Preparation of Copolymerized Phenylsilsesquioxane-Benzylsilsesquioxane Particles

Copolymerized phenylsilsesquioxane-benzylsilsesquioxane particles were prepared from their corresponding organotriethoxysilanes by the sol-gel method. Transparent thick films of a few microns in thickness have been successfully prepared on glass substrates coated with indium tin oxide (ITO) by heat-treating the copolymerized particles which had been electrophoretically deposited on the substrates. The on-set temperature for thermal sintering of the copolymerized particles decreased from 150 to 50°C with increasing the benzylsilsesquioxane content. These on-set temperatures for thermal sintering of the particles were found to be higher by 10 to 50°C than the glass transition temperatures of the particles of the corresponding composition. The thermal sintering of the particles should occur due to a large decrease in viscosity of the particles at temperatures higher than the glass transition temperatures. The decrease in the on-set temperature with composition for thermal sintering as well as in the glass transition temperature of the particles can be related with the decreases in average molecular weight and in distribution of the molecular weight of the particles with an increase in the benzylsilsesquioxane content.     

(Pi-allyl)palladium complexes bearing diphosphinidenecyclobutene ligands (DPCB): highly active catalysts for direct conversion of allylic alcohols

The (pi-allyl)palladium complex bearing an sp2-hybridized phosphorus ligand (DPCB-OMe: 1,2-bis(4-methoxyphenyl)-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene) efficiently catalyzes direct conversion of allylic alcohols in the absence of activating agents of alcohols such as Lewis acids. N-Allylation of aniline proceeds at room temperature to afford monoallylated anilines in 90-97% yields. C-Allylation of active methylene compounds is also successful at 50 degrees C using a catalytic amount of pyridine as a base, giving monoallylation products in 85-95% yields. The catalytic mechanism involving hydrido- and (pi-allyl)palladium intermediates has been proposed on the basis of stoichiometric examinations using model compounds of presumed intermediates.     

Relativistic Gaussian basis sets for radon through plutonium

Summary Relativistic Gaussian basis sets of neutral atoms Rn-Pu and ions Th⁺⁴, U⁺³ and Pu⁺³ in the configurations of average energies are presented. The exponent parameters of the basis sets are determined by least-squares fitting to the numerical Dirac-Fock wave functions. The total energies obtained are within 0.155 a.u. of the Dirac-Fock limits and the qualities of the basis sets are between double-zeta and triple-zeta in the valence parts. Using the exponent parameters the Breit interaction energies have been calculated by perturbation theory and the self-consistent field treatment.     

Novel synthesis of polymeric phase transfer catalyst containing polar unit

Soluble polymeric phase transfer catalysts (PTCs) containing benzyltributylphosphonium chloride moieties and p-nitrophenoxy group or N,N-dimethylacrylamide as a polar unit were prepared via two-step reactions from polymers with chloromethyl group and polar units. These polymers were synthesized by copolymerization of p-chloromethylstyrene and the corresponding monomer or substitution of some parts of chloromethyl group with potassium p-nitrophenoxide. When the obtained polymers were added, the phase transfer catalyzed reaction of benzylchloride with solid potassium acetate to proceed smoothly. The catalytic activity was strongly affected by the content of phosphonium chloride and the varieties of comonomer unit in the polymeric PTC. The polymeric PTC containing N,N-dimethylacrylamide unit showed much higher catalytic activity than the corresponding low molecular weight PTC when the phase transfer catalyzed reaction was carried out in low polar solvent. © 1994 John Wiley & Sons, Inc.     

Effects of UV-irradiation on the formation of oxide thin films from chemically modified metal-alkoxides

The effects of UV-irradiation on the properties of ZrO₂ and TiO₂ gel films prepared from corresponding metal-butoxides modified with acetylacetone (AcAc) or benzoylacetone (BzAc) have been studied. It was found that the chelate bonds of -diketones remaining in the gel films were dissociated by the UV-irradiation. The UV-irradiation also changed the properties of the gel films such as solubility; the solubility in acidic solutions was decreased for ZrO₂ gel films modified with AcAc and TiO₂ gel films modified with BzAc became insoluble in alcohol. Based on these findings, a new fine-patterning process has been established, which enables us to make fine-patterns of ZrO₂ and TiO₂ films on a variety of substrates.     

Local fluctuation of the spectrum of a multidimensional Anderson tight binding model

We consider the Anderson tight binding modelH=–+V acting inl ²(Z ^d ) and its restrictionH to finite hypercubes Z ^d . HereV={V _x ;xZ ^d } is a random potential consisting of independent identically distributed random variables. Let {E _j ()} _j be the eigenvalues ofH , and let _j (,E)=||(E _j ()–E),j1, be its rescaled eigenvalues. Then assuming that the exponential decay of the fractional moment of the Green function holds for complex energies nearE and that the density of statesn(E) exists atE, we shall prove that the random sequence { _j (,E)} _j , considered as a point process onR ¹, converges weakly to the stationary Poisson point process with intensity measuren(E)dx as gets large, thus extending the result of Molchanov proved for a one-dimensional continuum random Schrödinger operator. On the other hand, the exponential decay of the fractional moment of the Green function was established recently by Aizenman, Molchanov and Graf as a technical lemma for proving Anderson localization at large disorder or at extreme energy. Thus our result in this paper can be summarized as follows: near the energyE where Anderson localization is expected, there is no correlation between eigenvalues ofH if is large.     

Giant quadrupole moment andproton halo discovered in8B

The nuclear quadrupole moment of⁸B(I =2⁺,T _1/2=769 ms) has been determined by use of a modified -NMR detection as |Q(⁸B)|=68.3±2.1 mb, which is twice the prediction of the Cohen-Kurath shell model calculation. The anomalous quadrupole moment which is carried mainly by the protons in the nucleus, has been accounted for by the proton halo effect.