的含酰胺和席夫碱单元的杯[4]芳烃衍生物3a～3c和一例新型杯[4]冠醚4. 阳离子萃取实验表明新型杯芳烃衍生物比只含有酰胺基或席夫碱基的杯芳烃衍生物有更强的软金属离子配合性能, 杯[4]冠醚4还对Ag^＋有较好的选择性萃取能力.     

新型杯[4]芳烃氨基苯酚类衍生物的合成及对La3 的选择性识别

设计合成了下缘连有氨基苯氧基结构的杯[4]芳烃衍生物:5,11,17,23-四叔丁基-25-[2-(2-氨基苯氧基)乙氧基]-27-(2-羟基乙氧基)-26,28-二羟基杯[4]芳烃(化合物C),增加了与阳离子的结合位点,有利于通过配位作用对金属离子进行识别。化合物C的结构通过红外光谱、1H NMR、13C NMR和质谱进行了表征。通过紫外可见光谱和荧光发射光谱对化合物C与24种金属阳离子的络合作用进行了研究,结果发现,其对La3+有特殊的识别作用,化合物C与La3+的络合比为1∶1。     

Synthesis of calix[4]arene(amido)monocrowns and their photoresponsive derivatives

A series of new calix[4]arene(amido)mono-crown compounds have been synthesized through aminolysis of calix[4]arene esters and intramolecular cyclization of the intermediates. The title compounds were converted into their nitro and azo substituted derivatives to provide novel photoresponsive molecular receptors for transition metal ions. Single crystal X-ray analysis of calix[4]arene(ethyleneamido)mono-crown (2a) revealed that the compound is present in a cone conformation with an amido loop that caps the lower rim of calix[4]arene cavity to result in stacking along axis a and axis c to provide supramolecular aggregates in the solid state. Evaluation of synthesized macrocycles in the solution phase for recognition of transition metal cations (Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Cd²⁺, Pb²⁺, Hg⁺, Hg²⁺, Pd²⁺, and Pt²⁺) by UV-visible spectroscopy revealed that p-tert-butyl-calix[4]arene mono-(amidocrown) 1c selectively shows a blue shift at 38 nm on interaction with Hg⁺ ions.     

新型经由三氮唑连接的含芘基团的杯[4]芳烃：对锌离子的比率荧光识别及其在组合逻辑门中的应用

通过“click”反应合成了两个新的由三氮唑连接的含芘的杯[4]芳烃。 化合物1含有两个芘单元,对Zn2+表现出比率荧光响应,且对Cu2+, Hg2+ 和 Pb2+表现出选择性的荧光淬灭;而化合物2只含一个芘单元,对铜离子有显著的荧光淬灭,对汞离子有中等程度的荧光淬灭。利用化合物1对锌离子和铜离子不同的荧光响应,设计了INH和NOR逻辑门。     

Synthesis and complexation study of calix[4]arene diamine derivative incorporated in a polymeric backbone with chiral monomers

The novel chiral polymeric compounds containing more than one calix[4]arene have been synthesized by reacting a new calix[4]arene diamine derivative with two chiral monomers. These newly prepared compounds were studied by extraction of toxic heavy metal (Cu²⁺, Co²⁺, Cd²⁺, Hg²⁺), silver and alkali metal (Na⁺, K⁺) cations from aqueous phase. It was observed that the resulting calixarene-based polymers have a good complexing ability towards silver, alkali metal and toxic heavy metal cations.     

1,3-Bis(pyren-1-yliminomethyl)calix[4]arene as a selective fluorescent turn-on sensor for mercury(II) ion

A novel calixarene-based diimine, 1,3-bis(pyren-1-yliminomethyl)calix[4]arene (5), serves as a turn-on-type fluorescent sensor, which selectively detects Hg²⁺ in THF/H₂O (99:1, v/v) in the presence of various other metal ions. Such selectivity is not seen with half salen 1 derived from salicylaldehyde and 1-aminopyrene. ¹H NMR analysis reveals that it is a chemodosimetric sensor based on its hydrolysis mediated by Hg²⁺ to release 1-aminopyrene molecules as fluorescent chromophores.     

