High extraction ability of 1,3-dialkynyl calixarene towards mercury(Ⅱ) ion

The reaction of 1,3-dipropyn-2-yloxycalix[4]arene with mercury（U） acetate could give mercury-containing alkynyl calixarene polymer. The extraction behavior of 1,3-dipropyn-2-yl-oxycalix[4]arene towards mercury（Ⅱ） ion was examined. When the mole ratio of Hg^2＋/calixarene was 1：1, the extractive percent can reach to 99.1%, and the extraction capacity was up to 431 mg/g. It could also decrease the Hg^2＋ concentration from 5 to 0.85 mg/L, which was only 17% of the national standard of effluent and satisfied the national standard of drinking water. The extraction process included chemical reaction.

New Chiral Calixarene Derivatives: Syntheses and Their Chiral Recognition Toward Amino Acids by UV-Vis Spectroscopy

Three novel types of chiral calixarene derivatives 5, 8, and 10 were designed and synthesized by introducing chiral units to parent calixarenes. Their chiralities were confirmed by rotational analysis. Chiral recognition properties of these host compounds towards L- and D-threonine were studied by UV-Vis spectroscopy. The results indicated that calixarene derivatives 5 and 8 exhibited good chiral recognition capabilities toward L- or D-threonine. Although calixarene derivative 10 had no evident chiral recognition ability, the supramolecules of calixarene derivative 10 with L- or D-threonine showed a hypochromic effect or hyperchromic effect respectively. Therefore, calixarene derivative 10 might serve as a good chiral UV-indicator.

NOVEL WATER SOLUBLE HOST MOLECULE DERIVED FROM CALIXARENE

Reaction of p-t-butylcalix[6]arene with ethylene oxide gives a water soluble host compound with a hydrophobic cavity and it can include organic molecules and ions in aqueous solution.

CATALYTIC ACTIVITIES OF RARE-EARTH CALIXARENE COMPLEXES IN POLYMER SYNTHESES

The studies of our group on the catalytic activities of rare earth calixarene complexes in polymer syntheses are reviewed. Rare earth calixarene complexes are effect catalysts for the polymerizations of butadiene, isoprene, ethylene, styrene, propylene oxide, styrene oxide, trimethylene carbonate and 2,2-dimethyl-trimethylene carbonate.

RING-OPENING POLYMERIZATION OF TRIMETHYLENE CARBONATE CATALYZED BY NOVEL SINGLE COMPONENT RARE EARTH CALIXARENE COMPLEXES

In this paper,ring-opening polymerization of trimethylene carbonate(TMC)with rare earth(Nd,Y,La)ρ-tert- butylcalix[n]arene(n=4,6,and 8)complexes as catalysts has been studied.Poly(trimethylene carbonate)(PTMC)with M_v of 21,400 was produced by bulk polymerization under the conditions as follows:[TMC]_0/[Nd](molar ratio)=1000,80℃, 8 h.Mechanism study reveals that the polymerization proceeds via a coordination mechanism.

A New Type of Dibenzoyl Tartaric Acid Selective Electrode Based on Polymer Membrane Containing Calixarene Ionophore

A new type of di benzoyl tartaric acid selective electr ode has been developed. Three double\| arm calixarene derivatives were emp loyed as the neutral ionophores. The poly(vinyl chloride) membrane electrode containing an amide derivative of ca lixarene as the neutral carrier an d a dibutyl phthalate as the plastici zer exhibited the highest sensitivity for dibenzoyl tartaric acid. The slop e of linear portion was 27.8 mV per c oncertration decade. The electrode has a fast response and a long lifetime .

Transports of K^+,Ca^(2+) Ions in Liquid Membrane with Calixarene Derivatives as Carriers

A few derivatives of calixarenes have been synthesized and characterized by IR, ^1H NNtR, thermal and elemental analysis. The transport of potassium or calcium ion through the liquid membrane, in which the derivatives act as carriers, has been studied. The electron-effect of the substituent on the upper rim of calixarene possesses important effect on the net transport of metal ions. The p- tert-butylcalix[4]arene is the best carrier of calcium ion, compared with p-tert-calix[4]arene（n = 4, 6, 8）. The ptert-butylcalix[4]arene acid is better than p-tert-butylcalix [4]arene. The calixr43crown is the best carrier of calcium ions of all the carriers. The pH gradient between the source and receiving phase, and the concentration of K^＋ , Ca^2＋ ions in the source phase affect mainly transport. After the transport, the pH value of the source phase is found to be decreased, once the calix [n ] arene derivatives act as carrier. But it is not the case for the calix[n] crowns. It might be interpreted as the result of their different mechanisms.

