氨基硫脲基新型杯[4]芳烃衍生物的合成

通过1,3-环氧丙基杯[4]烃与硫代氨基脲开环反应,合成硫代氨基脲基杯[4]芳烃衍生物,研究了其对阳离子的吸附性能后发现,与其他氨基杯芳烃相比,该衍生物对铜离子的吸附性能较好,并且有很好的选择性。     

氮杂杯[6]芳烃的合成与表征

以三聚氯氰和对苯二胺为原料,碳酸钾或氢氧化钾作为缚酸剂,合成氮杂杯[6]芳烃第一步中间体N,N’-二(4,6-二氯-1,3,5-均三嗪-2-基)-1,4-苯二胺(Ⅰ)和第二步中间体2,4-二(4-胺基苯胺基)-6-氯-1,3,5-均三嗪(Ⅱ),再由(Ⅰ)和(Ⅱ)合成最终产物氮杂杯[6]芳烃。通过红外光谱分析法和核磁共振氢谱法对产物进行了表征,证实其为目标产物,从而验证了合成路线的可行性。     

Polymer supported calix[6]arene hydroxamic acid, a novel chelating resin

A new polymer-supported calix[6]arene hydroxamic acid has been synthesised by reacting the acid chloride 37,38,39,40,41,42 hexahydroxy 1,8,13,19,25,31 hexacarboxy calix[6]arene with poly(styrene β-hydroxylamine). The synthesised resin was characterised by elemental analysis, FT-IR and mass spectra. Physicochemical properties viz. swelling, wet-density, void-volume, exchange capacity etc. were determined. The resin has 4.46 mmol/g exchange capacity for rare elements. The resin was used for the chromatographic separation of U(VI), Th(IV) and Ce(IV) by the judicious adjustment of pH 4.0, 6.0 and 7.5, respectively. The thorium and cerium were eluted with 0.1 M HCl while uranium was eluted with 2 M HCl. These rare elements were preconcentrated and determined in the presence of each other, monazite sand and environmental samples.     

Electrochemical response of ferrocenium filled calix[4]arene capsules in solution and immobilized on gold

Hydrogen-bonded dimers of tetra-urea calix[4]arenes are able to include ferrocenium ions as a guest. Heterodimeric capsules are exclusively formed in 1:1 mixtures of tetra-arylurea calix[4]arene 1 with tetra-tosylurea calix[4]arene 2. Sulfide groups attached via spacers on the urea rim of 1 allow their binding to metal surfaces rendering simultaneously their dissociation more difficult. Thus, the electrochemical response of encapsulated ferrocenium could be studied in a self-assembled monolayer (SAM) in addition to the solution electrochemistry with cyclic voltammetry. The stability of the electrochemically active monolayers was tested after a heat treatment (225 °C for 30 min in N₂ atmosphere) and multiple cycling (up to 1200 cycles), which could be required for a possible application as molecular based information storage.     

Preparation and characterization of p-tert-butyl thiacalix[4]arene imbedded flexible polyurethane foam: An efficient novel cationic dye adsorbent

In this study, a new type of flexible polyurethane foam containing p-tert-butyl thiacalix[4]arene (TC4A) macrocycle was synthesized. TC4A macrocycle was incorporated into polyurethane foam as a part of crosslinking agent as well as glycerol. Structural, morphological, thermal and mechanical properties of this prepared foam were studied and compared with a polyurethane foam based on only glycerol as crosslinking agent, by Fourier transform infrared (FTIR), Scanning electron microscopy (SEM), Thermal gravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). The effect of introduction of TC4A crosslinker on cream time, rise time, apparent density, and water absorbency of the PU foams was evaluated. Moreover, it was shown that new TC4A-based polyurethane foam (TC-PUF) can be a high performance adsorbent for removal of malachite green from aqueous media using batch adsorption technique. The adsorption results indicated that TC-PUF has a high adsorption capacity of 58.82 mg/g for malachite green due to the presence of TC4A macrocycles in the structure of polyurethane foam. The kinetics of adsorption of malachite green was also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The results of kinetic studies showed that the adsorption of malachite green onto TC-PUF followed pseudo-second-order kinetic model.     

Alkali metal ions transfer across a water/1,2-dichloroethane interface facilitated by a novel monoaza-B15C5 derivative

In this paper, a novel monoaza-B15C5 derivative, N-(2-tosylamino)-isopentyl-monoaza-15-crown-5 (L), is used as an ionophore to facilitate alkali metal cations transfer across a water/1,2-dichloroethane (W/DCE) interface. Well-defined voltammetric behaviors are observed at the polarized W/DCE interfaces supported at micro- and nano-pipets except Cs⁺. The diffusion coefficient of this ionophore in the DCE phase is calculated to be equal to (3.3±0.2)×10⁻⁶ cm² s⁻¹. The experimental results indicate that a 1:1 (metal:ionophore) complex is formed at the interface with a TIC/TID mechanism. The selectivity of this ionophore towards alkali ions follows the sequence Na⁺>Li⁺>K⁺>Rb⁺>Cs⁺. The logarithm of the association constants (log β₁^o) of the LiL⁺, NaL⁺, KL⁺ and RbL⁺ complexes in the DCE phase are calculated to be 10.6, 11.6, 9.0 and 7.1, respectively. The kinetic parameters are determined by steady-state voltammograms using nanopipets. The standard rate constants (k⁰) for Li⁺, Na⁺, K⁺ and Rb⁺ transfers facilitated by L are 0.54±0.05, 0.63±0.09, 0.51±0.04 and 0.46±0.06 cm s⁻¹, respectively. The pH values of aqueous solution have little effect on the electrochemical behaviors of these facilitated processes. The results predicate that this new type of ionophore might be useful to fabricate electrochemical sensor of sodium ion.     

