新型主体分子噻唑偶氮基杯[n]芳烃衍生物的合成及其对重金属离子的识别

以2－氨基噻唑为原料，经重氮化－偶联反应合成了5，11，17，23－四（2－噻唑）偶氮基－25，26，27，28－四羟基杯[4]芳烃和5，11，17，23，29，35－六（2－噻唑）偶氮基－37，38，39，40，41，42－六羟基杯[6]芳烃，产物的结构经IR，^1H NMR和元素分析表征；研究了它们的光谱性能和对金属离子的识别状况，发现在pH=7.2的Tris介质中对Ag^ 和Hg^2 等有较好的光谱变化识别。     

The Electrochemical Behavior of p‐tert‐Butyl‐sulfonylcalix[4]arene and Its Selective Complexation with Metal Ions at Water‐Air Interface

The electrochemical behavior of p‐tert‐butyl‐sulfonylcalix[4]arene (SCA) has been investigated by cyclic voltammetry. The results show that there is an irreversible electrochemical oxidative wave when the potential ranges from 0.9 to 1.9 V versus saturated calomel electrode (SCE) in CH₂Cl₂ at a glassy carbon electrode. The kinetic parameters of the andic wave, such as α,n, k_s, D and the diffusion activation energy (E_d), were discussed. In addition, the interaction of SCA with metal ions at the water‐air interface was also discussed by Langmuir‐Blodgett (LB) techniques. The results confirm that the selectivity of SCA as ligand for Pb²⁺ in monomolecular film is very high by complexation action, which provide the foundation that LB film of SCA modified glassy carbon electrode (GCE) as voltammetric sensor to detect trace amounts of Pb²⁺.     

Synthesis and Fluorescence Sensing Properties of Calix[4]arenes Containing Fluorophores

New fluoroionophores 4 and 5 derived from calix[4]arene triester monoacid chloride with 2-amino-4-(1,3-benzothiazol-2-yl)phenol and 4-aminoquinaldine, respectively, have been synthesized. A preliminary test showed that the fluorescence intensity of 5 was very low, so only 4 was subjected to cation recognition investigation. In methanol, the fluorescence intensity of 4 was quenched by Na⁺. The fluorescence intensity decreased linearly with increasing Na⁺ concentration with a stability constant of log K = 2.91 ± 0.08. No significant response was observed for other alkali metal ions under the same experimental conditions.     

钳状杯[4]芳烃为探针的固态PVC膜汞离子选择性电极

全固膜选择性电极(All solid-state selective electrode,ASSE)综合晶体电极和膜电极的优点,具有线性范围宽、检测限低,能真实地体现膜性能等特点,ASSE主要有涂线电极(Coated wire electrode,CWE)、填充固体电解质或配合物的膜电极和电沉积型聚合物膜电极等。     

新型杯[4]芳烃衍生物的合成及其对镧系金属离子的识别研究

超分子化学是与材料化学、信息科学和生命科学等学科紧密相关的一门交叉学科, 近年来得到了人们越来越多的关注. 分子识别是超分子化学的核心研究内容之一, 也是生命体系中普遍存在的现象. 目前分子识别的主体化合物有3代: 冠醚、 环糊精和杯芳烃. 杯芳烃因具有空腔大小可调、构象可变换、易于化学修饰和既是离子受体又是分子受体等特点, 而成为近年来的研究热点.     

Electronic Tuning of Host-Guest Interactions within the Cavities of Fluorophore-Appended Calix[4]arenes

A series of fluorescent calix[4]arene scaffolds bearing electron-rich carbazole moiety conjugated at the lower rim have been prepared. Studies of the fluorescence quenching in the presence of the N-methyl pyridinium guest revealed that the electronic properties of the distal phenolic ring play a major role in the host–guest complexation. In particular, placing an electron-donating piperidine fragment at that ring significantly increased the host–guest interactions, while introducing the same fragment into the proximal phenolic ring weakened the fluorescence response. These results suggest that the dominant interactions between the guest and calixarene cavity involve the oxygen-depleted fluorophore-bearing aromatic ring and not the more electron-rich unsubstituted phenolic fragments.     

