Studies on extraction of copper(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone

The extraction of Cu(II) with 1-phenyl-3-methyl-4-acyl-5-pyrazolone (HA), in different organic solvents has been studied. The extraction mechanism of Cu(II) and the composition of the extracted species has been determined. Cu(II) was extracted as CuA₂, or in the presence of TOPO, as CuA₂TOPO. The extraction constants do not change regularly with increasing the length of acyl chain in the 1-phenyl-3-methyl-4-acyl-5-pyrazolone derivatives. The effect of the temperature on the extraction of Cu(II) has also been investigated.     

Cleavage of vinyl carbon-silicon bond with tetrabutylammonium fluoride

Dimethylphenylsilyl group is removed from a vinyl carbon with tetrabutylammonium fluoride. The presence of phenyl group on silicon atom plays a critical role. The cleavage of allyldimethylsilyl- and alkoxydimethylsilyl groups also proceeds very easily.     

Turbulent heat transfer in a flat plate boundary layer disturbed by a cylinder

Augmentation of heat transfer from a flat plate using a turbulence promoter has been studied. A circular cylinder 8 mm in diameter was placed in the turbulent boundary layer detached from the flat plate. It was located parallel to the plate and perpendicular to the flow direction. Clearance, c, between the cylinder and the flat plate was varied in nine steps: c=0, 1, 2, 3, 4, 6, 11, 20 and 29.5 mm. Measurements were made of the local heat transfer coefficients, mean velocity profiles, turbulence intensity profiles, static pressure and skin friction. Experimental results showed that the heat transfer deterioration which occurs just downstream of the cylinder at c=0 mm can be removed by displacing the cylinder a small distance from the wall. The improvement in heat transfer is mainly due to the unsteadiness of the recirculating flow on the plate and the effect of intense turbulence arriving at the near wall region from the lower shear layer of the cylinder wake. Heat transfer augmentation is most effective when c=4 mm and becomes less effective when c is increased more than 6 mm. The enhancement disappears far downstream from the cylinder.     

A note on stochastic phase lockings in a relaxation oscillator forced by a sine input with additive noise

Summary Noise effects on phase lockings in a system consisting of a piecewise-linear van der Pol relaxation oscillator driven by a periodic input are studied. The problem of finding the period of the oscillator is reduced to the first-passage-time problem of the Ornstein-Uhlenbeck process with time-varying boundary. Using the probability density functions of the first-passage time, the operator which governs a transition of an input phase density after one cycle of the oscillator is defined. Phase lockings in a stochastic sense are investigated on the basis of the density evolution by the operator. Paper presented at the International Workshop ?Fluctuations in Physics and Biology: Stochastic Resonance, Signal Processing and Related Phenomena?, Elba, 5–10 June 1994.     

Ultraviolet photoemission spectroscopy of (TaSe4)2I

The vacuum ultraviolet photoemission spectra of quasi-one-dimensional charge density wave ( CDW ) system, (TaSe₄)₂I, were measured for photon energies between 32 and 100 eV at room temperature ( in the normal phase ) and at about 100 K ( in the CDW phase ). The spectrum of Ta 4f core-levels has shown no additional splitting due to the two different Ta sites. The spectra of the valence and conduction bands have revealed the resonant enhancement for the excitation of the Ta 5p core states, which demonstrates the remarkable hybridization of Ta 5d orbitals with Se 4p orbitals with binding energies smaller than 4 eV. In the CDW phase, the partial cross section decreases for both Ta 5d bands and Se 4p bands with Ta 5d components.     

Statistical mechanics of thermal diffusion

Expressions of the flows of atoms A and B of a binary system in a crystal are derived as the response to the imposed gradients of temperature and chemical potentials. The formulation is done using the pair approximation of the Path Probability Method of irreversible statistical mechanics and atomic migration is assumed to be via the vacancy mechanism. The energy carried by photons (and electrons) under the temperature gradient is assumed to be independent of the atomic flux. For the case near equilibrium, linear relations are derived among the atomic fluxes, the energy flux (associated with atomic flux) and the gradients. The Onsager reciprocal relations are proved to hold among the coefficients, including those related to energy flows. The heat of transport (energy carried by a diffusing atom) and the heat conduction due to atomic flux are thus unambigously derived.     

Infinite Divisibility for Stochastic Processes and Time Change

General results concerning infinite divisibility, selfdecomposability, and the class L _m property as properties of stochastic processes are presented. A new concept called temporal selfdecomposability of stochastic processes is introduced. Lévy processes, additive processes, selfsimilar processes, and stationary processes of Ornstein–Uhlenbeck type are studied in relation to these concepts. Further, time change of stochastic processes is studied, where chronometers (stochastic processes that serve to change time) and base processes (processes to be time-changed) are independent but do not, in general, have independent increments. Conditions for inheritance of infinite divisibility and selfdecomposability under time change are given.     

Synthesis and biological evaluation of optically active 3-H-1-carbacephem compounds

3-H-1-Carbacephem nuclei with or without a 2 alpha- or 2 beta-methyl group were prepared via 2 + 2 cycloaddition followed by intramolecular Horner-Emmons cyclization. Optically active 3-H-1-carbacephem compounds were efficiently prepared by employing a penicillin acylase-producing microorganism in two ways. That is, the 7-phenylacetamide of a racemic carbacephem nucleus was hydrolyzed enantioselectively with the enzyme to afford the optically pure nucleus, which was then acylated to give antimicrobial compounds. Alternatively, a racemic carbacephem nucleus was directly and enantioselectively phenylglycylated with the enzyme. 3-H-1-Carbacephem nuclei appeared to be better substrates for penicillin acylase than penam or cephem nuclei of natural origin. 3-H-1-Carbacephem compounds showed potent antimicrobial activity; compound 32a exhibited activity comparable to that of ceftizoxime, a cephem analog with the same acyl group. It is of interest that the 3-H-1-carbacephem compound turned out to have more potent antimicrobial activity than its 3-substituted methyl analog.