Darstellung und NMR-spektroskopische charakterisierung einiger di-n-alkyl- und n-alkylaryl-chlorphosphane

A series of di-n-alkyl and n-alkylaryl chlorophosphines has been prepared by the reaction of tetraorganodiphosphines with chlorodiphenyl or dichlorophenyl phosphine and characterized by ³¹P and ¹³C NMR spectra.     

Trifluoromethyl and mixed hydrido trifluoromethyl complexes of iridium(III) as potential precursors of an iridium(I) trifluoromethyl complex

Abstraction of iodide from Ir(CF₃)ClI(CO)(PPh₃)₂ (1) by AgSbF₆ in the presence of acetonitrile yields the cationic complex [Ir(CF₃)Cl(MeCN)(CO)(PPh₃)₂]⁺ [SbF₆]⁻ (2). The acetonitrile group of 2 is readily displaced, and 2 reacts with para-tolyl isocyanide to yield [Ir(CF₃)Cl(CN-p-tolyl)(CO)(PPh₃)₂]⁺ [SbF₆]⁻ (3). The addition of NaOMe to 3 results in the methoxyester complex Ir(CF₃)(COOMe)Cl(CN-p-tolyl) (PPh₃)₂ (4). The acetonitrile ligand of 2 is also displaced by anions, including H⁻. Thus, 2 reacts with LiEt₃BH to give Ir(CF₃)HCl(CO)(PPh₃)₂ (5), in which the hydrido and trifluoromethyl ligands are mutually trans. In contrast, the addition of excess NaBH₄ to 2 affords the novel dihydrido complex trans-Ir(CF3)H₂(CO)(PPh₃)₂ (6). Investigations into the potential use of 5 and 6 as precursors of an iridium(I) complex such as Ir(CF₃)(CO)(PPh₃)₂ are also described.     

导电聚苯胺线膜修饰ZnO纳米棒阵列的可控制备及其紫外探测性能

基于p-n结的光生伏特效应可构筑性能优异的UV探测器,本文采用水热法可控制备竖直排列的氧化锌纳米棒阵列(n型ZnO-NRs),利用原位聚合法在ZnO-NRs表面上修饰p型聚苯胺线膜(PANI-NWs),再组装成ZnO-NRs与ZnO-NRs/PANI-NWs紫外探测器.通过扫描电镜(SEM)、X射线衍射仪(XRD)、紫...     

Thermal analysis for generating phase diagrams of systems alkali metal chloride/divalent metal chloride

After a historical survey of the application of differential thermal analysis (DTA) for the generation of phase diagrams, particularly those of pseudobinary halide systems, the authors' research work on the systems ACl/MCl₂ (A = NaCs) is reported. In addition to DTA measurements the thermodynamic properties of the ternary compounds A_nMCl_n+2 are investigated by solution calorimetry and EMF measurements dependent on temperature with a newly developed galvanic cell for solid electrolytes. This method is also a useful tool for elucidating phase diagrams, especially for reactions occurring in the solid state.     

On the curie temperature of an anisotropic Heisenberg-Ising ferromagnet with crystal-field anisotropy

The effect of crystal-field anisotropy on the Curie temperature is studied in an S = 1 anisotropic Heisenberg-Ising ferromagnet. The Green function technique with a Callen-type approximation is used. The results show that, when the correlations between spins of nearest neighbouring sites are taken into account, the change in the Curie temperature with crystal-field anisotropy is not so great as that calculated in the random phase approximation.     

The effect of bending vibrations on the dipole moment of a linear polyatomic molecule: A theoretical treatment of the vibrational changes and transition moments

The vibrational effect on the dipole moment of a linear molecule is theoretically considered from the aspects of the dipole moment changes with the excitation of bending vibrations and the transition moments for the overtone, combination, and difference bands associated with bending modes. Such dipole moment changes and transition moments consist of two components, one depending on the first dipole moment derivatives with respect to bond lengths and the other depending on the second dipole moment derivatives with respect to bond angles. We show that the first component normally contributes little, and propose an approximation in which only the second component is retained. This approximation is practically important because the second component can be calculated without the anharmonic force constants. We derive formulas for the dipole moment changes and transition moments to facilitate a simultaneous analysis of different isotopic species. We introduce the concept of the equivalent mode, by which we may readily understand the correlation between the dipole moment change for a bending mode and the transition moment for a vibrational band.     

Fermi resonance - the theory of isotropic and anisotropic Raman spectra in dilute solutions

Raman scattering from dilute solution was studied limiting considerations to one active molecule, in which the Fermi resonance occurs, interacting with the molecules of an inert solvent. For such a system, the isotropic and anisotropic correlation functions ⧸CFs⧸ for symmetric top molecule have been calculated and examples of Fermi resonance spectra ⧸FRS⧸ are presented.     

Correlations entre defauts ponctuels et proprietes de transport dans PbF2 dope

The investigation of the transport properties of the Pb_1−xM²⁺ⁿ_xF_2+nx(n = 1,2) solid solutions shows a maximum of the activation energy ΔE_max associated to a minimum of the conductivity for a very small value of x : x_min. (x_min. ≅ 0.01 for n = 1; x_,in ≅ 0.005 for n = 2). The value of ΔE_max. depends closely on the nature of the substituting cation. Correlations have been established between the transport properties and the nature of the point defects which are supposed to occur in the considered composition range (nn or innn pairs) by analogy with similar alkali-earth fluorides. The size difference Δr between host and substitutional cations seems to play an essential role. The evolution of ΔE_max. and the preferential stability of the nn or nnn pairs is discussed as a function of Δr.     

DNA Interaction,DNA Photocleavage,Photocytotoxicity In Vitro,and Molecular Docking of Naphthyl-Appended Ruthenium Complexes

With the development of metal-based drugs, Ru(II) compounds present potential applications of PDT (photodynamic therapy) and anticancer reagents. We herein synthesized two naphthyl-appended ruthenium complexes by the combination of the ligand with naphthyl and bipyridyl. The DNA affinities, photocleavage abilities, and photocytotoxicity were studied by various spectral methods, viscosity measurement, theoretical computation method, gel electrophoresis, and MTT method. Two complexes exhibited strong interaction with calf thymus DNA by intercalation. Production of singlet oxygen (¹O₂) led to obvious DNA photocleavage activities of two complexes under 365 nm light. Furthermore, two complexes displayed obvious photocytotoxicity and low dark cytotoxicity towards Hela, A549, and A375 cells.     

Taxonomy approach to a cabinet formation problem

In this paper the problem of choosing a winning coalition in simple (voting) games is considered. It is assumed that voters (players) have different numbers of votes and definite preferences describing their willingness to enter into a coalition with other players. A function describing the willingness (preferation degree) of a given player to unite with each possible coalition is presented. Then, the method of an econometric template as a base for choosing the winning coalition most acceptable to all players is proposed as well as taxonomy approach leading to an order over all winning coalitions with regard to all players. An application of the proposed method is given by an example of the 1972 Italian Assembly. We obtain results in close agreement with reality.