生色冠醚研究

用４－甲基－７－羟基－８－甲酰基香豆素与三种４′－氨基苯并冠醚和４′，４″－二氨基二苯并－１８－冠－６反应，合成了四个新的Ｓｃｈｉｆ碱型苯并冠醚。它们都是有色化合物，具有强荧光性质。在这些Ｓｃｈｉｆ碱型苯并冠醚溶液中加入过渡金属盐时，不同程度地发生荧光猝灭现象，生成的配合物也是荧光化合物；而加入碱金属和碱土金属盐时，则荧光性质几乎不受影响     

Assembly Behavior and Binding Ability of Double-armed Benzo-15-crown-5 with the Potassium Ion

Two novel supramolecular aggregations possessing column structures have been prepared from double-armed benzo-15-crown-5 ether (2) and its complex with potassium ion, respectively. Their molecular assembly behavior has been evaluated by calorimetry, ¹H NMR, X-ray crystallography and STM images, revealing that the molecular assembly behavior of 2 in the solid state can be controlled by the stepwise sandwiching complexation with the cation.     

Fluorescence emission control and switching of oxymethylcrowned spirobenzopyrans by metal ion

Oxymethylcrowned spirobenzopyran 1 and pyrenylspirobenzopyran 2 were synthesized, and fluorescence emission of their corresponding merocyanine form was examined in the presence of metal ions. For 2, fluorescence emission derived from the pyrene moiety was completely quenched by photoinduced electron transfer (PET) of the nitrogen atom when the merocyanine form was not produced, namely, without metal ions. However, when 2 was converted to the merocyanine form by the complexation of its crown ether with a metal ion, fluorescence resonance energy transfer (FRET) from the pyrene to the merocyanine moieties took place to produce fluorescence emission. This result demonstrates that the spirobenzopyran isomerization can function as a fluorescence emission switch. Fluorescence quantum yield measurement for 1 and 2 showed that fluorescence emission depends on the binding metal ion in which the fluorescence quantum yield generally increased with the increase of metal ion radius.     

铟（Ⅲ）的碱金属卤化物与冠醚配合物的合成及表征

在萃取研究过程中,合成了10种由四溴(或碘)合铟(Ⅲ)配阴离子与苯并-15-冠-5或二苯并-18-冠-6合钾(或钠)配阳离子相结合所形成的新型固体配合物。经元素分析、红外光谱及差热-热重等方法对配合物进行了表征。通过与相应的冠醚碱金属苦味酸盐配合物结构性质的对比,较合理地解释了这两类萃取体系之间存在的某些差别。     

超分子化合物构筑的碱金属离子传输膜的制备与性能

采用苯并15冠5、没食子酸甲酯以及1-溴十一烯等物质为原料,合成超分子化合物2-(1-甲基羟甲基)-[1,4,7,10,13-苯并15冠5]-3,4,5-三[4-(10-十一烯-1-羰基)苄氧基]苯甲酸酯.然后用紫外光接枝法将其接枝到聚丙烯腈(PAN)微孔膜表面,构筑具有离子传输功能的离子传输复合膜,接枝量为3.025 mg/cm2.通过ATR,XPS,SEM以及AFM等手段对离子传输膜的结构性能进行表征.结果表明,这种超分子化合物在PAN膜的表面自组装成柱状通道,并形成致密皮层.采用自行设计的膜运输装置对膜的离子识别和运输功能进行评测.通过与非功能材料(丙烯酸)接枝膜的对比,可以认为本文制备的离子识别膜可以选择性识别和运输碱金属阳离子,其运输能力顺序为Na+>K+>Li+.     

Molecular Structure of RbSCN Complex with N-(4′-hydroxy-3′,5′-diisopropylbenzyl)-monoaza-15-crown-5 Ether: Two Structures in a Unit Cell

