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

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Calixarenes enabling well-adjusted organic-inorganic interface for inverted organic solar cells with 18.25%efficiency and multifold improved photostability under max power point tracking

Compared with organic solar cells(OSCs) adopting conventional architecture,inverted OSCs have offered generally better stability,where Zn O is the most widely used electron transporting layer(ETL) material.For ZnO-based inverted OSCs,a welltuned interface of organic(active layer)-inorganic(Zn O film) with matched surface energy(γS) is critical for both high performance and high stability.In this work,two typical calixarenes,C4A and Bu C4A,were employed as the tuning agents to adjust this organic-inorganic interface for ZnO-based inverted OSCs.As a result,with PM6:L8-BO as the active layer,significantly promoted power conversion efficiencies(PCEs) from 17.14%(for ZnO) to 18.25%(for ZnO/C4A) and 17.80%(for ZnO/Bu C4A) were achieved.Photodynamic studies indicate that the enhanced performance is due to the faster charge extraction process,the suppressed recombination and more ideal internal electric field in ZnO/calixarene-based devices.In addition,wellmatched interface energy and more ordered molecular aggregation in active layer effectively improved photostability and thermal stability for ZnO/calixarene-based devices.These results indicate that calixarenes could act as effective modifying agents of ZnO to improve inverted OSCs’ performance and stability simultaneously,and likely also stimulate calixarenes’ and other macromolecules’ broader studies in other organic electronic devices.

Natural Silicate as a Solid Support for the Calix[4]Thiophosphorus Derivative for Removal Mercury (II), as Picrate from Water

Currently a technique widely used for gold extraction is mercury by amalgamation technique, the tailing produced pollutes water of all kinds, so it is necessary to develop a form of selective mitigation, for which it is necessary to use complexing agents based on calixarene functionalized with mercury sequestering agents. These are immobilized by adding supports based on natural silica to form polymers and make them insoluble in all types of solvents, so that they can be used as an extractor and at the same time regenerate to their original properties for continuous reuse.

Extraction of copper with p-tert-butyl-calixarenes

The extraction of copper with calixarenes was researched by comparing the results from calix[4]-,calix[6]-and calix[8]-arenes.Hie extraction ability increased as the order:calix [4]-】 calix[8]-】 calix[6]-arenes,with the binding ratio being 1:1.The extraction mechanism was also discussed,and itsequation Cu(NH3)42+ +H2L(0)Cu(NH3)4L(0)+ 2H+ and the extraction equilibrium constants(Ker)for calix[6]-and calix[8]-arenes were obtained respectively.

Study on the Complexation Property of Calixarenes

Calixarenes are macrocyclomolecules consisting of phenol units bridged together bymethylene groups. Their structure may be expressed

Synthesis and inclusion properties of amphiphilic calixarenes

Study of host-guest interaction with the aid of proper model system is helpful to the understanding of complicated chemical reactions in biological processes on the molecular level. Cyclodextrins and crown ethers are two kinds of the most extensively studied host molecules and enzyme mimics. The cyclodextrins are very hydrophilic on their out rims but lipophilic on the inner remainder; the crown ethers are highly lipophilic on the outside and hydrophilic on the inside. In recent years, calixarene has been found a new kind of host compounds, which can form host-guest inclusion complexes with many kinds of

Organic supramolecular aggregates based on water-soluble cyclodextrins and calixarenes

Macrocycle-induced formation of pure organic supramolecular aggregates is a challenge that has attracted considerable attention from researchers in the fields of chemistry,biology,and materials science.In particular,aggregation induced by water-soluble cyclodextrins and calixarenes,which are two classic of macrocycles with a hydrophobic cavity and a hydrophilic external surface,has attracted interest because these host molecules can form aggregates with guest molecules via various noncovalent interactions,including hydrophobic interactions,van der Waals forces,hydrogen bonds,and electrostatic interactions.In this review,we focus mainly on some impressive recent progress,both by our group and other groups,on the construction of cyclodextrin-and calixarene-based organic supramolecular aggregates,control of their topological morphology,and their use for biological applications such as molecular recognition and bioimaging,photodynamic therapy,light-harvesting energy transfer,and targeted drug delivery.We also discuss shortcomings of the current reported results and future prospects for the development of multifunctional organic supramolecular aggregates for use in various fields.

Studies on the Intramolecular Inclusion Complexes of Functionalized Calixarenes with CH_3X (X=CN, NO_2)

Two functionalized calixarenes in cone conformation L 2-3 have been synthesized and their intramolecular inclusion complexes (1∶1) with organic neutral molecules CH 3CN and CH 3NO 2 have been prepared and characterized, respectively. The X-ray crystallographic analysis shows that L 2 in L 2·CH 3CN·C 2H 5OH has C 4 symmestry and L 3 in L 3·CH 3NO 2 exhibits C 2 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-π interactions, suitable geometrical parameters have been calculated from the crystal data of intramolecular inclusion complexes. The results show that L 3·CH 3NO 2 with L 3 in C 2 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 L 1·CH 3CN and L 1·CH 3NO 2 were also given and discussed.

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.