COVALENTLY ATTACHED MULTILAYER ULTRA-THIN FILMS FROM DIAZORESIN AND CALIXARENES

A kind of photosensitive ultra-thin film was fabricated from diazoresin (DR) and various calixarenes by using theself-assembly technique. Under UV irradiation both the ionic- and hydrogen bonds between the layers of the film will convert into covalent bonds. As a result, the stability of the film toward polar solvents increases dramatically.

The Synthesis of a New Type of Calixarene with Chiral Pendant

Two new chiral calixarenes were synthesized by condensing 1,3 bis chlorocarbomethyl calixarenes with (1S, 2S) 2 amino 1 (4 nitrophenyl) 1,3 propanediol, a by product from antibiotic industry , and were characterized by 1H NMR , MS FAB, and elemental analysis. The 1H NMR spectra show that those molecules assume a cone conformation in solution.

Hydrothermal Synthesis of [ Mn_5(H_2PO_4)_2(PO_4)_2(H_2O)_4]Templated by Calixarene Under Mild Conditions

The title compound [ Mn5 （ H2PO4 ）2 （ PO4 ）2 （ H20）4 ] was hydrothermally synthesized in the presence of calix[4]arene-p-tetrasulfonate. The title compound was structurally characterized by X-ray single crystal diffraction. It crystallizes in the monoclinic space group C2/c with α = 1.762 9（4） nm, b = 0.913 44（18） nm, c=0.94977（19） nm, β=96.52（3）°, V=1.5195（5） nm^3, Z=4 and R1=0.0283, and exhibits a three-dimensional framework and channel structure. It was proposed that calixarene can act as template during the formation of the title compound because calixarene can bind Mn^2＋ through second-sphere coordination.

Synthesis of Two Blue-light emitting Complexes with Schiff Base Calixarene as the Ligand

Two new blue luminescent zinc and beryllium complexes with Schiff base calixarene derivative as the ligand were prepared. Their luminescent properties were determined, which indicated that they had strong blue fluorescent properties. They also had good solubility and film formation. These new complexes can be used as blue organic electroluminescent materials (OELMs) in organic electroluminescent devices.

Bridging of Calixarenes with N,N′-Bis(Chloroacetyl)Propylenediamine

A new bridging reagent, N,N ′\|bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p \|tert\|buty lcalix\arene, p \|tert\|buty lcalix\arene and butylcalix\arene. It was found that the bridging reaction is selectively, at least, preferably at 1,3\|position for p \|tert\|butylcalix\arene and p \|tert\|b utylcalix\arene, 1,5\|position for p \|tert \|butylcalix\arene. Taking the yield of bridged calixarene as a comparsion standard, the activity decreases with the increasing of the number of phenolic units in calixarene.

Study on the Surface Acoustic Wave Sensor with Self-Assembly Imprinted Film of Calixarene Derivatives to Detect Organophosphorus Compounds

The molecularly imprinted technology and the self-assembly technique were used together on the calixarene surface acoustic wave (SAW) chemical sensors to detect organophosphorus compounds. 25-(thioalkyl-alkoxy)-p-tertbutylcalix[4] arene with self-assembled monolayer character was the sensitive coating of the sensors. The sensors had a special response to organophosphorus compounds and the response frequency shift of this sensor to organophosphorus compounds in 0.1 mg/m3 was 350 Hz. The response frequency increased linearly with the increase of the concentration of DMMP in the range from 0.1 to 0.6 mg/m3. The possible explanation of the interaction between the coatings and organophosphorus compounds was discussed.

STUDIES ON CALIXARENES I THE CNDO/2 CALCULATION OF EQUILIBRIUM MOLECULAR GEOMETRY OF CALIX[4]ARENE IN CONE CONFORMATION

The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with those obtained from X-ray analysis.