Abstract

Molecular structures of the RbSCN complexes with N-(4′-hydroxy-3′,5′-diisopropylbenzyl)-monoaza-15-crown-5 ether (2-RbSCN) and N-(4′-hydroxy-3′,5′-di-tert-butylbenzyl)-monoaza-15-crown-5 ether (3-RbSCN) are reported. Crystal data (2-RbSCN) C₂₄H₃₉N₂O₅SRb, M = 553.11, monoclinic, space group P2₁, a = 9.835(4), b = 15.44(3), c = 18.563(6) Å, β = 99.58 (4), U = 2779(4) ų, Z = 4, Dc = 1.322 gcm^?3, v = 18.87 cm^?1, R = 0.047, Rw = 0.049 for the 5339 independent reflections (of 5712 measured reflections) and 590 parameters. (3-RbSCN) C₅₂H₈₆N₄ O₁₀S₂Rb₂, M = 1162.32, triclinic, space group P2₁, a = 9.917(2), b = 24.644(6), c = 12.572(3), α = 89.38(2), γ = 96.13(2), γ = 89.34(2) Å, U = 3054(1) ų, Z = 2, Dc = 1.264 g cm^?3, μ = 17.20 cm^?1, R = 0.051, R = 0.053 for the 6864 independent reflections (of 7201 measured reflections) and 316 parameters. The molecular structures of the RbSCN complexes with a series of N-(4-hydroxy-3′,5′-dialkylbenzyl)-monoaza-15-crown-5 ethers (1, 2 and 3) were systematically changed depending upon the size of the R groups at positions 3′ and 5′ in the side arm; 1 (R=Me), a polymer-like (1:1)_n complex; 2 (R = i-Pr), a mixture of 1:1 complex and polymer-like (1:1)_n complex; 3 (R = t-Bu), a dimeric 1:1 complex.     

Synthesis and metal ion complexation of spin labeled 18-crown-6 ethers containing an acridone or an acridine fluorophore unit

Double (spin and fluorescence) labeled pyrroline derivatives of crown ethers containing an acridone or an acridine fluorophore unit (1 and 2) and their diamagnetic analogues (3 and 4) were synthesized. Their fluorescent behavior as well as their complexation properties toward selected metal ions (Na⁺, K⁺, Mg²⁺, Ca²⁺, Zn²⁺) were examined.     

Fluorescence Suppression of 7-Methoxycoumarin upon Inclusion into Cyclodextrins

The fluorescence intensity of 7-methoxycoumarin (7MC) in aqueoussolution is found to significantly decrease upon addition of variouscyclodextrins. This observed phenomenon is described asfluorescence suppression, to distinguish it from fluorescencereduction via bimolecular quenching. The decrease in fluorescenceof 7MC is proposed to be the result of the formation of ahost–guest inclusion complex with cyclodextrin. Since 7MC isa polarity-sensitive fluorophore, which is less fluorescent ina nonpolar environment, its fluorescence decreases uponinclusion into the relatively nonpolar internal cavity of thecyclodextrin. The same equation used for extracting the associationconstant in the case of 1 : 1 host–guest inclusion-induced fluorescenceenhancement is shown to be applicable to the case of fluorescencesuppression. In the case of β-cyclodextrin, the degree of fluorescencesuppression, as well as the value of the binding constant for formationof the inclusion complex, are found to be unaffected by modificationof the cyclodextrin rims, suggesting that the molecule iscompletely included within the β-cyclodextrin cavity. In the case ofγ-cyclodextrin, the degree of fluorescence suppression, butnot the value of the binding constant, is found to be significantlyaffected by modification of the cyclodextrin rims, suggesting thatthe molecule is experiencing a less polar environment in the modifiedγ-cyclodextrin cavity. The binding constant is three timeslarger in β- as compared to γ-cyclodextrin, indicatinga much better size match in the smaller β-cyclodextrin cavity.     

Synthesis, complexation properties and crystal structure of 4'''',5''''-dibromo-oxylyl-17-crown-5 ether

4',5'-Dibromo-o-xylyl-17-crown-5 ether (2BrB17C5) was synthesized,starting from 1,2-dibromo-4,5-bis(bromomethyl)-benzene and tetraethylene glycol,and was characterized by 1H NMR,MS and elemental analysis.Pale yellow prismatic single crystal obtained from anhydrous ethanol was investigated by X-ray structural analysis.The complexation properties toward alkali metal ions were examined using the solvent extraction method and UV absorption spectroscopy.The crown ether was found to be conformationally deformed and oblate-like and is highly selective for lithium ion.     