Thermal Behaviors of Bisazocalix[4]arene Derivatives

In this article, calix[4]arene (4) was prepared by debutylation and hydrolyses reacting from 25,27-dibenzoyl-26,28-dihydroxy-5,11,17,23-tetra(tert-butyl)calix[4]arene (2). Azocalix[4]arenes (6a-c) were coupled by linking 4-methoxy, 4-ethyl, and 4-nitroaniline to calix[4]arene (4) through a diazo-coupling reaction. Thermal behavior characteristics and decomposition routes of 25,26,27,28-tetrahydroxy-11,23-di(tert-butyl)-5,17-(p-substitue phenyl)azocalix[4]arene (6a-c) were investigated in air atmosphere by means of thermogravimetry (TG), differential thermogravimetry (DTG), and differential thermal analysis (DTA) analyses. It was found that the decomposition of all compounds complete with two exothermic stages which corresponded to removal of substitute groups (methoxy-, ethyl-, nitro-) and second stage rest of structure decomposition.     

对叔丁基杯[4]芳烃巯基吡啶衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合得到对叔丁基杯[4]芳烃,再对其下沿酚羟基进行化学改性,得到具有化学活性的杯[4]衍生物中间体,该中间体与具有活泼氢的2-巯基吡啶反应制得新的含N、S杯芳烃衍生物,总收率14.4%。     

杯[8]芳烃萃取稀土金属离子的研究

合成了对叔丁基杯[8]芳烃,研究了其对稀土金属钕、铕、镨离子(Nd^3 、Eu^3 、Pr^3 )在溶液中的萃取。测定了在25℃,离子强度I=0．1g／mol时Nd^3 、Eu^3 、Pr^3 的萃取平衡常数。探讨了杯[8]芳烃萃取分离这3种稀土金属离子的条件、萃取反应机理及其规律性。     

相转移催化合成四乙酰氧基对叔丁基杯[4]芳烃

以聚乙二醇(PEG)600为相转移催化剂合成四乙酰氧基对叔丁基杯[4]芳烃。实验结果表明：当对叔丁基杯[4]芳烃1．0g,乙酸酐9mL,0．0224g浓98％H2SO4(质量分数)和0．4gPEG600,回流反应20min,产率达到75．1％。     

杯[4]芳烃巯基吡啶衍生物的合成

以对叔丁基苯酚为起始原料,通过缩合得到对叔丁基杯[4]芳烃,再对其下沿酚羟基进行化学修饰,得到具有化学活性的杯[4]衍生物,该化合物与具有活泼氢的4巯基吡啶反应制得新的含N、S杯芳烃衍生物,总收率15.3%。     

Spectrophotometric and electrochemical behavior of a novel azocalix[4]arene derivative as a highly selective chromogenic chemosensor for Cr

In this study, a novel azocalix[4]arene derivative, 5,11,17-tris[(1-naphtyl)azo]-25,26,27,28-tetrahydroxy-calix[4]arene (NAC4) bearing napthyl groups on the upper rim was synthesized. Its complexation behavior for alkali, alkaline-earth and various heavy metal ions (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺, Hg²⁺, Ni²⁺, Cd²⁺, Cu²⁺, Zn²⁺, Co²⁺, Fe²⁺, Cr³⁺, Ag⁺) was investigated by spectroscopic and voltammetric methods. This chemosensor exhibits decreased absorbance in the presence of Hg²⁺ and a unique absorbance quenching effect only for Cr³⁺. In addition, a new absorption band centered at 565 nm with the formation of the 1:1 host–guest complex (Cr³⁺-NAC4) was observed in the case of Cr³⁺, leading to an obvious color change from light orange to dark lilac. In voltammetric experiments, Cr³⁺ ions decreased voltammetric peaks of NAC4, whereas no significant changes occurred in the presence of the other metal ions. The Benesi–Hildebrand method was used to determine a logarithmic value of 3.76 for the association constant of the complex between Cr³⁺ and NAC4.     

