Efficient palladium(II) catalysis under air. Base-free oxidative heck reactions at room temperature or with microwave heating

Scope and limitations of the base-free oxidative Heck reaction with arylboronic acids have been explored. Under our conditions, the dmphen-palladium(II)-catalyzed arylation proceeded with air or p-benzoquinone as reoxidants of palladium(0). We found that ambient temperature and mild aerobic conditions allow for the use of substrates sensitive to palladium(II)-catalyzed oxidation. Oxidative Heck couplings, employing different arylboronic acids, were smoothly and regioselectively conducted with both electron-rich and electron-poor olefins, providing high yields even with disubstituted butyl methacrylate, sensitive acrolein, and a vinylboronate ester. Controlled microwave processing was used to reduce reaction times from hours to minutes both in small scale and in 50 mmol scale batch processes.     

Super fast cobalt carbonyl-mediated synthesis of ureas

Fast cobalt carbonyl-mediated generation of ureas from primary amines was performed using high-density microwave irradiation. This enhanced method permitted the preparation of symmetrical ureas in good yields and unsymmetrical ureas in moderate yields. The reaction times varied between 10 s and 40 min. The proposed mechanism for the reaction includes in situ generation of an intermediate isocyanate that subsequently traps the free amine, producing the urea product.     

Self-sustained kinetic oscillations in CO oxidation over silica-supported Pt

Isothermal self-sustained kinetic oscillations in CO oxidation over silica-supported Pt at near-atmospheric pressure were studied by combined in situ Fourier transform infrared spectroscopy and mass spectrometry. The use of a specially designed reactor and careful choice of the physical properties of the catalyst and reaction conditions made it possible to eliminate diffusion limitations, to determine the maximum CO oxidation rate per Pt site in the purely kinetic regime and to clarify the mechanism of the oscillations. Specifically, our results indicate that during the high reactive periods the reaction mainly occurs on the oxide surface.     

Atomic layer deposition of organic-inorganic hybrid materials based on saturated linear carboxylic acids

Atomic layer deposition (ALD) has successfully provided thin films of organic-inorganic hybrid materials based on saturated linear carboxylic acids and trimethylaluminium (TMA). Films were grown for seven carboxylic acids: oxalic, malonic, succinic, glutaric, pimelic, suberic and sebacic acid, i.e. ranging from 2 to 10 carbon atoms in the molecular structure. These processes show exceptionally high growth rates; up to 4.3 nm/cycle for the pimelic acid-TMA system. Quartz crystal microbalance measurements of the growth dynamics indicate that all systems are of a self limiting ALD-type. Nevertheless, temperature dependent growth was observed in several systems. The width of the ALD windows shows correlations with the length of the carbon chains. Fourier transform infrared spectroscopy clearly proved that the deposited films are of a hybrid character, where the carboxylic acids primarily form bidentate complexes, though bridging complexes may also form. All films are X-ray amorphous as deposited. The films were further analyzed by atomic force microscopy for surface roughness and topography, UV-Vis spectroscopy and ellipsometry for optical properties, and the goniometer method for measuring sessile drops for surface wetting properties. Apart from the oxalic and malonic acid-TMA systems, the films are stable in contact with water. The films are generally smooth, transparent and have a refractive index close to 1.5. The complete coverage and accurate growth control offered by the ALD technique is here proven to provide surface-functionalized hybrid materials resembling metal-organic frameworks (MOF), probably as rather dense structures, yet with substantial potential for applications.     