Synthesis of Chiral Calix[4]arene Derivative and Evaluation of its Recognition Properties

The article describes the synthesis and extraction properties of a new chiral calix[4]arene Schiff base ligand 5, which has been synthesized from 5,17-diformyl-25,27-bis-(4-nitrobenzyloxy)-26,28-dihidroxycalix[4]arene (4) by treatment with (S)-(-)-1-phenylethylamine. In this synthesis, it was thought to explore the role of chiral, as well as Schiff base sites in the recognition of targeted species ions (such as dichromate anions) as well as neutral/chiral molecules. At low pH, the ligand 5 is more effective for transferring the dichromate anions from an aqueous into a dichloromethane layer; may be due to the protonation of nitrogen atoms.

The extraction properties of ligand 5 towards the some selected α -amino acid methylesters are also reported. However, the ligand 5 did not display any selectivity towards the selected α-amino acid methylesters.     

下缘芳香取代结构对杯[4]芳烃Langmuir膜的影响

The Langmuir monolayer properties of lower rim aromatically substituted calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis（2-naphth-1＇-ylacetylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BNAEC）, 5,11,17,23-tetra-tert- butyl-25,27-bis（2-benzoylamino ethoxy）-26,28-dihydroxylcalix[4]arene （BBAEC） and 5,11,17,23-tetra-tert-butyl- 25,27-bis（2-cinnamoylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BCAEC）, have been studied. Film balance measurements and Brewster angle microscopy （BAM） observation demonstrate that all the compounds can form Langmuir monolayers with different molecular limiting areas. BNAEC or BBAEC monolayer is able to form condensed domains during compression, while BCAEC monolayer can never form condensed domain. BNAEC monolayer is more readily to form condensed domain than BBAEC monolayer. Moreover, BNAEC monolayer can form the total condensed phase during compression even when T=28℃, while BBAEC monolayer can not when T 〉 10 ℃. The results imply that different lower rim aromatic substitutions affect essentially the intermolecular interaction and molecular packing in the monolayer at air/water interface.     

新型钳状芳杂环杯[4]芳烃修饰电极对银离子的分子识别研究

合成了25,27-二羟基-26,28-双(3-苯并噻唑基硫代丙氧基)-5,11,17,23-四叔丁基杯[4]芳烃,并将其研制成PVC膜化学修饰电极.探讨了膜电极的修饰方法及伏安性能对金属离子的识别及其识别机理.结果表明,采用涂层-刻痕法制备的修饰电极在0.2mol/LHNO₃溶液中对银离子有很灵敏的伏安响应,在5.0×10^-8～1.3×10^-6mol/L范围内氧化峰电流与银离子呈线性关系,检测限为3.8×10^-8mol/L.用该法测定了一些实际样品,结果令人满意.     

Studies on the Intramolecular Inclusion Complexes of Functionalized Calix[4]arenes with CH3X (X = CN,NO2)

Two functionalized calix[4]arenes in cone conformation L_2–3 have been synthesized and their intramolecular inclusion complexes (1:1) with organic neutral molecules CH₃CN and CH₃NO₂ have been prepared and characterized, respectively. The X‐ray crystallographic analysis shows that L₂ in L₂·CH₃CN. C₂H₅OH has C₄ symmestry and L₃ in L₃.CH₃NO₂ exhibits C₂ symmestry. The CH‐π aromatic interactions between the CH group of the guest and the phenyl rings of the calix backbond have been proved to be able to stabilize the intramolecular inclusion complexes formed. The interaction is directional, but it is independent of the acidity of the guest. To gain information on CH‐s interactions, suitable geometrical parameters have been calculated from the crystal data of intramolecular inclusion complexes. The results show that L₃.CH₃NO₂ with L₃ in C₂ symmestry can also be bound stably in the intramolecular inclusion complex, being consistent with the thermal analysis. The geometrical parameters and the results of the thermal analysis of L₁.CH₃CN and L₁.CH₃NO₂ were also given and discussed.     