Synthesis of calixarenes and their extraction performance for ester catechins

A series of extractants （tert-butylcalix[6]arene, tert-butylcalix[8]arene and octeacetate of tert-butylcalix[8]arene） were synthesized, and their structures were identified by IR and JH-NMR. The distribution behavior of ester catechins monomer in the aqueous and chloroform two-phase system containing one of calixarene was studied. The influences of different extractants, concentration of tert-butylcalix[8]arene and extraction temperature on the partition coefficients and the separation factors were investigated. The experiment results show that tert-butylcalix[8]arene is the best extractant that forms a more stable supramolecular compound with gallocatechin gallate （GCG） than with epigallocathechin gallate （EGCG） or epicatechin gallate （ECG）. When the concentration ofp-tert-butylcalix[8]arene is 3.79 mmol/L, the extraction temperature is 4 ℃, the partition coefficients ofKGCG, KECG, KEGCG are 0.987, 0.629, 0.449, the separation factors of al and a2 are 1.450 and 1.596, respectively. The important factors influencing the extraction properties of calixarene are discovered to be its cavity size and hydrogen bonding.

应用于纳米制造的新型电子束抗蚀剂Calixarene的工艺研究

为了满足电子束光刻(EBL)对高分辨率、性能优秀抗蚀剂的需求,研究了将Calixarene衍生物作为电子束抗蚀剂在胶液配制、电子束曝光及显影等工艺过程中的相关技术.其中电子束曝光实验在JEOL JBX-5000LS系统上进行.实验结果表明,在入射电子能量50 keV、束流50 pA的条件下,Calixarene可以方便地形成50 nm的单线、50nm等线宽与间距的图形结构.通过与常用电子束抗蚀剂的对比,总结了Calixarene在电子束光刻性能上的优缺点,并分析了其成因.作为一种新型的高分辨率电子束光刻抗蚀剂,Calixarene有望应用在纳米结构制造、纳米尺寸器件及电路的研制等领域.

Controlled drug delivery systems based on calixarenes

In recent years, cancer has become the number two cause of death around the world, and scientists have exploited various treatment maps. Calixarenes, with diversified features, have been widely applied into drug delivery systems, which can respond to multi-stimuli and exhibit excellent performance. In this mini-review, we summarize the recent advances on controlled drug delivery systems based on calixarenes, in the form of inclusion complexes, amphiphilic self-assembly nanocarriers including micelles, hydrogels, vesicles and liposomes, and supramolecular nanovalves on mesoporous silica nanomaterials.

Upper Rim Diester-bridged Calixarenes and Oligocalix-arenes: the Effects of the Length of Bridged Reagents on Their Distribution

A series of monobridged calixarenes 3a-f, cyclic biscalix arenes 4a-f, diametrically bridged at the upper rim with saturated aliphatic diester chains, have been synthesized. The results at dilute conditions show that the percentage of yields of mono , bis and oligo calixarenes are related to the length of the chains. With the shortening of the chains, the percentage of monocalixarenes decreased. All the calixarene moieties are in a cone conformation according to the AB quartet pattern of the methylene protons between the phenolic rings in the 1H NMR spectra.

Extraction and Separation of Rare Earths from Nitrate Medium by Mixtures of p-Phosphorylated Calixarene and 1-Phenyl-3-methyl-4-benzoyl-pyrazalone-5

The gadolinium extraction by the mixtures of p-phosphorylated calixarene and 1-phenyl-3-methyl-4-benzoylpyrazalone-5 from nitrate medium was studied,which indicated an obvious synergistic effect between these two extractants.The extractants exhibit no interaction with each other before the metal extraction.Gadolinium(Ⅲ)was extracted by the species of Ln(PMBP)_(2)L_(2)(NO_(3))instead of Ln(PMBP)_(3)•(HPMBP)or Ln(NO_(3))_(3)•2L which are extracted by HPMBP or L alone.Thermodynamic functions(ΔG,ΔH,ΔS)were calculated.The extraction of other rare earths was also investigated and compared.Possible single rare earth separation was discussed.

Synthesis of Ultra-high Molecular Weight Polystyrene with a Catalyst System Based on Calixarene-yttrium Complex

Polymerization of styrene (St) with a new catalyst system composed of calixarene yttrium complex, magnesium aluminium alkyls and hexamethyl phosphoramide was studied. The catalyst system shows extremely high activity (>7×10 6 g PSt/mol Y·h) and gives polystyrene with very high viscosity average molecular weight (>5×10 5) .