以两种杯[4]芳烃衍生物为载体的PVC膜季铵盐正离子选择电极的研究

研究了两种新型杯[4]芳烃衍生物5，ll，17，23-四叔丁基-25，26，27，28-四-[3．(甲氧基羰基)苄氧基]杯[4]芳烃(I)和5，ll，17，23-四叔丁基-25，26，27，28-四-[3-(乙氧基羰基)苄氧基]杯[4]芳烃(Ⅱ)为载体的PVC膜电极的响应行为；实验结果表明，两电极对季铵盐正离子均具有优良的能斯特电位响应性能，以(I)为载体的电极对Bu4N^ 、Et4N^ 和Me4N^ 的线性响应范围分别为10^-6～10^-1mol／L、10^-6～10^-1mol／L和10^-4～10^-1mol／L，相应的斜率为59．2、55．0和55．9mV／pc；以(Ⅱ)为载体的电极对Bu4N^ 、Et4N^ 和Me4N^ 的线性响应范围分别为10^-6～10^-1mol/L，10^-5～10^-1mol/L和10^-4～10^-1mol／L，相应的斜率为59．8、56．6和56．0mV／pc；电极具有读数稳定，重复性好，可在pH值较宽范围内测定等优点；将该电极用于药品溴丙胺太林中丙胺太林含量的测定，所得结果与药典法基本一致。     

Synthesis and Crystal Structure of Complex of Sodium Perrhenate with Tetraethyl p-tert-Butylcalix[4]arene Tetraacetate

Recently,theconformationofthecalixarenehasbeenshowntobeimportantincontrollingtheseIectivityofthereceptor.Forexample,sodiumioncouldbeboundverystronglybyesterderivativesofcalix[4]areneintheconeconformationl.Wehavefoundthatinthepresenceofcertainamountofsodiumion,microamountofReO4-canbequantitativelyextractedintol,2-dichloroethanebytheligandtetraethylp-tert-butylcalix[4]arenetetraacetate(L).ItshowsthatthepresenceofNa inaqueoussolutioncanpromotetheformationofhydrophobiccomplex[NaL] .ReO'-whichc…     

Synthesis of Flavin–Calix[4]arene Conjugate Derivatives

The synthesis of two new flavin substituted calix[4]arene derivatives, 9 and 10 , is described. The first flavin substituted calix[4]arene derivative 9 was synthesized by the reaction of 3‐methylalloxazine ( 5 ) with 25,27‐bis(3‐bromopropoxy)‐26,28‐dihydroxy‐5,11,17,23‐tetra(tert‐butyl)calix[4]arene ( 4 ) in high yield (92%). The other derivative 10 was prepared from 3‐methylalloxazine‐1‐acetic acid ( 7 ) and 25,27‐bis(3‐cyanopropoxy)calix[4]arene ( 3 ). All new compounds were characterized by a combination of FT‐IR and ¹H‐NMR spectroscopy, and elemental‐analysis techniques.     

新型杯[4]芳烃衍生物的合成

以对叔丁基杯[4]芳烃为起始原料,通过一步或两步取代反应合成了对叔丁基杯[4]芳烃的衍生物(1和2),其结构经FT-IR,^1H NMR,FAB-MS表征．     

p-tert-Butyldihomooxacalix[4]arene/p-tert-Butylcalix[4]arene: Transition and Heavy Metal Cation Extraction and Transport Studies by Ketone and Ester Derivatives

The binding properties of two phenylketones (2a and 3a) and two ethylesters (2b and {3b) derived from p-tert-butyldihomooxacalix[4]arene or from p-tert-butylcalix[4]arene, in the cone conformation, towards transition (Ag⁺, Ni²⁺, Cu²⁺, Co²⁺, Zn²⁺, Fe²⁺ and Mn²⁺) and heavy (Cd²⁺, Hg²⁺ and Pb²⁺) metal cations have been determined by extraction studies with metal picrates and liquid membrane transport experiments with the same salts. The affinity of these ligands for Ag⁺ has also been investigated by ¹H NMR spectroscopy. Both ketones are better extractants than the esters, and show a strong preference for Ag⁺, while Cu²⁺ is the most extracted cation with the esters. ¹H NMR titrations with AgSO₃CF₃ indicate 1 : 1 complexes for all ligands, those with ketones are more stable, on the NMR time scale, than those with esters. Both esters are good carriers for Ag⁺, and 2b exhibits the highest transport rate (4.7 mol h^-1) found until now with dihomooxacalix[4]arene derivatives.     