靛酚型生色杯［4］芳烃及其与金属离子络合的紫外－可见光谱研究

合成了新型的具有二氯代醌亚胺基的稳定生色杯［４］芳烃。用紫外－可见光谱研究其对碱金属、碱土金属、过渡金属和铀酰离子的络合行为，发现具四个生色取代基的杯［４］芳烃对铀酰离子和铜离子表现出高选择性，同时伴随可见光区的吸收完全消失。这一络合时的颜色变化现象有可能用于分析化学。     

The Preorganization Effect of the Calix[4]arene Platform on the Extraction Properties of Acetylhydrazide Groups with Transition Metal Ions

The binding properties of the cone conformer of O,O,O,O-tetrakis[hydrazinocarbonylmethyl]-4-tert-butylcalix[4]arene, the cone and the 1,3-alternate conformers of the corresponding thia analogue have been evaluated by means of liquid–liquid extraction for a large variety of metal ions. The extraction constants and the stoichiometries of the complexes formed have been determined. Comparison of the extraction properties of calix[4]arenes with their acyclic monomeric analogue clearly demonstrated, that the preorganization of acetylhydrazide groups on the calix[4]arene platform is the cause for a significant improvement of its binding properties. The presence of additional “soft” nitrogen binding sites in acetylhydrazide derivatives of calix[4]arenes compared to their amide derivatives leads to a shift from their classical selectivity for alkali and alkaline earth cations to transition metals. The cone conformer of tetrathiacalix[4]arene shows higher selectivity in a series of d-metal ions compared with its “classical” analogue. The 1,3-alternate conformer exhibits an excellent extraction selectivity for Cu²⁺ and Hg²⁺.     

Synthesis of Coumarin-functionalized Calix[4]arene and Selective Recognition for L-Tryptophan

We report a novel calixarene derivative using 4-bromomethyl-7-methoxycoumarin as the pre-organized unit and apply it to investigate selectively discriminate L-tryptophan from other amino acids in DMF-acetonitrile. 5, 11, 17, 23-Tetra-tert-butyl-25,27-bis-…     

含腺嘌呤的杯芳烃衍生物的合成、表征及其对核苷碱基的分子识别性质

设计合成了一种新型含腺嘌呤基的杯芳烃衍生物(AC)5,11,17,23-四叔丁基-25, 27-二羟基-26-[1-(9-腺嘌呤)-丙氧基]-28-溴丙氧基杯芳烃, 通过红外光谱、元素分析、核磁共振谱和电喷雾质谱等手段对其进行了表征,确认为目标产物; 并采用紫外分光光度法研究了AC的分子识别作用, 通过测定AC与不同浓度、不同组分的核苷、碱基混合体系的吸光度, 证明了AC对尿嘧啶、尿苷具有分子识别作用, 能从其它核苷或碱基共存的体系中将尿苷或尿嘧啶识别出来.     

Synthesis and Crystal Structure of a [Mo8O26]4– Cluster Derivative with 4‐MePyH+. First β‐Octamolybdate Derivative with π–π Stacking

Dioxobis(pyridine‐2‐thiolate‐N, S)molybdenum(VI) (MoO₂(Py‐S)₂), reacts with of 4‐methylpyridine (4‐MePy) in acetonitrile, by slow diffusion, to afford the title compound. This has been characterized by elemental analysis, IR and ¹H NMR spectroscopy. The X‐ray single crystal structure of the complex is described. Structural studies reveal that the molecular structure consists of a β‐Mo₈O₂₆ polyanion with eight MoO₆ distorted edge‐shared octahedra with short terminal Mo–O bonds (1.692–1.714 Å), bonds of intermediate length (1.887–1.999 Å) and long bonds (2.150–2.473 Å). Two different types of hydrogen bonds have been found: N–H···O (2.800–3.075 Å) and C–H···O (3.095–3.316 Å). The presence of π–π stacking interactions and strong hydrogen bonds are presumably responsible for the special disposition of the pyridinic rings around the polyanion cluster.     