Synthesis and characterization of linear molecular assembly of crystalline calix[4]arenes dithianes

A family of six new variously substituted calix[4]arene dithianes has been prepared from respective formyl and acetyl derivatives. Shorter reaction time, mild conditions, and facile isolation of desired products are attractive features of the described method. The new 1,2-dithiane derivatives have been characterized by ¹H NMR, ¹³C NMR spectroscopy, and FABMS analysis. The crystal structure of one of the acetyl calix[4]arene dithiane was determined by X-ray diffraction analysis, which revealed a dithiane capped linear molecular organization. Preliminary evaluation of bis (dithiane) calix[4]arene derivatives as molecular receptor for transition metal ions has revealed strong interaction with Hg²⁺ in 1:1 stoichiometry.     

Polymer Supported Calix[4]arene Schiff Bases: A Novel Chelating Resin for Hg2+ and Dichromate Anions

This article describes the synthesis and characterization of two new calix[4]arene Schiff bases and their polymeric resins. The extraction properties of these “proton switchable extractants” with alkali, transition, post transition metal cations and for dichromate anions are reported. The two new calix[4]arene based Schiff bases (5 and 6) have been synthesized from 5,17‐diformyl‐25,27‐dipropoxy‐26,28‐dihydroxycalix[4]arene (4) by treatment with 3‐amino‐methylpyridine and 1,8‐diaminooctane in two separate reaction flasks following the same procedure. Compounds 5 and 6 have been appended to a polymeric resin by treatment with Merrifield resin through a nucleophilic substitution reaction. The receptor compounds (3 and 5–8) do not extract alkali metal cations, but show some selectivity toward transition metal cations, and a particularly high selectivity to Hg²⁺ and Pb²⁺. The protonated forms of all of the calixarene‐based receptors are good extractants for transferring Cr₂O₇ ^2?/HCr₂O₇ ^? anions from an aqueous into a dichloromethane layer.     

A novel hybrid macrocyclic receptor based on bile acid and calix[4]arene frameworks for metal ion recognition

A novel hybrid macrocyclic receptor based on bile acid and calix[4]arene has been synthesized using the α-face of the bile acid and cone-conformation of calix[4]arene. Metal recognition properties of receptor were investigated. The receptor showed the strongest affinity for Hg²⁺ in acetonitrile. The stoichiometry of the Receptor:Hg²⁺ was 1:1.     

Synthesis of a Tweezer—like Bis（Phenylthiapropoxy）calix[4]—arene as a Cation／π Enhanced Sensor for Ion—Selective Electrodes

Two novel 25,27-dihydroxy-26,28-bis(3-phenylthiapropxy)-calix[4]arene(3) and 25,27-dihydroxy-26,28-bis(3-phenylthiapropoxy)-5,11,17,23-tetra-tert-butylcalix[4] arene (4) were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes(ISEs).ISEs based on 3 and 4 as neutral ionophores were prepared,and their selectivity coefficients for Ag^ (lg KAg,M^pot)were investigated against other alkali metal,alkaline-earth metal,aluminum,thallium(Ⅰ）,Lead and some transition metal ions using the separate solution method (SSM).These ISEs showed excellent Ag^ seletivity over most of the interfering cations examined,except for Hg^2 and Fe^2 having relative smaller interference(lg KAg,M^pot≤-2.1).     

Sorption of heavy metal ions by silica gel-immobilized, proton-ionizable calix[4]arenes

Silica gel-immobilized, di-ionizable calix[4]arenes are employed as stationary phases in ion-exchange chromatography for selected heavy metal ions. Sorption efficiencies for Pb²⁺ are dependent on the structure of the calix[4]arene ligand and the linker that joins the ligand to the silica gel, as well as the acidity of the sample solution. Although the resins exhibit only poor sorption of Cd²⁺, they are found to be scavengers for Hg²⁺. Competitive sorption studies are conducted with selected resins.     

单氧代-二硒烷基-1, w-二氧取代杯[4]衍生物的合成,结构及萃取性能研究

Novel macrocyclic monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a were synthesized by the reaction of calix[4]arene dibromides 1-5 with the disodium salt of bis（2-selenylethyl）ether in the yields between 28% and 64%. Their structures were characterized by proton and carbon NMR spectra. X-Ray structure analysis of la further confirmed the cone conformation of compounds 1a-5a. An interesting host-guest complex of la with dichloromethane via CH/π and C1/π interactions was elucidated. Extraction experiments showed that these novel monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a had strong extraction ability towards mercury ion. The interaction of Hg^2＋with the calix ligand has also been investigated by 1^H NMR titration.