Azocalixarenes: a scaffold of universal excipients with high efficiency

Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including molecular-level protection, small sizes,fast kinetics of host-guest recognition, and modular construction. With the continuous advances in the medical field, personalized and precision medicine requires the development of excipients with low dosages, integrated modifying effects, universality,and controlled release. To meet these requirements, we have developed a new family of macrocyclic excipients based on calixarenes by integrating their covalent(broad chemical design space) and noncovalent(wide range of substrates) advantages.Accordingly, azocalixarenes(Azo CAs) were designed, showing high binding affinities to a broad spectrum of active pharmaceutical ingredients(APIs), selectivity to interferents, and responsiveness to hypoxic microenvironments. Due to their highly efficient and controllable recognition, Azo CAs serve as low-dose excipients for 30 APIs. Molecular encapsulation by Azo CAs results in the integrated modification of the physicochemical properties of APIs, including solubility, stability, bioavailability,and biocompatibility. Moreover, Azo CAs can be reduced by azoreductases overexpressed in hypoxic microenvironments,leading to the controlled release of APIs. Collectively, Azo CA excipients have broad application prospects for a series of diseases such as enteritis, arthritis, stroke, cancer, bacterial infection and kidney injury, with diverse therapeutic modalities,including chemotherapy, photodynamic therapy, photothermal therapy, immunotherapy, boron neutron capture therapy, radiotherapy, fluorescence imaging, and their combinations.

Synthesis and Conformational Studies of Some Metacyclophane Compounds

Various [3.3.3]metacyclophane derivatives were synthesized from 6,15,24-tri-tert-butyl-9,18,27-trimethoxy [3.3.3] metacyclophane-2,11,20-trione 1 using simple chemical reactions. The conformations of the synthesized compounds were studied using mainly solution Proton Nuclear Magnetic Resonance (1H NMR) spectroscopic methods. Two of the synthesized compounds 5, 6, were found to have a partial cone conformation with the third, 4, having the cone conformation. Detailed variable temperature Proton Nuclear Magnetic Resonance studies further confirmed the partialcone conformation for the two products, 5, 6. During the variable temperature nuclear magnetic resonance spectroscopic studies, 6,15,24-tri-tert-butyl-9,18,27-trimethoxy[3.3.3]metacyclophane-2,11,20-triol was found to have a coalescence temperature of about 0?C.

Functioned Calix[4]arenes as Artificial Enzymes Catalyze Aldol Condensation

Aldolase models derived from calix[4]arene were designed and synthesized. The aldol condensation of p-nitrobenzaldehyde with acetone was catalyzed by the synthetic enzymes proceeded under mild conditions to offer chiefly aldol-type product in good yield.

Inclusion Property and Molecular Modeling of Calix[4]arene Derivatives

The inclusion properties of two calix[4]arene derivatives 5,11,17,23 tetra tert butyl 25, 27 bis (isopropyl carbamoyl methoxy) 26,28 diundecenyloxy calix[4]arene (C[4]A) and 25,27 dibutoxy 5,11,17,23 tetra tert butyl 26,28 diundecenyloxy calix[4]arene (C[4]B) were studied by gas chromatographic method. It was found that C[4]A could form inclusion complexes with benzene, toluene, methanol and ethanol while C[4]B could only form inclusion complex with methanol, which might be due to the different conformations of C[4]A and C[4]B. Molecular modeling showed that CH/π and OH/π interactions played important roles in the forming of inclusion complexes.

Synthesis and Characterization of New Calix[4]arene Amino Acid Ester Derivatives and Their Metal Extraction Properties

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Synthesis of Calix[4] dithiacrown PlatinumComplexes and Their Catalytic Behavior in the Hydrosilylation of Olefins with Triethoxysilane

5, 11, 17, 23-Tetrakis-1’, 1’-dimethylethyl-25, 27-dihydroxy-26, 28-1", 7", 13"-trioxa-4", 10-dithia-tridecylcene-calix [4] arene (calix [4]dithiacrown-5 ) and its O-methylated derivate (dimethylcalix [4]dithi-acrown-5 ) were synthesized from p-tert-butylcalix [4] arene vla 1, 3-lower rim functlonalization withchloroethyltosylate, followed by rlng-closlng condensation with β,βP’-dimercaptoethyl ether in the presence of sodium ethoxide as a base in reflux ethanol under nitrogen atmosphere, rollowed hy methylation with methyl-tosylate in the presence of NaH as a base in dioxane. It was round that they can coordinate with platinous chloride and the Platinous complexes are efficient catalysts ror the kydrosilylation of olefins with triethoxysi-lane.

Fabrication of Chemically-Modified Electrode Containing 1:12 Phosphomolybdic Anions by Sol-Gel Technique and Its Electrocatalytic Reduction of BrO_3 ^-Anions

A novel chedrically-modified electrode containing 1:12 phosphomolybdic anions wasachieved on the surface of platinum electrode by the sol-gel technique. The electrode exhibits ahigh catalytic activity towards the electroreduction of BrO3- anions.

Studies on the Synthesis and Property of A New Podand-armed Calix[4]arene Derivative

A new ligand 25, 26, 27, 2 8 -tetrakis [2-(o- methoxyphenoxy]ethoxy] calix [4] arene 3 was synthesized by direct base-strength-driven O-alkylation of calix[4]arene 1. 3 has been used as ionophore for cesium selective PVC membrane electrode. The extraction for cesium and sodium with 3 have been also studied.

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.

Synthesis of Tetra-O-Alkylated Calix[4]arenes under Phase-Transfer Conditions

A modified PTC method of preparing tetra-O-aIkylated callx[4]arenes is described. Using PEG-400 as phase-transfer catalyst and solld sodlum hydrate as a base, full alkylatlon of calix[4]arenes has beenproceeded smoothly in toluene at 9℃. The debutylated callx[4]arene can also be fully alkylated by thismethid.

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.