Synthesis, structure and properties of the macrocyclic ferrocenophanes with cyclopentadienyl ligands tethered by oligo(ethylene glycol) chain

Cyclization reactions of Fe{C₅H₄OCH₂(CH₂OCH₂)_nCH₂OTs}₂ (n = 1, 2) with C₆H₄-1,2-(OH)₂, C₆H₄-1,3-(OH)₂, and Fe(C₅H₄OAc)₂ under basic conditions yield the corresponding macrocyclic 1,1′-ferrocenophanes. The ferrocenophane having a pyrido-crown ether structure was also synthesized. These ferrocenophanes were characterized by X-ray crystallography and NMR spectroscopy. Cyclic voltammograms of the ferrocenophanes exhibited reversible redox peaks assigned to the oxidation and reduction of the ferrocene unit. The macrocyclic pyrido-containing ferrocenophane forms pseudorotaxane with [NH₂{(CH₂)₉Me}₂]BARF (BARF = B{C₆H₃-3,5-(CF₃)₂}₄) in CDCl₃.     

含冠醚结构单元螺吡喃化合物的逆光致变色性质及其对碱金属离子的识别作用

吲跺啉螺吡喃是一类重要的有机光致变色化合物,当被紫外光和可见光照射时可逆地异构化．一系列的研究表明它在非银材料、非线性光学器件以及高分辨率的信息存贮和再现等诸方面的应用价值［１］．９０年代以来,Ｉｎｏｕｙｅ［２,３］,Ｋｉｍｕｒａ［４－６］和吴成泰等［７－９］曾将冠醚结构单元引入螺吡喃,研究了对碱金属离子的识别作用及其由此诱导含冠醚螺吡喃化合物的异构化现象．由于冠醚化合物对金属离子具有特定的络合作用,当在含冠醚螺吡喃化合物中加入某些金属离子时,能诱发螺吡喃结构的异构化,从而强烈地影响异构化平衡,…     

冠醚修饰的固体支撑双层类脂膜的形成及性能研究

用饱和了胆固醇和饰用冠醚的角鲨烷／氯仿溶液作成膜液，制备了冠醚修饰的固体支撑双层类脂分子膜。重点考察了成膜物种及技术对膜稳定性及电特生影响。其膜电势随接触水相中的变化呈现Ｎｅｒｎｓｔ响应，线性范围１０＾－４－１０＾－１ｍｏｌ／Ｌ。     

The effects of alkali cation complexation on the fluorescence properties of crown ethers

The effects of alkali metal complexation on the fluorescence properties of two crown ethers (a podand and a coronand) were investigated. Metal ion binding leads to changes in fluorescence intensity along with slight shifts in the emission maxima. This is attributed to a rigidization of the fluorophore and an interaction of the metal ion with non-bonding electrons of the crown ethers. The effects on the spectra are more pronounced in fluorescence than in absorption.Fluorescence titration with metal ions provides a simple and sensitive means for the determination of complexation constants, which were found to be highly dependent upon the water content of the methanol solution. Halide counterions, in particular iodide, act as dynamic fluorescence quenchers withStern-Volmer constants that are different for the sodium and potassium complexes, respectively.

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Die Effekte der Komplexierung von Alkalimetallionen auf die Fluoreszenzeigenschaften von Kronenethern

Zusammenfassung Die Effekte der Komplexierung von Alkalimetallionen auf die Fluoreszenzeigenschaften zweier Kronenether (eines Podanden und eines Coronanden) wurden untersucht. Die Bindung des Metallions fürt zu Veränderungen in der Fluoreszenzintensität und zu Verschiebungen in den Emissionsmaxima. Dies wird einer gesteigerten Starrheit des Fluorophors und einer Wechselwirkung des Metallions mit nichtbindenden Elektronen des Kronenethers zugeschrieben. Die Auswirkungen auf die Spektren sind in der Fluoreszenz ausgeprägter als in der Absorption.Fluoreszenztitrationen mit Metallionen bieten eine einfache und empfindliche Möglichkeit zur Bestimmung von Komplexkonstanten, welche stark vom Wassergehalt der methanolischen Lösung abhängig befunden werden. Halogenidgegenionen, insbesonders Iodid, wirken als dynamische Fluoreszenzlöscher und weisenStern-Volmer-Konstanten auf, welche für die Natrium- bzw. Kalium-Komplexe verschieden sind.