Solvent Extraction of Sodium and Potassium Ions by Dicarboxylated Calix[4]arenes

The extraction of sodium and potassium ions by 25,27-dicarboxymethyl-26,28-dimethoxy-5,11,17,23-tetra-tert-butyl calix[4]arene (L1H2) in chloroform shows the formation of MLIH and M2LI complexes (M = Na, K). In 1,2-dichloroethane, the MLIH species are formed in the acidic pH range, while only the Na2LI species is found at high pH values. The corresponding extraction equilibrium constants K11 (M) and K21 (M) have been evaluated and show a selectivity in favour of Na+ as compared to K+, whatever the nature of the complexes. In chloroform, this selectivity is much more pronounced considering the 2 : 1 complexes: K11(Na)/K11(K) K21(Na)/K21(K).The coexistence of 1 : 1 and 2 : 1 metal : ligand complexes is also shown in the extraction of sodium in 1,2-dichloroethane by the 25,27-dicarboxymethyl-26,28-dimethoxyethoxy-5,11,17,23-tetra-tertbutyl calix[4]arene (LIIH2), locked in the cone conformation.Structural data of the complexes are discussed on the basis of 1H-NMR spectra. In particular, for LIH2, a conformational change from cone to partial cone upon metal complexation has been evidenced for the complexes KLIH, K2LI and Na2LI.     

Calix[4]arenes with Pendant Amide and Phosphine Oxide Functionalities: Use as Extractive Agents and Carriers for Silver (I) Ions

The solvent extraction properties towards Ag⁺ of5,11,17,23-tetra-tert-butyl-25,27-diX-26,28-bis(diphenylphosphinoylmethoxy)calix[4]arenes (X = CH₂C(O)NEt₂ (1), CH₂P(O)Ph₂ (2), CH₃ (3), CH₂C(O)Et (4))have been studied. Each ligand forms a 1 : 1 complex with silver(I). Ligand1, which bears two amide functionalities, is the most efficacious,emphasizing the crucial role played by the polar amide groups. The rate oftransport of AgNO₃ through a bulk liquid membrane with this ligand ascarrier was shown to be superior to that of DC18C6, a structurally-relatedmulti-oxygen donor carrier. NMR and IR data suggest that Ag⁺ is coordinatedto each of the oxygen atoms in the ligand leading to an encapsulatedstructure [Ag 1]⁺.     

Properties of two-component Langmuir monolayer of single chain perfluorinated carboxylic acids with dipalmitoylphosphatidylcholine (DPPC)

The surface pressure (π)– and the surface potential (ΔV)–area (A) isotherms were obtained for two-component monolayers of four different perfluorocarboxylic acids (FCns; perfluorododecanoic acid: FC12, perfluorotetradecanoic acid: FC14, perfluorohexadecanoic acid: FC16, perfluorooctadecanoic acid: FC18) with dipalmitoylphosphatidylcholine (DPPC) on substrate solution of 0.15 M NaCl (pH 2.0) at 298.2 K as a function of compositions in the mixtures by employing the Wilhelmy method, the ionizing electrode method, the fluorescence microscopy, and the atomic force microscopy. The data for the two-component monolayers on these systems were analyzed in terms of the additivity rule. Assuming a regular surface mixture, the Joos equation which allows one to describe the collapse pressure of a two-component monolayer with miscible components was used to declare the miscibility of the monolayer state, and an interaction parameter and an interaction energy were calculated. The new finding was that FCns and DPPC are miscible or immiscible depending on chain length increment of fluorocarbon part. That is, FC12/DPPC monolayer was perfectly miscible, and FC14/DPPC, and FC16/DPPC (0 ≤ X_FC16 ≤ 0.3) monolayers were partially miscible. While FC16/DPPC (0.3 < X_FC16 < 1) and FC18/DPPC systems are immiscible in the monolayer state. Furthermore, the mean molecular area, the surface dipole moment, and the phase diagrams enabled us to estimate the molecular orientation of four different perfluorocarboxylic acids/DPPC in the two-component monolayer state. One type of phase diagrams was obtained and classified into the positive azeotropic type. The miscibility of FCns and DPPC in the monolayer was also supported by fluorescence microscopy and atomic force microscopy. FC12/DPPC, FC14/DPPC and FC16/DPPC (0 ≤ X_FC16 ≤ 0.3) two-component monolayers on 0.15 M NaCl (pH 2) showed that FC12, FC14 and FC16 (0 ≤ X_FC16 ≤ 0.3) can dissolve or partially dissolve the ordered solid DPPC domains formed upon compression. This indicates that these fluorinated amphiphiles soften or harden the lipid depending on their chain length.     

杯芳烃树枝型酰胺衍生物的合成和对金属离子的识别

杯芳烃树枝型酰胺衍生物的合成和对金属离子的识别;杯芳烃;树枝型化合物;酰胺;离子识别;紫外-可见光谱