高选择性比色识别碘离子的氨基硫脲类阴离子受体

设计合成了一系列基于氨基硫脲的阴离子受体（M1～M4）.此类受体以氨基硫脲基团为识别位点,以硝基苯基为信号报告基团,其中受体M1和M3可在乙腈溶液中高选择性的比色识别碘离子.在受体M1或M3的乙腈溶液中加入I^–时,溶液的颜色由浅红色变成无色,而加入其他离子如F^–,Cl^–,Br^–,AcO^–,HSO4^–,H2PO4^–,ClO4^–等阴离子时,受体溶液不会褪色.通过紫外滴定和核磁滴定等方法研究了受体选择性比色识别碘离子的机理.结果表明,受体通过其氨基硫脲基团上的三个NH质子与碘离子形成的三重氢键选择性的结合碘离子.在此过程中,受体构型发生转变,从而导致了颜色变化,产生了比色识别的效果.此类阴离子受体具有合成方法简便,产率高,识别效果好等优点.     

Preparation of a new receptor for anions, macrocyclic polythiolactam—structure and high anion-binding ability

Thiocarbonylation of a macrocyclic tetralactam gave a new macrocyclic tetrathiolactam. The chemical transformation enhances hydrogen-bonding ability of the NH protons in the cavity of the macrocycle, and provides strong affinity toward anions. The association properties of the polythiolactam with anions was examined, and molecular structures of the macrocycle and its Cl⁻ complex were determined.     

Study on the Anion Recognition Properties of Synthesized Receptors （Ⅲ）： Convenient Synthesis and Anion Recognition Property of Bisthiosemicarbazone Derivative

A new series of bisthiosemicarbazone derivative receptors(1,2 and 3)have been synthesized by simple steps ingood yields.Their anion recognition properties were studied by UV-Vis and ~1H NMR spectroscopy.The resultshowed that the receptors 1,2 and 3 all had a better selectivity to F~-,CH_3COO~- and H_2PO_4~-,but no evidentbinding with Cl~-,Br~-,I~-,NO_3~- and HSO_4~-.Upon addition of the three anions to the receptors in DMSO,thesolution acquired a color change from colorless to dark yellow that can be observed by the naked-eyes,thus the re-ceptors can act as fluoride ion sensors even in the presence of other halide ions.The data showed that it was regularthat the three receptors had different binding ability with the three anions.For the same anion,the association con-stants followed the trend:receptor 1>3>2.The UV-Vis data indicates that a 1:1 stoichiometry complex isformed through hydrogen bonding interactions between compound 1,2 or 3 and anions.     

一种三足型比色传感器对阴离子的颜色响应

A thiourea-based tripodal colorimetric anion sensor was synthesized. Its binding abilities with AcO^- and halide anions in DMSO were studied by UV-Vis spectra. The sensor showed different color responses to these anions. The association constants and different stoichiometries were deduced by nonlinear least-square curve fitting or linear fitting.     

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".     

A new anion receptor utilising aromatic and aliphatic C…H hydrogen bonds

We have synthesised 2, which bound weakly basic halide ions only with C–H…anion hydrogen bonds. Compound 2 utilised one aromatic C–H hydrogen bond and one benzylic C–H hydrogen bond to bind weakly halide ions such as chloride, bromide and iodide in solution. Ab initio calculations of binding energy values for these anions are in good agreement with experimental data. Although the binding affinities of 2 for these anions were low, 2 could be a unique example of host, which utilised only C–H hydrogen bonds to bind anion.     

多分支中性受体的合成及αω-二羧酸阴离子识别研究

Two new multi-armed neutral receptors 1 and 2 containing thiourea and amide groups were synthesized by simple steps in good yields. Receptors 1 and 2 have a better selectivity and higher association constants for malonate anion than other anions examined by the present work. In particular, distinct color changes were observed upon addition of dicarboxylate anions to the solution of 1 in DMSO. The UV-Vis and fluorescence spectra data indicate that a 1 ： 2 stoichiometry complex was formed between compound 1 or 2 and dicarboxylate anions of shorter carbon chain, and a 1 ： 1 stoichiometry complex was formed between compound 1 or 2 and dicarboxylate anions of longer carbon chain through hydrogen bonding interactions.     

