Hybrid polymerization of iso-butyl vinyl ether

The radiation-induced hybrid polymerization in the presence of the N-alkoxypyridinium salt having relatively stable nonnucleophilic anion (PF₆⁻) has been investigated in the paper. Based on the analysis of experimental data and the GPC spectrum, the onium salts not only oxidize -alkoxyalkyl radicals, produced from IBVE in dichloromethane by irradiation, to the corresponding cations, but also give nonnucleophilic anions PF₆⁻ for the polymerization system. The experimental results clearly demonstrate that free radical and cationic polymerization mechanisms occurred simultaneously in IBVE/EMP⁺PF₆⁻/CH₂Cl₂ systems on irradiation with γ-ray.     

Redox thermochemistry of SrFe1-xCoxO3-d

The enthalpy of oxidation of SrFe_1-xCo_xO_3-d with x=0.33 and 0.67 has been determined by adiabatic calorimetry; average values for x=0.33 and 0.67 are -67±11 and -49.5±9 kJ (mol O₂)^-1. These data and the previously reported value for SrFeO_3-d suggest that the enthalpy of oxidation for pure (perovskite-type) SrCoO_3-d is close to zero. Earlier reported composition - partial pressure data for SrFe_0.67Co_0.33O_3-d are reproduced when preferential oxidation of iron is assumed for low partial pressures of oxygen. This revised version was published online in August 2006 with corrections to the Cover Date.     

Fast Marching Method for Calculating Reactive Trajectories for Chemical Reactions

We present a method for computing classical Newtonian trajectories that minimize the path length or transit time from reactant to product. Our approach is based on a generalization of the fast-marching method, which allows us to construct the solution of the Hamilton-Jacobi equation for the action that optimizes the desired quantity. The resulting “reactive paths” can be interpreted as reaction coordinates but, unlike more conventional choices, they contain dynamical information about the chemical system of interest.     

Immobilization of copper in organic-inorganic hybrid materials: a highly efficient and reusable catalyst for the Ullmann diaryl etherification

The immobilization of copper in organic-inorganic hybrid materials catalyzing the Ullmann reaction has been described. Phenols reacted with aryl iodides, aryl bromides and aryl chlorides smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper catalyst. The protocol involved the use of DMSO as the solvent, and potassium fluoride as the base. The reactions generated the corresponding cross-coupling products in good to excellent yields. Furthermore, the silica-supported copper could be recovered and recycled by a simple filtration of the reaction solution and used for 10 consecutive trials without loss of its reactivity.     

New aspects of thermal analysis,Part I. Resolution of DSC and means for its optimization

The definitions of the temperature resolution, the so-called resolution of DSC instruments given in literature are discussed. A new definition of the resolution for DSC instruments is presented and outlined. The main characteristic introduced in this new definition is a minimum between two caloric events as a prerequisite of an existing resolution. Possible candidates of test substances have been evaluated. The oligomer n-hexatriacontane is revealing an interesting phenomenon, namely a lambda transition which is in the peak temperature only 2 K lower than the melting temperature of 76°C. The substance was selected as an ideal test substance for the quantification of the resolution of DSC instruments. The lambda transition is a second order process which may reach under certain conditions the saturation of the occurring molecular dislocation within 0.2 K, and after saturation the heat flow rate drops sharply down. Investigations concerning the main characteristics of n-hexatriacontane in respect to the temperatures of transition (lambda transition and melting), to the involved enthalpies, and to the resolution factors were performed as functions of the sample mass and the heating rate. The importance of relevant evaluation procedures increasing the resolution factors of DSC curves are discussed and these procedures are integrated into the testing of the resolution. The necessity for widening the experimental scope from instruments to evaluation procedures is forced by the existence of instruments with built-in signal treatments based on electronic devices and software procedures. A comparison with literature data is outlined for all of the mentioned characteristic values of n-hexatriacontane. This revised version was published online in August 2006 with corrections to the Cover Date.     

Catalytic combustion of chlorobenzene over V2O5/TiO2 catalysts prepared by the precipitation-deposition method

Catalytic combustion of chlorobenzene over supported vanadium oxides has been investigated. TiO₂ was prepared by the sol-gel method from titanium isopropoxide. The supported vanadium oxide catalysts have been prepared by precipitation-deposition and impregnation method and characterized by XRD, FT-Raman and TPR. In the VO_x/TiO₂catalysts prepared using the impregnation method, when vanadium loading reaches 3 wt.%, the activity shows a maximum. However, in the VO_x/TiO₂catalysts prepared by precipitation-deposition, when vanadium loading reaches 7 wt.%, the activity shows a maximum. This result suggests that the precipitation-deposition can yield a higher metal loading on the support and a high dispersion compared to the impregnation method. This revised version was published online in August 2006 with corrections to the Cover Date.     

Electroreduction of Pd(II) Complexes with α-Alanine on a Palladium Electrode

The kinetics of electroreduction of Pd(II) complexes with -alanine, Pd(ala)₂, is studied on a rotating Pd disk electrode in solutions of pH 8–13 containing large excess of -alanine and various supporting electrolytes (NaF, Na₂SO₄, NaClO₄). On a Pd electrode, complexes Pd(ala)₂ undergo reduction at potentials much more negative than on an Hg electrode. This is attributed to the chemisorption of water on the Pd electrode, which hampers adsorption of Pd(ala)₂ that take part in the slow electrochemical stage. As with the Hg electrode, perchlorate ions hinder the Pd(ala)₂ reduction on a Pd electrode. Studying adsorption of Pd(ala)₂ on a Pd electrode is hampered by parallel processes of hydrogen adsorption and absorption.     

新型双核铜配合物的合成,表征及其对苯乙烯环氧化的催化作用

设计合成了５种新型双核铜配合物，用ＥＡ，ＩＲ，ＵＶ－Ｖｉｓ，ＸＰＳ，ＥＰＲ等进行了结构表征，并研究了这些Ｃｕ２配合物模拟双核铜单加氧酶多巴胺β－羟化酶催化苯乙烯环氧化反应的特征。结果表明，这些配合物具有两种类型的结构：脱质子型Ｃｕ２ＬＯＨ和非脱质子型「（Ｃｕ２Ｈ２ＬＸ）Ｙ」Ｙ（Ｘ＝Ｙ＝Ｃｌ＾１－，Ｂｒ＾－；Ｘ＝ＯＨ，Ｙ＝Ｏ２ＣｌＯ＾－２），两类配合物可相互转化。非脱质子型配合物催化ＰｈＩＯ对苯乙烯     

Rigid aromatic fractal polyamides

The preparation of rigid aromatic, highly branched polyamides is described. Owing to the method of preparation and the chosen ratio of difunctional to trifunctional monomers, these entities are highly porous and not dendrimeric in nature. They better conform with the fractal model and are therefore called fractal polyamides (FPs). The effects of variations in the polymerization procedure, in total monomer concentration, in the ratio of amine to carboxyl groups and in the duration of the polycondensation reaction are investigated. Some characterization was performed and the results are presented and briefly discussed.     

The diamagnetic Kepler problem

It has turned out that the analysis ofclassical periodic orbits is the key to understanding the modulations in thequantal spectra of hydrogen Rydberg atoms in magnetic fields. Inspired by this quantum chaological connection, we analyse some fundamental periodic orbits of the diamagnetic Kepler problem, abandoning the condition of vanishing azimuthal angular momentuml _z used in the literature so far. We report the bifurcation and confluence schemes of the orbits in their dependence onl _z and discuss the structural changes in terms of catastrophe theory.