Synthesis and polymerization of a new nitrogen‐containing bis‐ortho‐diynylarene monomer

This study focuses on the preparation, characterization, and optical properties of new bis(3,4‐diphenylethynylphenyl)phenylamine. This is the first nitrogen‐containing bis‐ortho‐diynylarene (BODA) monomer having a nitrogen atom as the spacer group. BODA monomers are usually prepared from common bisphenols, thereby providing great synthetic versatility and the opportunity to develop a wide array of novel polyarylene thermosets by varying the aromatic spacer group. The new bis(3,4‐bisphenylethynylphenyl)phenylamine was synthesized in five steps. This compound emits an intense blue color (λ = 438 nm) upon irradiation by UV light and may be suitable for use as an emitting layer in electroluminescent devices. Bis‐(3,4‐bisphenylethynylphenyl)phenylamine and its polymer have photoluminescence quantum yields 34 and 38%, respectively, and long excited‐state lifetimes of 3.2 and 3.6 ns, respectively. The structure of the monomer and its polymer were characterized using spectroscopic techniques including Ultraviolet–visible Spectrophotometer, Photoluminescence Spectrophotometer, Fourier Transform infrared spectroscopy, and Gel Permeation Chromatography. The polymerizations were studied by Differential Scanning Calorimeter. The amount of weight loss and the thermostability of the nitrogen‐containing polymer were determined from thermogravimetric analysis. The electrical conductivity of neat HCl‐doped BODA‐derived polymer film was measured according to the standard four‐point probe technique. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6988–6996, 2006     

Cationic polymerization of diglycidyl ether of bisphenol A

The cationic nonlinear polymerization of diglycidyl ether of Bisphenol A (DGEBA) in the presence of a diluent γ-butyrolactone (BL) was initiated by the BF₃-4-methoxyaniline (MA) complex. The reaction was studied by size exclusion chromatography, DSC, and dynamic mechanical analysis. Reaction mechanism involves a fast formation of adducts of DGEBA with MA released from the initiator. Formation of spiro orthoesters (S) by reaction of BL with DGEBA and homopolymerization of DGEBA as well as copolymerization with S follow. Gelation occurs at 60°C within a few minutes at conversion of epoxy groups (ξ_E)_c = 0.20–0.45. The networks cured under optimum conditions show high glass transition temperature, T_α = 178°C. The mechanism-structure-property relations are discussed. © 1994 John Wiley & Sons, Inc.     

~(14)N ENDOR Study on Bis(2-Hydroxylphenyl Ketoxime)-~(63)Cu(Ⅱ) Complex

The ENDOR spectrum of ~(14)N-~(63)Cu-HAP complex in DMSO/EtOH (5:1) freezing solution at 20 K has been studied using orientational selective method in this paper. The anisotropic superhyperfine coupling tensor and qusdrupole coupling tensor of ligand ~(14)N nucleus, and the superhyperfine coupling tensor of various ~1H nuclei have been measured precisely. Comparing the superhyperfine coupling tensor of ~(14)N-nucleus with previous work shows that the analytical method of spectrum is reasonable and the data are reliable in our previous work.     

Catalysis of ring-opening and vinyl polymerizations by dicobaltoctacarbonyl

In the presence of Si? H containing cocatalysts, dicobaltoctacarbonyl has been found to very efficiently catalyze the ring-opening polymerization of cyclic ethers, especially epoxides, as well as certain vinyl monomers. The reaction conditions employed are very similar to those used in Co₂(CO)₈ catalyzed hydrogenation and hydrosilylation reactions. Detailed investigations have been carried out to elucidate the nature of the active species for this catalytic system. A cationic mechanism is proposed based on the experimental results of those investigations.     

Extraction and coordination studies of carbamoyl methyl sulfoxide (CMSO) with uranyl bis(β-diketonates). Synthesis and molecular structure of [{UO2(DBM)2}2C6H5CH2SOCH2CONHC6H5]

The carbamoyl methyl sulfoxide compounds of uranyl bis(β-diketonate) of the types [UO₂(DBM)₂CMSO] and [{UO₂(DBM)₂}₂CMSO] (where HDBM = C₆H₅COCH₂COC₆H₅; CMSO = C₆H₅CH₂SOCH₂CONHC₆H₅ or C₆H₅SOCH₂CONⁱPr₂) have been synthesized and characterized by IR and NMR spectroscopic techniques and elemental analysis. Spectral studies show that CMSO acts as a monodentate ligand in [UO₂(DBM)₂CMSO] compounds and bonds through the sulfoxo oxygen atom to the uranyl group. It acts as a bridging bidentate ligand in [{UO₂(DBM)₂}₂CMSO] compounds and bonds through both the sulfoxo and carbamoyl oxygen atoms to two different uranyl groups. The structure of the compound [{UO₂(DBM)₂}₂C₆H₅CH₂SOCH₂CONHC₆H₅] confirms the bridging bidentate mode of coordination for the CMSO ligand. Extraction studies show an enhancement in solvent extraction for the uranyl ion from nitric acid medium when a mixture of thenoyl trifluoroacetone (HTTA) and CMSO was employed.     

