Photoelectron spectra and angular distribution in reson three-photon ionization of atomic iron: J dependence

Kenetic energies and angular distributions of photoelectrons emitted by three-photon ionization fo atomic iron through two-photon resonant state e⁷D_J and e⁵ D_J, were measured, by using visible lasers. J-resolved photoelectron bands attributab to the a⁶D_J and a⁴F_j ionic states are reported.     

Determination of threo and erythro configurations of 3-fluorophenylalanine for verifying stereochemical aspects of recently reported syntheses

Determination of threo and erythro configurations of both diastereoisomers of 3-fluorophenylalanine on the basis of chemical transformation and X-ray analysis has confirmed that the aziridine ring opening reaction gives the threo isomer stereoselectively, whereas the fluorodehydroxylation reaction affords both isomers nonselectively.     

Preparation of Saccharide-Silica Composites by a Sol-Gel Method and the Application for Optical Resolution of Metal Chelate Compounds

A novel organic-inorganic composite was prepared by a sol-gel process using hydrolysis and condensation of tetraethoxysilane (TEOS) reacted with a saccharide. During the process, ethoxy groups of the TEOS were replaced with hydroxyl groups of the saccharide and, consequently, saccharide molecules were combined with silica through their hydroxyl groups. Samples obtained under different reaction conditions were used for optical resolution of a metal chelate compound. The resolution ability of the composites was affected by the amount of water added for hydrolysis and of the saccharide. In particular, the amount of water drastically influenced the optical resolution performance. Composites obtained at the lower H2O/TEOS ratio gave the metal chelate compound a higher optical rotation. Three types of composites with the same composition were prepared by kneading, impregnation and by the sol-gel method, and were compared. The sol-gel composite showed the best optical resolution ability. It was concluded that the optical resolution ability was closely related to dispersibility of saccharide in the silica matrix.     

Cascade Rearrangement of 5-Cyclopentylidenecyclooctanones

Acid-catalyzed rearrangement of 5-cyclopentylidenecyclooctanone derivatives 9a-c was examined to obtain polyspiropolyquinanes 11a-c, considered to have a unique helical structure, through cascade rearrangement pathways consisting of continuous transannular cyclization followed by successive 1,2-alkyl shifts. The substrates were prepared easily by use of the Wittig or McMurry reaction. Reaction of the 5-cyclopentylidenecyclooctanone (9a) with acid gave the expected dispirotriquinane ketone 11a in high yield. The precise mechanism was elucidated by a deuterium-labeling experiment. In the case of the ketone 9b, having another spiroannulated cyclopentane ring attached on 9a, the trispirotetraquiane 11b was not obtained but the bis-propellane-type tetrahydrofuran 25 was produced exclusively. The 5-(5'-cyclopentylidenecyclooctylidene)cyclooctanone (9c) afforded the polycyclic compounds 27-31, depending on the acid used, instead of the desired tetraspiropentaquinane 11c. The structures of the products were determined by NMR spectral data including 2D (13)C INADEQUATE spectra and X-ray crystallographic analyses. The unexpected rearrangement pathways are also discussed.     

Scalar auxiliary variable approach for conservative/dissipative partial differential equations with unbounded energy functionals

BIT Numerical Mathematics - In this paper, we present a novel investigation of the so-called SAV approach, which is a framework to construct linearly implicit geometric numerical integrators for...     

Stochastic phase lockings in a relaxation oscillator forced by a periodic input with additive noise: A first-passage-time approach

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. The probability density functions of the first-passage time are used to define the operator which governs a transition of an input phase density after one cycle of the oscillator. Phase lockings in a stochastic sense are investigated on the basis of the density evolution by the operator.     

Mössbauer spectroscopic study of ferrocene derivatives in the adsorption and liquid-crystalline states

Mössbauer spectra of ferrocene derivatives in the solid, adsorption and liquidcrystalline states were measured at temperatures ranging from 78 to 423 K. The peak intensities of the Mössbauer spectra of ferrocene derivatives adsorbed on silica gel decreased markedly with an increase in temperature. The Mössbauer absorption of [4-(4-methoxyphenoxycarbonyl)-phenoxycarbonyl]alkyl 4-ferrocenylbenzoate at 295 K during the cooling process was observed in what was assumed to be the liquid-crystalline state.