对叔丁基杯[4]及杯[6]芳烃的合成及其对铜离子的萃取研究

以对叔丁基苯酚和甲醛为原料,分别对对叔丁基杯[4]及杯[6]芳烃的合成和萃取性质进行了研究．结果表明,在本研究范围内,以KOH为催化剂,对叔丁基杯[6]芳烃的最高产率为77．8％;以NaOH为催化剂,对叔丁基杯[4]芳烃的最高产率为47．3％。对于对叔丁基杯[4]和杯[6]芳烃,最佳的反应回流温度都为140℃。对叔丁基杯[6]芳烃对模拟废水中的铜离子具有一定的萃取效果,最高萃取率为70．3％。     

Removal of cesium by countercurrent solvent extraction with a calix[4]crown derivative

A macrocyclic 1,3-di(1-dodecyloxy)-2,4-crown-6-calix[4]arene (DodCalix[4]C6) was synthesized and characterized. The extraction of Cs(I) and more than 10 typical metals with DodCalix[4]C6/octanol in HNO₃ medium was investigated. DodCalix[4]C6 exhibited strong extraction ability and high selectivity for Cs(I) over others except for Rb(I). The optimum acidity in Cs(I) extraction was 3.0 M HNO₃. The Cs(I) separation from a simulated highly active liquid waste by five-stage countercurrent extraction was performed. The extraction efficiency of Cs(I) for five-stage extraction was greater than 99%. The effective partitioning of Cs(I) by DodCalix[4]C6/octanol through multistage countercurrent extraction was achieved.     

氮杂杯[6]芳烃迭氮化衍生物的合成与表征

以氮杂杯[6]芳烃和迭氮化钠为原料,四氢呋喃为溶剂,在为40~45℃合成了氮杂杯[6]芳烃迭氮化衍生物,通过薄层色谱分析法、红外光谱分析法和核磁共振氢谱法对产物进行了表征,证实其为目标产物,从而验证了合成路线的可行性。     

Anion complexation by calix[4]arene-TTF conjugates

Calix[4]arenes bearing tetrathiafulvalene (TTF) moieties appended to the upper rim via the amidic functions were synthesized and used for ¹H NMR and UV/Vis complexation studies towards selected anions. It was found that the complexation affinity towards H₂PO₄⁻ dramatically depends on the substitution pattern of the calixarene moiety. As a result, the proximally disubstituted derivative has a complexation constant by two orders of magnitude higher than the distally disubstituted analogue. The differences between proximal and distal receptors were also documented by their behaviour during the oxidation of the attached TTF units.     

杯[4]芳烃醚类衍生物的合成(Ⅱ)

以对叔丁基苯酚和甲醛为起始原料，通过选用不同的催化剂，合成了一系列新的杯[4]芳烃的四醚化衍生物，并对其结构用IR、^1HNMR、^13CNMR、MR进行了表征。     

Droplet-based microreactor system for stepwise recovery of precious metal ions from real metal waste with calix[4]arene derivatives

ABSTRACT

Stepwise recovery of silver(I), palladium(II) and platinum(IV) with suitable calix[4]arene extractants was carried out by investigating the extraction and stripping process using a droplet-based microreactor system. The highest percentages of silver, palladium (100%) and platinum ion (37.2%) were extracted from a real waste only within 4.00s using a microreactor system compared with 24 and 72 h to reach extraction equilibrium in a batch method. Fourier transform infrared spectroscopy studies revealed a very good relation in peak shifts on the metal complexation with calix[4]arene derivatives after extraction and stripping. The droplet-based microreactor system emerges as an effective tool to be applied in metal recovery.     

蒽醌冠醚双功能化杯[4]芳烃的合成与表征

以对叔丁基杯[4]芳烃为原料,经碱催化两步合成了26,28-双（2-亚甲基蒽醌）-5,11,17,23-四叔丁基杯[4]-25,27-冠-6。产物经IR、1HNMR表征和元素分析表征,该衍生物为锥形结构并与设计思想一致。     

Electroanalytical studies on cadmium(II) selective potentiometric sensors based on t-butyl thiacalix[4]arene and thiacalix[4]arene in poly(vinyl chloride)

Cd²⁺-selective sensors have been fabricated from poly(vinyl chloride) (PVC) matrix membranes containing t-butyl thiacalix[4]arene (I) and thiacalix[4]arene (II) as electroactive materials. The addition of sodium tetraphenylborate and the plasticizer 2-nitrophenyl octyl ether has been found to improve the performance of the sensors substantially. The membranes of various compositions of the two thiacalixarenes have been investigated and it was found that the best performance was obtained for the membrane of composition II:PVC:NaTPB:NPOE in the ratio 5:120:3:150. The sensor shows a linear potential response for Cd²⁺ over a wide activity range 3.2 × 10⁻⁶ to 1.0 × 10⁻¹ M with Nernstian compliance (29.5 mV decade⁻¹ of activity) in pH range 4.5-6.5 and a fast response time of ∼8 s. The potentiometric selectivity coefficient values determined by matched potential method indicate excellent selectivity for Cd²⁺ ions over mono-, di- and trivalent interfering cations. The sensor exhibits adequate shelf life (∼3 months) with good reproducibility (S.D. ±0.2 mV) and can also be used in partially non-aqueous media having up to 20% (v/v) methanol, ethanol or acetone content with no significant change in the value of slope or working activity range. The sensor has been used in the potentiometric titration of Cd²⁺ with EDTA. The sensor could be successfully used for the quantification of cadmium in river water samples.