Application of N,N‐bis(diphenylphosphino)aniline palladium(II) complexes as pre‐catalysts in Heck coupling reactions

Palladium(II) complexes with N,N‐bis(diphenylphosphino)aniline ligands catalyse the Heck reaction between styrene and aryl bromides, affording stilbenes in good yield. The structures of two of the complexes used as pre‐catalysts have been determined by single‐crystal X‐ray diffraction. Copyright © 2007 John Wiley & Sons, Ltd.     

Regiospecifically controlled formation of tetrasubstituted tributyltin ketone enolates catalyzed by a palladium complex

The palladium-catalyzed hydrostannolysis of α-disubstituted allyl β-keto esters yields the corresponding tributyltin β-keto carboxylates which loose carbon dioxide at very moderate temperature, thus leading to the regiospecific formation of tributyltin tetrasubstituted enolates.     

The algorithm of substructure recognition in organic compounds by the artificial intelligence method on the basis of IR-spectra

An algorithm for identification of the IR-active substructures has been developed. In the algorithm, which recognizes about 100 substructures, the analysis is based on three parameters for a set of characteristic bands: position, intensity and arbitrarily chosen diagnostics. The algorithm provides two ways of identification: a. standard method, which compares an IR spectrum with the correlation tables contained in the algorithm, b. dynamic method advanced here which consists in that the recognized substructures cause blocking of their characteristic bands making them almost inaccessible for further analysis.     

Stereospecific total synthesis of (±)-strempeliopine

The 18-methylene-1,2-dehydroaspidospermidine (III) was stereospecifically transformed into the schizozygane alkaloid strempeliopine (II) in 16,6 % overall yield.     

Gas chromatographic method for the determination of N-acetyl-S-(N-methylcarbamoyl)cysteine, a metabolite of N,N-dimethylformamide and N-methylformamide, in human urine

A simple method has been developed for the determination of N-acetyl-S-(N-methylcarbamoyl)cysteine in human urine. Treatment of a urine sample (1 ml) with ethanol (2 ml) and potassium carbonate (1.5 g) produces ethyl N-methylcarbamate, which is extracted into ethanol and measured by packed column gas chromatography with nitrogen-sensitive detection. The limit of quantitation in human urine is 1 microgram/ml and the between-sample coefficient of variation is 5-11%. Simultaneously, N,N-dimethylformamide, N-methylformamide and formamide can also be determined.     

Calorimetric study of the glassy state XII. Plural glass-transition phenomena of ethanol

Ethanol was found to give a metastable crystalline phase (crystal-II) when the liquid was cooled at a moderate rate. Glassy states of liquid and of newly found crystal-II were obtained in the calorimeter cell by controlling the cooling rate of the liquid. The heat capacities of these phases as well as that of the stable crystal-I were measured by an adiabatic calorimeter in the temperature range between 14 and 300 K. The glass transition temperature T_g, the heat-capacity jump at T_g, and the residual entropy were found to be 97 K, 35.3 J K^?1 mol^?1, and 8.93 J K^?1 mol^?1 for the glassy liquid, and 97 K, 22.8 J K^?1 mol^?1, and 4.24 J K^?1 mol^?1 for the glassy crystal-II, respectively. The values for the residual entropy are referred to the third-law entropy for crystal-I.The heat capacities reported previously for the supercooled liquid by Gibson et al. and by Parks and Kelley agree well with those for the metastable crystal-II. Those of the supercooled liquid connect smoothly with those obtained for the liquid above the melting temperature. Thus, ethanol is found to be another example of a low-molecular-weight compound which shows multiple glass-transition phenomena.     

Azocalixarenes: Synthesis, Characterization, Complexation, Extraction, Absorption Properties and Thermal Behaviours

Azocalixarenes, which have a conjugated chromophore azo (–N=N–) group in p-positions, are synthesized in “one-pot” procedures in satisfactory yields. Their structures in the solid and solution are elucidated by UV–vis, FT-IR, ¹H and ¹³C NMR spectroscopic methods as well as elemental analysis techniques. Some of them are complexed with metal ions (alkali, alkaline-earth and transition metal ions) under neutral conditions. A wide variety of applications is expected by the functionalization of the side arms. The selective liquid–liquid extraction of various alkali, alkaline-earth and transition metal cations from the aqueous phase to the organic phase is carried out by using azocalixarenes. Furthermore, the synthesized azocalixarenes are utilized for selective extraction of Fe³⁺ cations from the aqueous phase to the organic phase. The effects of varying pH and solvent upon the absorption ability of azocalixarenes substituted with electron-donating and electron-withdrawing groups at their o-, m-, p-positions are examined. The thermal behaviours of azocalixarenes containing upper rim functionalized groups are investigated by means of thermogravimetry (TG), differential thermal analysis (DTA) and differential thermogravimetry (DTG).     

Photoelectrochemical Properties of Annealed Anodic TiO2 Layers Covered with CuOx

In this work, we present a systematic study on the influence of Cu²⁺ ion concentration in the impregnation solution on the morphology, structure, optical, semiconducting, and photoelectrochemical properties of anodic CuO_x-TiO₂ materials. Studied materials were prepared by immersion in solutions with different concentrations of (CH₃COO)₂Cu and subjected to air-annealing at 400 °C, 500 °C, or 600 °C for 2 h. The complex characterization of all studied samples was performed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), reflectance measurements, Mott–Schottky analyses, and photocurrent measurements. It was found that band gap engineering based on coupling CuO with TiO₂ (E_g~3.3 eV) is an effective strategy to increase the absorption in visible light due to band gap narrowing (CuO_x-TiO₂ materials had E_g~2.4 eV). Although the photoactivity of CuO-TiO₂ materials decreased in the UV range due to the deposition of CuO on the TiO₂ surface, in the Vis range increased up to 600 nm at the same time.     

Thermodynamic investigation on glassy states of pure simple compounds

The present review deals primarily with glass transition phenomena in pure simple compounds and pays special attention to the thermodynamic aspects of the vitrification process. The concept of glassy state is extended to liquid crystalline and even to crystalline materials which have any type of disorder. Thus the familiar supercooled liquid-glass transition is shown to be just one example of a class of ‘glass transitions’ due to loss of equilibrium which must occur quite frequently in condensed matter. Evidence of several glass transition phenomena in one and the same compound is given. The fact that glass should be considered as one of the states of aggregation of matter, irrespective of either the method of formation or the existence of three-dimensional periodicity in molecular arrangements, is stressed.     

10MW串级脉冲发电机的理论、设计、实验及应用研究

 脉冲发电机具有小型、机动、灵活、可靠、寿命长等特点, 作为高功率固体激光器和加速器电源是一新的技术路线。比较了各种类型脉冲电源的性能指标,解释了旋转磁通压缩和串级原理,提出串级脉冲发电机的自激、偏极与双机同壳概念,给出电机的设计公式,10MW串级脉冲发电机的设计、实验及在强激光与粒子束领域中的潜在应用。