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.     

Electronic properties of model quantum-dot structures in zero and finite magnetic fields

We have computed electronic structures and total energies of circularly confined two-dimensional quantum dots and their lateral dimers in zero and finite uniform external magnetic fields using different theoretical schemes: the spin-density-functional theory (SDFT), the current-and-spin-density-functional theory (CSDFT), and the variational quantum Monte Carlo (VMC) method. The SDFT and CSDFT calculations employ a recently-developed, symmetry-unrestricted real-space algorithm allowing solutions which break the spin symmetry. Results obtained for a six-electron dot in the weak confinement limit and in zero magnetic field as well as in a moderate confinement and in finite magnetic fields enable us to draw conclusions about the reliability of the more approximative SDFT and CSDFT schemes in comparison with the VMC method. The same is true for results obtained for the two-electron quantum dot dimer as a function of inter-dot distance. The structure and role of the symmetry-breaking solutions appearing in the SDFT and CSDFT calculations for the above systems are discussed. Received 16 October 2001 and Received in final form 17 January 2002     

Barrier-free intermolecular proton transfer in the uracil-glycine complex induced by excess electron attachment

The photoelectron spectra (PES) of anions of uracil-glycine and uracil-phenylalanine complexes reveal broad features with maxima at 1.8 and 2.0 eV. The results of ab initio density functional B3LYP and second order M?ller-Plesset theory calculations indicate that the excess electron occupies a π^* orbital localized on uracil. The excess electron attachment to the complex can induce a barrier-free proton transfer (BFPT) from the carboxylic group of glycine to the O8 atom of uracil. As a result, the four most stable structures of the anion of uracil-glycine complex can be characterized as the neutral radical of hydrogenated uracil solvated by the anion of deprotonated glycine. The similarity between the PES spectra for the uracil complexes with glycine and phenylalanine suggests that the BFPT is also operative in the case of the latter anionic species. The BFPT to the O8 atom of uracil may be related to the damage of nucleic acid bases by low energy electrons because the O8 atom is involved in a hydrogen bond with adenine in the standard Watson-Crick pairing scheme. Received 6 April 2002 Published online 13 September 2002     

High temperature annealing effect on structural and magnetic properties of Ti/Ni multilayers

High temperature annealing effect on structural and magnetic properties of Ti/Ni multilayer (ML) up to 600 °C have been studied and reported in this paper. Ti/Ni multilayer samples having constant layer thicknesses of 50 Å each are deposited on float glass and Si(1 1 1) substrates using electron-beam evaporation technique under ultra-high vacuum (UHV) conditions at room temperatures. The micro-structural parameters and their evolution with temperature for as-deposited as well as annealed multilayer samples up to 600 °C in a step of 100 °C for 1 h are determined by using X-ray diffraction (XRD) and grazing incidence X-ray reflectivity techniques. The X-ray diffraction pattern recorded at 300 °C annealed multilayer sample shows interesting structural transformation (from crystalline to amorphous) because of the solid-state reaction (SSR) and subsequent re-crystallization at higher temperatures of annealing, particularly at ≥400 °C due to the formation of TiNi₃ and Ti₂Ni alloy phases. Sample quality and surface morphology are examined by using atomic force microscopy (AFM) technique for both as-deposited as well as annealed multilayer samples. In addition to this, a temperature dependent dc resistivity measurement is also used to study the structural transformation and subsequent alloy phase formation due to annealing treatment. The corresponding magnetization behavior of multilayer samples after each stage of annealing has been investigated by using Magneto-Optical Kerr Effect (MOKE) technique and results are interpreted in terms of observed micro-structural changes.     

Quadrupole interactions at 57Fe and 119Sn in 3d-metal antimonides

3d-metal antimonides: Fe_1+x Sb, N_+x Sb, Co_+x Sb and the (Ni_1?y Fe _y )Sb solid solution have been studied by the Mössbauer effect method at ⁵⁷Fe and ¹¹⁹Sn. It was found that the quadrupole interactions at the Fe and Sn nucleus in 3d-metal antimonides are very sensitive to the filling of different crystallographic sites with metal atoms. The metal atoms in trigonal-bipyramidal sites have a strong effect on the quadrupole splitting of ¹¹⁹Sn. They are nearest to anions (Sb or Sn) with the typical axial ratio of c/a = 1.25. The QS(x) dependence of ¹¹⁹ Sn in 3d-metal antimonides in the 0 ≤ x ≤ 0.1 concentration range can be used to determine x – the concentration of transition metal excess relative to the stoichiometric composition.     

Natural vibrations of a strip made of a composite material with a locally curved structure

The possibility of using the finite-element method for investigating two-dimensional problems on natural vibrations in the mechanics of composite materials with curved structures is considered. With the example of a hinge-supported strip made of a composite material with a locally curved structure, the influence of geometrical and mechanical parameters of the strip on its eigenfrequencies is examined. It is established that the presence of local curving in the structure of strip material decreases the magnitude of eigenfrequencies.Translated from Mekhanika Kompozitnykh Materialov, Vol. 41, No. 1, pp. 71–78, January–February, 2005.     

Dynamic mechanical thermal analysis transitions of partially and fully substituted cellulose fatty esters

The main transitions of cellulose fatty esters with different degrees of substitution (DSs) were investigated with dynamic mechanical thermal analysis. Two distinct main relaxations were observed in partially substituted cellulose esters (PSCEs). They were attributed to the glass‐transition temperature and to the chain local motion of the aliphatic substituents. The temperatures of both transitions decreased when DS or the number of carbon atoms (n) of the acyl substituent increased. Conversely, all the transitions of fully substituted cellulose esters occurred within a narrow temperature range, and they did not vary significantly with n. This phenomenon was explained by the formation of a crystalline phase of the fatty substituents. The presence of few residual OH groups in PSCEs was responsible for a large increase in the storage bending modulus, and it eliminated the effect of n on damping. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 281–288, 2003     

Charge density study under high pressure

The experimental and analytical method of the high-pressure powder experiment at BL10XU, SPring-8, is described. There is no doubt that BL10XU must be one of the most appropriate beam lines for high pressure X-ray diffraction experiment taking advantage of third generation synchrotron source. As an example of the advanced charge density study under high pressure, the structural change of Cs₂Au₂Br₆ by applying pressure is studied by Rietveld/MEM analysis. It reveals that the structural change of Cs₂Au₂Br₆ by applying pressure occurs basically at electron level, such as valence state change and chemical bonding, which may be called the electronic phase transition.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶 凝胶法以磷钼酸 (MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2 催化剂 .使用ICP、XRD、TG DTA、IR、TPD MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能 .杂多钼酸盐与TiO2 通过O2 -在TiO2 表面发生了键合 .在 6 2 3K下 ,杂多阴离子仍保持原有的Keggin结构 .CO2 在Lewis酸位Ni(Ⅱ )和Lewis碱位Ni-O -Mo的桥氧协同作用下生成CO2 卧式吸附态Ni(Ⅱ )←O - (CO)← (O--Ni) .丙烯有多种吸附态在催化剂上吸附 .在 5 6 3K、1MPa和空速 15 0 0h-1的反应条件下 ,丙烯的摩尔转化率为 3.2 % ,产物MAA选择性为 95 % .