Transition metal ion selective ortho-ester diazophenylcalix[4]arene

New chromogenic dizophenylcalix[4]arene 1 showing selective color change to transition metal ions over other alkaline and alkaline earth metal ions has been prepared in the cone conformation and tested for its usefulness.     

p-tert-Butylcalix[4]arene Functionalised with Bipyridyl Carboxylates for Lanthanide Complexation: Synthesis,Photophysical Properties,Solution and Solid State Behavior

A new ligand based on a p-tert-butylcalix[4]arene functionalised with three 6-carboxylato-2,2′-bipyridine arms reacted with lanthanide(III) cations to form 2:2 complexes in the solid state, whereas in solution, a concentration-dependent equilibrium is observed between 2:2 and 1:1 species, as evidenced by ES-MS and metal luminescence measurements. In the X-ray molecular structure of the terbium complex two branched calixarene platforms share one pendant arm in order to provide a neutral dimeric structure which is held together by a strong hydrogen bonded network together with efficient π–π stacking of two pyridine rings belonging to each ligand.     

杯[4]芳烃衍生物的合成和构象研究

以对取代酚亚甲基桥三聚体和２，６－二溴甲基对取代酚为原料，在ＴｉＣｌ４催化下环化得到６种新的含不同取代基［Ｃｌ，Ｂｒ，ＣＨ３，Ｃ（ＣＨ３）３］的杯［４］芳烃衍生物，核磁共振谱研究表明：它们在溶液中的优势构象为锥形构象。     

单炔基桥联双杯[4]芳烃的合成与对溶剂分子的包合性能

对叔丁基杯[4]芳烃直接与1,4-二氯-2-丁炔反应,一步制备了单炔基单桥联双杯[4]芳烃和单炔基双桥联双杯[4]芳烃,并证实单桥联双杯[4]芳烃是双桥联双杯[4]芳烃的中间产物.经¹HNMR,¹³CNMR和ESI-MS分析证实了产物的结构.ESI-MS结果表明两种产物对DMF和H₂O有不同的包合能力.     

Synthesis and structures of malonate derivative-calix[4]arene conjugates

A series of novel malonate derivatives-calix[4]arene conjugates were synthesized through Knoevenagel condensation reaction, and the structures of these functionalized calix[4]arenes have been determined     

稀土(III)与不饱和冠醚配位作用的热力学性质

用量热滴定法测定了2，3－二苯基-烯-[2]-1，4，7，10，13-五氧杂环十五烷（以下称2，3-二苯基-烯-[2]-15-冠-5）与稀土（Ⅲ）硝酸盐（La，Ce，Pr，Nd，Sm，Eu）在无水乙腈溶液中，298.15 K时配位作用的热力学性质．化学计量法表明，所有的稀土硝酸盐均与不饱和冠醚形成了1:1的配合物．实验中，由联接的计算机直接算出了配位物的稳定常数和配合作用的焓，进而算出了吉布斯自由能和配位熵. 结果表明，2，3-二苯基-烯-[2]-15-冠-5与Pr(NO_3)_3形成的配位化合物，其稳定常数最高，并与15-冠-5的实验结果作了比较．从热力学的观点讨论了不饱和冠醚分子结构和阳离子的性质对配位稳定性的影响．     

杯[4]芳烃黄原酸酯衍生物的合成与阳离子萃取性能

以二氧六环作溶剂, 杯[4]芳烃二甲氧基二羟乙氧基衍生物2与氢氧化钾、二硫化碳作用合成了杯芳烃黄原酸盐衍生物3, 并进一步与碘甲烷或氯化苄反应首次合成了含黄原酸酯基的杯芳烃衍生物4a和4b. 阳离子萃取试验表明该新型杯芳烃衍生物比单硫杂杯芳烃衍生物具有更好的过渡金属离子萃取性能.     

Thermodynamics of the Complexation of the p-Sulfonatocalix[4]arene with Simple Model Guests in Water: a Microcalorimetric Study

The formation of supramolecular complexes in water involves interactions of various types which are not always easy to identify, especially when complicated species are involved. A complete thermodynamic characterization of the binding process, which includes the enthalpies and entropies of complexation, is obviously one of the key elements in identifying the stabilizing factors and in understanding how the host and guest assemble. In order to thermodynamically characterize typical interactions of various types, we have thus undertaken a microcalorimetric study of the complexation of p-sulfonatocalixarenes with simple guests bearing different functional groups. Association constants, free energies, enthalpies and entropies for the complexation of the p-sulfonatocalix[4]arene with normal alcohols, alkylammonium, carboxylate and guanidinium ions in water, at pH 7.5 and 298.15?K, are reported. The properties for the binding of lysine and arginine, which bear similar functional groups, are also given. The comparison of the thermodynamic behaviour of these different guests allows the driving factors to be identified. This may constitute a starting point for the understanding of the recognition of more complicated guests.     