Study on Synthesis and Binding Ability of a New Anion Receptor Containing NH Binding Sites

A new colorimetric recognition receptor 1 based on the dual capability containing NH binding sites of selectively sensing anionic guest species has been synthesized. Compared with other halide anions, its UV/Vis absorption spectrum in dimethyl sulfoxide showed the response toward the presence of fluoride anion with high selectivity, and also displayed dramatic color changes from colorless to yellow in the presence of TBAF （5 × 10^-5 mol/L）. The similar UV/Vis absorption spectrum change also occurred when 1 was treated with AcO^- while a little change with H2PO^-4 and OH^-. Receptor 1 has almost not affinity abilities to Cl^-, Br^- and I^-. The binding ability of receptor 1 to fluoride with high selectivity over other halides contributes to the anion size and the ability of forming hydrogen bonding. While the different ability of binding with geometrically triangular （AcO^-）, tetrahedral （H2PO^-4 ） and linear （OH^-） anions maybe result from their geometry configuration.     

Acetate-Selective Anion Receptor with Methylene-Bridged Bis-Imidazolium Rings

Methylene-bridged bis-imidazolium receptor 1 has been synthesized. Anion binding studies carried out using ¹H NMR revealed that this compound displayed good affinities for acetate, while binding spherical halide anions weakly.     

Utilization of a Crown Ether/Amine‐Type Rotaxane as a Probe for the Versatile Detection of Anions and Acids by Thin‐Layer Chromatography

A crown ether/amine‐type [2]rotaxane was synthesized and utilized as a probe for the detection of acids and anions. The addition of acids to the amine‐type [2]rotaxane solution generated corresponding crown ether/ammonium‐type [2]rotaxanes, which were purified by silica gel column chromatography as ammonium salts. The isolated yields of the [2]rotaxanes, possessing a variety of anions, depended on the acidity and polarity of the counter anions. The behaviours of the ammonium‐type [2]rotaxanes on thin‐layer chromatography (TLC) silica gel reflected the properties of the counter anions. The treatment of the amine‐type [2]rotaxane with acids afforded the corresponding ammonium‐type [2]rotaxanes bearing several different anions. The ammonium‐type [2]rotaxanes behaved similarly to the purified [2]rotaxanes on the TLC silica gel. Furthermore, we succeeded in the analysis of anions using mixtures of the amine‐type [2]rotaxane and salts in an appropriate solvent. We demonstrated the detection of anions by the combination of TLC and the utilization of the [2]rotaxane probe.     

Chemistry of allenic/propargylic anions generated by base treatment of sulfonylallenes: synthesis of 1-alkynyl-1-sulfonylcycloalkanes and cycloalkanols

The intramolecular trapping of allenyl/propargyl anions, generated from sulfonylallenes with the proper base, by a haloalkyl group or an aldehyde functionality was investigated. The treatment of 1-(ω-iodoalkyl)-1-(phenylsulfonyl)allenes with TBAF or NaH in DMF efficiently produced the 1-alkynyl-1-(phenylsulfonyl)-substituted three- to seven-membered carbocycles. The allenyl/propargyl anions could also be intramolecularly trapped using a terminal aldehyde to stereoselectively afford the 2-alkynyl-2-(phenylsulfonyl)-substituted five- and six-membered cycloalkanols. The latter reaction could be performed using a catalytic amount of TBAF or DBU.     

Comparison of pillar[5]arene and calix[4]arene anion receptor ability in aqueous media

Abstract

Recognition ability of both cationic pillar[5]arene and calix[4]arene has been studied in aqueous media. Anion complexation can be evaluated from their ability to complex their counterions as well as an added external organic anion. DOSY NMR experiments and fluorescence quenching show that pillararenes have a larger ability for including their own counterions than calixarenes irrespective of the anion (tetrafluoroborate or chloride or bromide) and the structure of the cationic moiety (trimethylammonium or methylimidazolium). Counterion complexation shows a picture where four to five positive charges of the pillar[5]arene are neutralised, meanwhile only one positive charge of the calixarene is neutralised for a 1 mM solution of the macrocycle. Irrespective of the smaller net positive charge in the pillar[5]arene, its binding ability for organic anions (toluenesulfonate or hydroxybenzoate) is larger than for calix[4]arene allowing a better accommodation of the guest in its cavity. The larger separation between the cationic groups of the receptor and its electron-rich aromatic region improves the anion recognition ability for pillar[5]arene.     

Anion binding to a tetracopper resorcinarene-based complex

UV–vis and electron paramagnetic resonance (EPR) spectroscopic studies have been carried out on the multinuclear copper(II) complex Cu₄BpaRes. The copper atoms are in a tetragonal distorted geometry with nitrogens from bispicolylamine (Bpa) coordinating in the equatorial plane and water molecules or anions completing four coordination sites. The interaction of anions with this polynuclear copper complex in aqueous solution supports the formation of different complex species, which depend on the type and the concentration of the anions. In the presence of excess anions, frozen solution EPR parameters show the formation of species in which the in-plane coordination is characterised by the presence of three nitrogen atoms coming from the ligand and a donor atom from the specific anion. For the bidentate anion ligands and especially for malonate, UV–vis titrations indicate the formation of a 1:4 (Cu₄BpaRes:anion) species. EPR experiments support the formation of such a species and indicate that the four copper centres are equivalent and reach penta-coordination via the coordination of both oxygens from the bidentate ligand.     