Synthesis of Cobalt Bis(Dicarbollide)—Curcumin Conjugates for Potential Use in Boron Neutron Capture Therapy

A series of novel cobalt bis(dicarbollide)—curcumin conjugates were synthesized. Two conjugates were obtained through the nucleophilic ring-opening reaction of the 1,4-dioxane and tetrahydropyran derivatives of cobalt bis(dicarbollide) with the OH group of curcumin, and using two equiv. of the oxonium derivatives, two other conjugates containing two cobalt bis(dicarbollide) units per molecule were obtained. In contrast to curcumin, the conjugates obtained were found to be non-cytotoxic against both tumor and normal cell lines. The analysis of the intracellular accumulation of the conjugates by flow cytometry showed that all cobalt bis(dicarbollide)—curcumin conjugates entered HCT116 colorectal carcinoma cells in a time-dependent manner. New non-cytotoxic conjugates contain a large amount of boron atoms in the biomolecule and can potentially be used for further biological research into boron neutron capture therapy (BNCT).     

甲醛还原 Ag(S0）3以沉析银的研究

本文在绘制出Ag-SO_3~(2-)-H_2O系电势—pH图,且对各种还原剂还原Ag(SO_3)_2~(3-)进行热力学分析的基础上,采用静态法测试了甲醛、联氨、连二亚硫酸钠、抗坏血酸及硼氢化钾与Ag(SO_3)_2~(3-)溶液等当量混合以还原沉析银的得率,获得甲醛是最有效的还原剂。通过正交试验,得知甲醛和Ag(SO_3)_2~(3-)等当量反应沉析银的最佳条件是:pH=12.00,T=35℃±0.2,Ag~+∶SO_3~(2-)=1∶4(摩尔比)。经综合试验获得银的还原沉析率在98.5％以上。     

Spectral,X-ray diffraction,surface morphological and thermal studies of gamma-irradiated potassium bis(oxalato)zincate(II)dihydrate

ABSTRACT

Potassium bis(oxalato)zincate(II)dihydrate was prepared and characterized. The sample was irradiated with ⁶⁰Co gamma rays up to 900?kGy. Infrared, Raman and photoluminescence spectra, X-ray diffraction pattern, surface morphology by AFM and SEM and non-isothermal decomposition of the complex were studied before and after irradiation. Spectral studies suggested significant radiation damage. X-ray diffraction studies showed reduction in unit cell volume and average crystallite size. Both unirradiated and irradiated samples of the complex belong to the hexagonal crystal system. Surface morphology of the complex changed upon irradiation. Thermal decomposition was enhanced.     

EPR and optical spectra of cupric ions doped in powder strontium maleate tetrahydrate and magnesium Bis (hydrogen maleate) hexahydrate

Abstract

EPR spectra of Cu²⁺ ions doped in a strontium maleate tetrahydrate and magnesium bis (hydrogen maleate) hexahydrate have been studied in X-band at room temperature and at liquid nitrogen temperature. Spin-Hamiltonian parameters have been calculated. Molecular orbital coefficients are obtained by correlating optical absorption data with EPR results.     

两种以Znq2为基体的新型电致发光材料的合成与性能

以8-羟基喹啉为配体的金属配合物是一种性能优良的有机电致发光材料,其中有关8-羟基喹啉铝(Alq₃)研究已有大量报道,8-羟基喹啉锌(Znq₂)研究还有待发展。介绍了两种以Znq₂为基体的新型有机电致发光材料Znq₂(H₂O)₂和(Znq₂)₄的合成方法。用IR、XRD、TG、DTA和荧光测试方法进行表征与分析表明:Znq₂(H₂O)₂和(Znq₂)₄的玻璃化温度(T_g)分别为104.2℃和204.9℃;在161℃下Znq₂(H₂O)₂脱去水分子成为Znq₂,在361℃高温下四聚体(Znq₂)₄裂解为单体Znq₂;Znq₂(H₂O)₂和(Znq₂)₄具有很好的发光性能,在光致发光谱中λ_max分别是505,550nm。