Synthesis, NMR, X-ray structural analyses and complexation studies of new Ag selective calix[4]arene based dipodal hosts—a co-complexation of neutral and charged species

New podands based on the p-tert-butylcalix[4]arene unit with substitution at the lower rim incorporating imine units, have been synthesized in high yield by simple condensation method. These podands have been shown to extract and transport Ag⁺ selectively over alkali, alkaline earth metal cations, Zn²⁺, Pb²⁺ and Hg²⁺ ions, from neutral aqueous phase to organic phase. In all the ligands the calix unit has been found to be present in a cone conformation except for the one having pyridine as end group, at the ortho position. It has been isolated in two conformations; cone and 1,2-alternate. To the best of our knowledge, this may be the first 1,3-lower rim substituted calix[4]arene to exist in a 1,2-alternate conformation and is among a few known compounds with this conformation in the general class of calix[4]arenes. A complex of this ligand, which happens to be the highest extractant of Ag⁺ has been isolated and characterized using mass, ¹H and ¹³C NMR spectroscopy's and elemental analysis. The spectroscopic evidence and molecular modelling studies performed on the complex suggest a participation of the imine and pyridine nitrogens and two of the ether oxygens in coordination to the metal ion. The X-ray crystal structures of three of the ligands establish the formation of inclusion complexes with polar acetonitrile solvent molecules. The ¹H and ¹³C NMR spectra of all the compounds, taken in CDCl₃, show the presence of acetonitrile molecules in the cavity of the calix[4]arene, indicating inclusion of the neutral guest molecules in the solution phase as well. For one of the podands X-ray crystal structure has shown a formation of clatharate complex of chloroform with the ligand which has rarely been found in the case of calix[4]arenes.     

1,3-Disubstituted p-tert-Butylcalix[4]arenes as Cholinesterase Inhibitors

The inhibitory effect of 1,3-substituted p-tert-butylcalix[4]arenes on butyrylcholinesterase from horse serum has been discovered and kinetically investigated with photometric microassay techniques. The interaction of calix[4]arene with the enzyme is described in accordance with the formal kinetics of competitive reversible inhibition. The inhibition constants calculated depend on the substituent in the lower rim of the calix[4]arene and vary in the range of (5–110) × 10^-6 M. The proposed mechanism of inhibition involves the cooperative interaction of indophenyl acetate used as a substrate, calix[4]arene and the enzyme without any covalent or electrostatic binding of the functional groups in the active site of cholinesterase. This results in the coordination of the calixarene on the enzyme surface in the proximity of the enzyme active site. Such interaction prevents the substrate from entering the enzyme active site.     

Calix[4]arene Polyaza Derivatives: Novel Effective Neutral Receptors for Cations and (a)-Amino Acids

Introduction Calixarenes are one of the most important supramolecular building blocks, which can be modified by introducing different functional and/or structrual groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules[1,2]. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry[3].     

Chlorination of Calix[4]arene Derivatives

New convenient method for synthesis of p-chlorinated calix[4]arenes is reported. The sulfuryl chloride was used for chlorination of unsubstituted at the lower rim calix[4]arenes. The products of this reaction were very suitable for further O-alkylation.     

Calix[4]quinones. Part 4: The ClO2 oxidation of calix[4]arene dialkyl ethers

Except for the special case of calix[4]arene diethyl ether 1, the chlorine dioxide oxidation of dialkyl ethers 2-5 yielded only the corresponding calix[4]diquinone dialkyl ethers 8-11. Chlorine dioxide oxidation of calix[4]arene diethyl ether 1 produced two isomeric products 6 and 7, which were stable enough to be isolated by column chromatography. However, a slow conformational interconversion between isomeric pair 6 and 7 was observed at room temperature, and the equilibrium was reached after 400 h at 18 °C with an amount of 5:3 in favor of syn-isomer.     

Syntheses and Binding Properties of Novel Calix[4]arene Derivatives Containing Multiple Azo-groups

Introduction Calixarenes are excellent scaffolds that can bemodified by introducing various functional groups tocreate specific interactions between the host and guestmolecules. Thus, many calixarene derivatives contai-ning special functional groups, such as ester, amideand thiourea, have been synthesized and their excellentcomplexing capability for cations have also been stud-ied[1—4]. Lately, calixarene derivatives containing twoor more sorts of functional groups have attracted muchattentio…     

Calix [ 4 ] arene Polyaza Derivatives： Novel Effective Neutral Receptors for Cations and α-Amino Acids

IntroductionCalixarenes are one of the most important supra-molecular building blocks, which can be modified byintroducing different functional and/or structural groupsto create a specific interaction between the host and thetarget molecules, such as meta…