     

Fluorescence Enhancement of Aflatoxins Using Native and Substituted Cyclodextrins

Cyclodextrins have been used as fluorescence enhancers in HPLC to improve thedetection limits of aflatoxins, cancerogens which can be found in severalfoodstuffs. In this work, a screening of several cyclodextrins has been performedin order to find the factors affecting the fluorescence enhancement. Evidence for formationof a 1 : 1 AF-CD inclusion complex has been achieved by titration and competitiveexperiments with adamantanecarboxylic acid and by fluorescence quenching by KI.Stability constants of the AF-CD complexes were evaluated.     

识别过渡金属离子的1,8-萘二甲酰亚胺多胺衍生物荧光传感器的研究

A series of fluorescent chemosensors 1-3 were synthesized to detect transition metal ions. At the room temperature, fluorescence intensities of these chemosensors in acetonitrile without transition metal ions were found to be very weak, due to the process of the e±cient intramolecular photoinduced electron transfer (PET). However, after addition of the transition metal ions, the chemosensor 1-3 exhibits obvious fluorescence enhancement. Moreover, the intensity of the fluorescence emission of chemosensors increases significantly in the presence of Zn2+ and Cd2+. The fluorescent chemosensors with different polyamine as receptors show diverse a±nity abilities to the transition metal ions and signal the receptor-metal ion interaction by the intensity change of fluorescence emission.     

Conductance and Thermodynamic Study of the Complexation of Ammonium Ion with Different Crown Ethers in Binary Nonaqueous Solvents

A conductance study of the interaction between ammonium ion and 18‐Crown‐6 (18C6), dicyclohexano‐18‐crown‐6 (DC18C6), ditertbutyl‐dicyclohexano‐18‐crown‐6 (t‐bu)₂DC18C6, diaza‐15‐crown‐5 (DA15C5), dibenzo‐21‐crown‐7 (DB21C7) and N‐Phenylaza‐15‐crown‐5 (NPA15C5) in acetonitril‐di‐methylsulfoxide mixture was carried out at various temperatures. The formation constants of the resultant 1:1 complexes were determined from the molar conductance‐mole ratio data and found to vary in the order of DA15C5 > DC18C6 > 18C6 > (t‐bu)₂DC18C6 > DB21C7 > NPA15C5. The enthalpy and entropy of the complexation reactions were determined from the temperature dependence of the formation constants.     

多胺修饰β-环糊精对铝-铁试剂荧光体系的增敏作用

研究了β－环糊精（1）、单－[6-乙二胺－6－脱氧]-β－环糊精（2）、单-[6-(二乙烯三胺）-6-脱氧]-β-环糊精（3）和单-[6-(三乙烯四胺）－6－脱氧]-β-环糊精（4）对铝－铁试剂荧光体系的增敏作用。实验结果表明：加入β－环糊精及其衍生物后体系的荧光强度均增强，增敏率为4＞3＞2＞1，其中4给出最大的荧光增敏率。研究了pH值在3.0-7.5之间酸度对主体化合物增敏能力的影响，发现体系的pH值对β－环糊精的增敏率影响较小，而随着体系酸性的增强，多胺修饰β－环糊精的增敏作用显著增强。探讨了修饰环糊精引入边臂的长度和主－客体间的尺寸适合等因素对铝－铁试剂体系荧光增敏率的影响。     

Structures of 18-Crown-6 Complexes with Alkali Cations in Methanolic Solution as Studied by X-ray Absorption Fine Structure

The structures of 18-crown-6 (18C6) complexes with K⁺ and Rb⁺ in methanolic solutions have been studied by X-ray absorption fine structure (XAFS) at the Br K-edge as well as at the K and Rb K-edges. The XAFS spectrum at the K or Rb K-edge has indicated that either Br⁻ or solvent (methanol) molecules are present in the first coordination shell of K⁺ or Rb⁺ complexed by 18C6. However, the spectra obtained at the Br-K edge have strongly suggested that the alkali cations do not exist in the vicinity of Br⁻, indicating that no direct ion-pairing occurs between the 18C6 complex and Br⁻. The 18C6-K⁺ complex maintains D _3d symmetry even in methanol, and two methanol molecules coordinate the cation possibly from above and below the crown plane. In contrast, the corresponding Rb⁺ complex possibly forms an umbrella-shaped complex, in which Rb⁺ is situated slightly off the crown plane and three solvent molecules bind With the cation.     

Fluorescence Enhancement of Samarium－Thenoyl－trifluoroacetone－Cetyltrimethylammonium Bromide－Triton X－100 by Scandium

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