Manganese(III)-Catalysed Oxidation of Sulphides with Sodium Chlorite in an Aprotic Solvent in the Presence of Alumina

A wide variety of sulphides can be readily converted to the corresponding sulphoxides in good to excellent yields by treatment with a combination of sodium chlorite, (salen)manganese(III) complex, and chromatographic alumina in dichloromethane under mild and neutral conditions.     

The Renner effect in triatomic molecules with application to CH+, MgNC and NH2

We have developed a computational procedure, based on the variational method, for the calculation of the rovibronic energies of a triatomic molecule in an electronic state that become degenerate at the linear nuclear configuration. In such an electronic state the coupling caused by the electronic orbital angular momentum is very significant and it is called the Renner effect. We include it, and the effect of spin-orbit coupling, in our program. We have developed the procedure to the point where spectral line intensities can be calculated so that absorption and emission spectra can be simulated. In order to gain insight into the nature of the eigenfunctions, we have introduced and calculated the overall bending probability density function f(p) of the states. By projecting the eigenfunctions onto the Born-Oppenheimer basis, we have determined the probability density functions f+(rho) and f-(rho) associated with the individual Born-Oppenheimer states phi(-)elec and phi(+)elec. At a given temperature the Boltzmann averaged value of the f(p) over all the eigenstates gives the bending probability distribution function F(rho), and this can be related to the result of a Coulomb Explosion Imaging (CEI) experiment. We review our work and apply it to the molecules CH2+, MgNC and NH2, all of which are of astrophysical interest.     

Self-oscillation of polymer chains with rhythmical soluble-insoluble changes

Self-oscillation of polymer chains in an aqueous solution has been achieved. The ruthenium catalyst for the Belousov-Zhabotinsky reaction was polymerized by using N-isopropylacrylamide and dissolved into the solution containing the BZ substrates. Periodical soluble-insoluble changes of the polymer chain were spontaneously induced by the BZ reaction. The conformational oscillations of the polymer were measured as the optical transmittance changes of the solution. This is the first report that rhythmical and reversible soluble-insoluble changes of polymer chains are realized under constant and homogeneous conditions. The transducing system from chemical energy of the BZ reaction to optical information has been constructed.     

Nonlinear effects of electrolyte diodes and transistors in a polymer gel medium

The polarization curve of an acid-base interface in a hydrogel medium has a diode characteristic. Two of each such electrolyte diodes can be combined to give an electrolyte transistor. When a salt is added to the alkaline or to the acidic part of a reverse biased electrolyte diode, the current response is highly nonlinear. If the salt is added to the acidic side, even bistability can be observed. This bistability can generate complex oscillations in a base-acid-base electrolyte transistor. These nonlinear effects are studied experimentally and theoretically. While the nonlinear salt effect can be explained with the Nernst-Planck equations, to understand the bistable behavior further investigations are necessary. (c) 1999 American Institute of Physics.     

?rganometallischer Komplex mit Lewis-Base. 3. Mitt. Polymerisationsmechanismen von Vinylverbindungen durch Al-Alkyl-Lewis-Basen-Komplex

Ohne Zusammenfassung     

Effect of sonication on the photo-catalytic mineralization of some chlorinated organic compounds

Effects of the irradiation of ultrasound (US) on the photo-catalytic mineralization of some chlorinated organic compounds such as dichloroethane, tri- and tetrachloroethylenes, chloroacetic acids and chloromethanes were examined in oxygen saturated aqueous solutions suspended titanium dioxide (P25) particles. The yields of the sonochemical mineralization for these compounds were found to be extremely low compared to the photo-catalysis. However, the pre-sonication, US irradiation on the sample solution before the photo-irradiation, enhanced significantly the following photo-catalytic degradation to the complete oxidation. The effect was investigated in detail and it was found that the effect was mainly owing to the increase in the capability of the catalysis of which particles were sparsely dispersed by the sonication. The other contribution of the pre-sonication effect was found to be "pre-sonolysis", the initial formation of some intermediated products sonochemically, which are oxidizable more rapidly further to carbon dioxide than the original compound by the following photo-catalytic reactions. The pre-sonolysis effect was observed remarkably for trichloroacetic acid and tetrachloromethane, both of which are known to be hardly reactive to the photo-catalytic degradation. The photo-catalytic degradation with simultaneous sonication were also carried out for these compounds. The synergetic effect in the mineralization was observed both for carbontetrachloride and for trichloroacetic acid, the higher carbon dioxide yield being obtained in the simultaneous reaction than the sum of the yields in the photo-catalysis and the sonolysis each alone, while no significant synergetic effect was observed in the mineralization of other compounds.     

<Emphasis Type="Italic">In Situ</Emphasis> Synthesis of Field-responsive Nanocrystalline BaTiO<Subscript>3</Subscript> Particles Modified with Functional Organics

Nanocrystalline BaTiO₃ particles modified with polarizable ligands were synthesized through hydrolysis of modified metal–organics below 100°C. BaTiO₃ precursor was synthesized from barium metal, titanium isopropoxide and polarizable ligands in a mixture of ethanol and 2-ethoxyethanol. The modified Ba–Ti complex alkoxide was hydrolyzed yielding BaTiO₃ particles modified with organics. The crystallinty of nanometer-sized particles was dependent upon the hydrolysis conditions, and increased with increasing water amount and time. The nanocrystalline particles were identified to be BaTiO₃ by X-ray diffraction (XRD) and electron diffraction. A fluid consisting of modified BaTiO₃ particles and silicone oil revealed a typical electrorheological (ER) behavior on applying DC field. The ER behavior was found to depend upon the kind of ligand. 4-Fluorobenzyloxy modifier revealed the highest yield stress in the ER measurement among 4-substitued benzyloxy ligands examined.     

3 dB squeezing by single-pass parametric amplification in a periodically poled KTiOPO4 crystal

We present the experimental observation of pulsed squeezed light from a degenerate optical parametric amplifier pumped by a second harmonic of a continuous-wave mode-locked Nd:YVO4 laser. With a single pass through a 10 mm long periodically poled KTiOPO4 crystal, the classical parametric gain of 11 is observed. The measured noise reduction in the quiet quadrature is 3.2 dB below the shot-noise level.