Highly effective synthetic methods for substituted 2-arylbenzofurans using [3,3]-sigmatropic rearrangement: short syntheses of stemofuran a and eupomatenoid 6

A new and efficient synthesis of 2-arylbenzofurans has been achieved via a route involving acylation and subsequent [3,3]-sigmatropic rearrangement of oxime ethers. Its synthetic utility is demonstrated by a short synthesis of stemofuran A and eupomatenoid 6 in which no procedure for protection of the phenolic hydroxyl groups is needed. [reaction--see text]     

Palladium-indium iodide-mediated allylation and propargylation of glyoxylic oxime ether and hydrazone: the role of water in directing the diastereoselective allylation

Allylation and propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(0) complex and indium(I) iodide were studied. Excellent diastereoselectivities in allylation were achieved in the presence of water, although low diastereoselectivities were observed in the absence of water. Propargylation of glyoxylic oxime ether proceeded with good diastereoselectivities in the presence of LiBr or LiCl.     

Periodic change of viscosity and density in an oscillating chemical reaction

It was found that the periodic change of the solution viscosity and density was generated in the Belousov-Zhabotinsky (BZ) reaction. This rhythmic phenomenon was observed in both the iron catalyst [[Fe(Phen)(3)](2+)-[Fe(Phen)(3)](3+)] and the cerium catalyst [Ce(III)-Ce(IV)] system, where the solution viscosity and density were synchronized with the redox potential in the in-phase mode. However, the time delay existed between the redox potential and the solution viscosity and density. The behavior of the BZ reaction was also monitored in the presence of the nonionic surfactant. This experiment revealed that, beyond the critical micelle concentration, the phase between the redox potential and the solution viscosity and density was synchronized into the antiphase mode. We suggested that the variation of the catalyst drove the oscillation of the solution viscosity and density in the BZ reaction.     

Magnetic penetration depth measurements of Pr2-xCexCuO4-delta films on buffered substrates: evidence for a nodeless gap

We report measurements of the inverse squared magnetic penetration depth, lambda(-2)(T), in Pr(2-x)Ce(x)CuO(4-delta) (0.115< or =x < or =0.152) superconducting films grown on SrTiO3 (001) substrates coated with a buffer layer of insulating Pr2CuO4. lambda(-2)(0), T(c), and normal-state resistivities of these films indicate that they are clean and homogeneous. Over a wide range of Ce doping, 0.124< or =x < or =0.144, lambda(-2)(T) at low T is flat: it changes by less than 0.15% over a factor of 3 change in T, indicating a gap in the superconducting density of states. Fits to the first 5% decrease in lambda(-2)(T) produce values of the minimum superconducting gap in the range of 0.29< or =Delta(min)/k(B)T(c)< or =1.01.     

Construction of a square-planar hydroperoxo-copper(II) complex inducing a higher catalytic reactivity

A novel hydroperoxo-copper(II) complex with a square-planar geometry has been prepared, which has exhibited a higher selectivity and catalytic reactivity for dimethyl sulfide, in contrast to that with a trigonal-bipyramidal one.     

Vortex core physics in the cuprate superconductor Nd2−xCexCuOy

Flux-flow voltage steps and negative differential resistivity in the cuprate Nd_2−xCe_xCuO_y are explained in terms of subbands between the Fermi energy and the energy gap affecting the quasiparticle dynamics.     

Simulation for internal energy deposition in sustained off-resonance irradiation collisional activation using a monte carlo method

This paper proposes a novel computational approach employing a Monte Carlo method, aimed at an improved understanding of the dynamics and energetics of activated ions in sustained off-resonance irradiation collisionally activated dissociation (SORI-CAD) experimental events of Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). In SORI-CAD events, internal energies of activated ions are complicatedly associated with their motion undergoing off-resonance excitation (i.e. alternate accelerations and decelerations) and inherently stochastic ion-neutral collisions. Several types of pseudo-random generators were adapted to probability density functions (PDFs) which characterize the ion-neutral collision process. Simulated ion trajectories involve the realistic feature of pressurized SORI-CAD events, such as a collisional damping and those which have not been illustrated in conventional analytical approaches. The proposed method can simulate the time-varying translational and internal energies of activated ions. The present result suggests that the internal energy of a SORI-activated ion should be inversely proportional to the cube of the SORI excitation frequency offset. Copyright 1999 John Wiley & Sons, Ltd.     

Gas sorption in poly(vinyl benzoate)

High-pressure sorption (up to 50 atm) for CO₂, N₂, and Ar in poly(vinyl benzoate) (PVB) was studied at temperatures from 25 to 70°C by a gravimetric method utilizing an electromicrobalance. The results are described by Henry's law above the glass transition temperature T_g for all gases. The dual-mode sorption model, Henry's law plus a Langmuir isotherm, applies to the sorption isotherms of N₂ and Ar in the glassy state, and the dual-mode parameters are given. For CO₂, a new type of sorption isotherm is observed below T_g. The isotherm is concave to the pressure axis in the low-pressure region and turns into a straight line with increasing CO₂ pressure which can be extrapolated back to the coordinate origin. The linear part of the isotherm is characteristic of the rubbery state, while the nonlinear part stems from glassystate behavior. The “glass transition solubility” of CO₂, at which PVB film changes from the glassy to the rubbery state, decrease as the temperature increases. The disappearance of microvoids, that is, the decrease of the Langmuir capacity, may be due to a large plasticizing effect of sorbed CO₂. The difference between the N₂ and Ar isotherms and the CO₂ isotherm is discussed from this standpoint.