Pentavalent and tetravalent uranium selenides, Tl3Cu4USe6 and Tl2Ag2USe4: syntheses, characterization, and structural comparison to other layered actinide chalcogenide compounds

The compounds Tl(3)Cu(4)USe(6) and Tl(2)Ag(2)USe(4) were synthesized by the reaction of the elements in excess TlCl at 1123 K. Both compounds crystallize in new structure types, in space groups P2(1)/c and C2/m, respectively, of the monoclinic system. Each compound contains layers of USe(6) octahedra and MSe(4) (M = Cu, Ag) tetrahedra, separated by Tl(+) cations. The packing of the octahedra and the tetrahedra within the layers is compared to the packing arrangements found in other layered actinide chalcogenides. Tl(3)Cu(4)USe(6) displays peaks in its magnetic susceptibility at 5 and 70 K. It exhibits modified Curie-Weiss paramagnetic behavior with an effective magnetic moment of 1.58(1) μ(B) in the temperature range 72-300 K, whereas Tl(2)Ag(2)USe(4) exhibits modified Curie-Weiss paramagnetic behavior with μ(eff) = 3.4(1) μ(B) in the temperature range 100-300 K. X-ray absorption near-edge structure (XANES) results from scanning transmission X-ray spectromicroscopy confirm that Tl(3)Cu(4)USe(6) has Se bonding characteristic of discrete Se(2-) units, Cu bonding generally representative of Cu(+), and U bonding consistent with a U(4+) or U(5+) species. On the basis of these measurements, as well as bonding arguments, the formal oxidation states for U may be assigned as +5 in Tl(3)Cu(4)USe(6) and +4 in Tl(2)Ag(2)USe(4).     

Quantized electron accumulation states in indium nitride studied by angle-resolved photoemission spectroscopy

Electron accumulation states in InN have been measured using high resolution angle-resolved photoemission spectroscopy (ARPES). The electrons in the accumulation layer have been discovered to reside in quantum well states. ARPES was also used to measure the Fermi surface of these quantum well states, as well as their constant binding energy contours below the Fermi level E(F). The energy of the Fermi level and the size of the Fermi surface for these quantum well states could be controlled by varying the method of surface preparation. This is the first unambiguous observation that electrons in the InN accumulation layer are quantized and the first time the Fermi surface associated with such states has been measured.     

Unoccupied electronic states in graphite oxides

Unoccupied electronic states of graphite oxides with different oxidation times have been investigated using X-ray absorption spectroscopy (XAS) in total electron yield (TEY) and total fluorescence yield (TFY) modes. The graphite oxides exhibit graphite-like sp² states with additional electronic states originating from functional groups. The intensity of the π^* state decreases as the atomic ratio O:C increases. The intensity ratio of carboxyl to π^* states in XAS TEY mode corresponds to the area ratio of carboxyl to sp² carbon in X-ray photoelectron spectroscopy. In addition, the two modes in XAS can identify electronic states of functional groups originating from surface or bulk regions.     

On the number of equivalence classes of attracting dynamical systems

We study discrete dynamical systems of the kind h(x) = x + g(x), where g(x) is amonic irreducible polynomial with coefficients in the ring of integers of a p-adic field K. The dynamical systems of this kind, having attracting fixed points, can in a natural way be divided into equivalence classes, and we investigate whether something can be said about the number of those equivalence classes, for a certain degree of the polynomial g(x). The text was submitted by the authors in English.     

Regularitätsuntersuchungen von Lösungen Elliptischer Systeme von Quasilinearen Differentialgleichungen Zweiter Ordnung

Solutions of general, uniformly elliptic systems of quasilinear second order partial differential equations in divergence form are studied under the assumption that the right hand side of the system grows at most quadratically with respect to the gradient of the solution. A partial regularity result is obtained, asserting that in the general case, any weak solution with sufficiently small modulus (an explicit bound is given) has hölder continuous first order derivatives in a neighbourhood of almost every point of the domain of definition. For diagonal systems where the coefficients depend on the modulus, but in no other way, of the gradient of the unknown function, it is shown that regularity in fact holds throughout the domain.     

X-ray spectroscopic study of the electronic structure of visible-light responsive N-, C- and S-doped TiO2

The electronic origins of the visible-light response of N-, C- and S-doped TiO₂ have been studied using X-ray absorption, X-ray emission, and X-ray photoelectron spectroscopies. New electronic states are observed in the bulk band gap, above the valence band edge of pure TiO₂, which can be directly related to the visible-light absorption of the N-, C- and S-doped TiO₂ materials.