Synthesis of Novel Anionic Receptors with （Thio）urea and Amide Binding Sites and the Recognition Properties for Anions

IntroductionSincemoreandmoreanionsplayanimportantroleinbiologicalandchemicalprocesses ,thedesignandsynthe sisofreceptorsforon lineandrealtimedetectionofbio logicallyimportantanions ,andforenvironmentalmonitor ingofharmfulanionpollutantshaveattractedparticularat tentioninsupramolecularchemistry .1Thebasicstrategyfortheconstructionofanion bindingreceptorsistoexploitthereceptorsthathaveelectrostatic ,2 hydrogenbonding ,3orLewisacidiccentralinteraction .4 Amongavarietyofnon covalentinteractions ,h…     

Amidocrownophanes as Anion Receptor

Crownophanes composed of 28-membered ring atoms having two hydroxy groups, two amide groups, and aromatic parts such as naphthalene rings and either pyridine or benzene ring, can bind anions with high affinity and selectivity. The anion-coordination ability of these species has been observed by ¹H NMR techniques. As anion guest molecules, we selected some halides, dihydrogenphosphate and acetate ions. It has been found that amidocrownophanes, 3 and 4, can recognize anions in the order;H₂PO ₄ ⁻ >F⁻>CH₃COO⁻>Cl⁻>>Br⁻ and I⁻, while not only 1, 2, and 5 having no hydroxy group but also 6 having 27-membered ring have no ability for anion recognition under the same conditions. In order to exhibit the recognition ability for anion receptor, plural amide groups, hydroxy groups, and m-phenylene or 1,6-pyridyl rigid part play an important role in this macrocyclic system.     

Simultaneous separation of 17 anions by capillary electrophoresis with the addition of an organic solvent

Seventeen inorganic and organic anions, that normally are insufficiently separated via ion chromatography, were completely separated by the addition of an organic solvent to a solution of BGE combined with an adjustment of the apparent pH via CE in combination with indirect UV absorbance detection. Methanol, ethanol, and acetonitrile were examined for their utility in manipulating the selective separation of anions. Methanol and acetonitrile were better modifiers than ethanol at enhancing the resolution of anions comigrating in an aqueous solution of BGE. Methanol was selected as the modifier that provided the largest separation window that could achieve a complete separation of the target analytes. Via the use of methanol, manipulation of the selectivity between inorganic anions and that between inorganic and organic anions was enhanced, but the separation between organic anions remained difficult when only methanol was used. By varying the apparent pH of the BGE in the presence of 10% v/v methanol, however, the separation selectivity between organic anions was substantially improved. Eventually, 7 inorganic and 10 organic anions were simultaneously separated using BGE at a pH of 6.3 in the presence of 10% v/v methanol.     

硝基取代苯腙类荧光受体的阴离子识别与传感性能

合成了含萘荧光基团的硝基取代苯腙类受体,利用紫外-可见分光光度法、荧光发射光谱法和核磁等方法研究了受体的阴离子识别与光化学传感性能. 结果表明,在DMSO有机溶剂体系中,单硝基取代受体选择性比色和荧光识别氟离子,而双硝基取代受体可以比色和荧光识别氟离子和醋酸根离子. 归因于腙=N-NH基团质子酸性的进一步增强,双硝基取代受体能够在DMSO-H2O体系中实现对氟离子的比色和荧光识别. 此类受体是有效的“off-on”型阴离子荧光传感分子.     

Anion-binding properties of the tripyrrolemethane group: a combined experimental and theoretical study

Tripyrrolemethane- and bistripyrrolemethane-containing systems were recently reported to be efficient and selective hosts for anions. Nevertheless, the basic intrinsic properties of tripyrrolemethane as a ligand for anions have not yet been explored. Here we report the study of the anion-binding properties of the tripyrrolemethane group. We applied a combined experimental and theoretical approach to determine the affinity of the tripyrrolemethane system for different anions in the gas phase, in solution and in the crystalline state. In the crystal, the tripyrrolemethane group forms a number of different complexes with the bromide ion, some involving the participation of more than one ligand species. Despite the very similar basicity of fluoride and dihydrogen phosphate, the tripyrrolemethane ligand exhibits a clear preference for the fluoride anion in solution, which indicates an anion-binding system and not merely deprotonation. Although the affinity of the tripyrrolemethane ligand for other ions was negligible in solution, gas-phase studies show that complexation with larger halide ions is favoured over complexation with fluoride.