Synthesis and reactions of a stable 1,2-diaryl-1,2-dibromodisilene: a precursor for substituted disilenes and a 1,2-diaryldisilyne

Synthesis and isolation of the stable diaryldibromodisilene, Bbt(Br)SiSi(Br)Bbt, has been accomplished for the first time. The dibromodisilene underwent substitution reactions with organometallic reagents on the low-coordinated silicon atom to afford the corresponding substituted disilenes. Furthermore, the reaction of 1 with t-BuLi afforded the corresponding 1,2-diaryldisilyne, BbtSi[triple bond]SiBbt, the characters of which were revealed by spectroscopic and crystallographic analyses.     

Hidden electronic excited state of enhanced green fluorescent protein

Precise two-photon absorption spectra of the green fluorescent protein (GFP) and the mutants sapphire-GFP (T203I) and enhanced GFP (S65T/F64L), as well as a model compound for the chromophore, 4'-hydroxybenzylidene-2,3-dimethylimidazolinone (HBDI) were measured by multiplex two-photon absorption spectroscopy. The observed TPA bands of the anionic forms of enhanced GFP and HBDI were significantly shifted to the higher energy compared with the lowest-energy bands in one-photon absorption spectra. This result indicated the existence of a hidden electronic excited state in the vicinity of the lowest excited singlet (S1) state of the anionic form of the GFP chromophore, which is the origin of the blue shift of the two-photon absorption spectra as well as two-photon fluorescence excitation spectra.     

Regioselective oxyfunctionalization of unactivated carbons in steroids by a model of cytochrome P-450: osmiumporphyrin complex/tert-butyl hydroperoxide system

tert-Butyl hydroperoxide catalyzed by (5,10,15,20-tetramesitylporphyrinate) osmium(II) carbonyl [Os(TMP)CO] complex was found to be a highly efficient versatile oxidant for C-H carbons in steroid substrates. When reacted with representative steroids with an estrane, pregnane, 5beta-cholane, or 5alpha-cholestane structure, regioselective oxyfunctionalization and/or oxidative degradation occurred to give a variety of novel and uncommon derivatives in one step.     

One-step synthesis of heteroaromatic-fused pyrrolidines via cyclopropane ring-opening reaction: application to the PKCbeta inhibitor JTT-010

A ring-opening reaction of cyclopropanes with five-membered heteroaromatics having a leaving group at C(2) was found to provide heteroaromatic-fused pyrrolidines in one step. This reaction was successfully applied to the synthesis of the protein kinase C-beta inhibitor JTT-010, which possesses a dihydropyrrolo[1,2-a]indole core.     

Effects of dipole interaction and solvation on the CO stretching band of N,N-dimethylacetamide in nonpolar solutions: Infrared, isotropic and anisotropic Raman measurements

The concentration dependence of the CO stretching (ν_CO) band of N,N-dimethylacetamide (NdMA) in cyclohexane, n-hexane, and CCl₄ has been investigated by infrared (IR) and polarized Raman spectroscopy. For the neat liquid of NdMA, the noncoincidence of the aniso- and isotropic Raman wavenumbers is evident. In the 0.47 M cyclohexane solution of NdMA, the noncoincidence effect almost disappears and the ν_CO envelopes in both the Raman and IR spectra are asymmetric to the low-wavenumber side. When the concentration of NdMA decreases from 0.33 to 0.023 M, the peak of these bands slightly shifts to a higher wavenumber and the band shape becomes symmetric. The shape of the ν_CO envelope does not show any significant change below 0.023 M. These results suggest that the asymmetric shape of the ν_CO band observed for the 0.33 M cyclohexane solution is associated with the intermolecular interaction among NdMA molecules, which vanishes at around 0.02 M. Spectral changes for the CCl₄ solution of NdMA show a similar tendency. However, the shape and peak wavenumber of the ν_CO band observed in a highly diluted CCl₄ solution (≤0.023 M) indicate that the solvation effect of CCl₄ is more complicated than those of cyclohexane and n-hexane. The analyses of the ν_CO band, which is sensitive to the intermolecular interaction between solutes and between solute and solvent for NdMA dissolved in nonpolar solvents, would serve to clarify the electronic property of the molecule in a solution.     

Preparation of highly oriented poly-diacetylene films with ion beam irradiation

Abstract

Substituting metallic or rare-earth atoms or removing O in the superconductor YBa₂Cu₃O₇ usually has a strong effect on the superconducting properties. We have made extensive XAFS studies on Co, Fe, Ni, Zn, Gd, and Pr substituted materials including some thin film samples. In nearly all cases, significant distortions are found. Although the lattice constant change is small (< 0.05 Å) the local distortions can be significant larger (～ 0.1 to 0.3 Å). The observed large local distortions of the lattice together with a change in the charge distribution at a site indicate that the interior of the unit cell is easily distorted. The correlation of a strong Tc suppression with large local distortions suggests that distortions of the nearby layers must play a significant role in models for superconductivity in high Tc materials.     

Semi-classical quantum mechanics and stochastic calculus of variations

Within the framework of the general theory of stochastic calculus of variations, we examine mainly the notion of second variation in the stochastic mechanics of E. Nelson, a representative of quantum mechanics in which the concept of path for particles keep a sense. We show that the two approaches used in classical calculus of variation to know if a path is not only an extremum but also the minimum of the action, namely, the local one (weak minimum) and the global one (strong minimum), can be generalized to include the quantum-mechanical paths. Thus, we can prove that locally, a solution of the classical equation of motion is really the minimum, even in a large class of quantum paths containing the semi-classical trajectories. By introducing a stochastic version of the excess function of Weierstrass, we show the analogous global property. There, of course, one can speak of the principle of least action in a strict sense. Several explicit examples are discussed.     

Automatic processing of Young''s fringes in speckle photography

A new method for the automatic processing of Young's fringes in speckle photography is described, based on the technique of spatial phase detection. The amount of calculation is reduced, yet accuracy is of an order comparable with that of the Fourier transform method. Furthermore, orientation of fringes is determined as well as fringe spacing.     

TheP +19Nes- wave resonant state in20Na at stellar energies

The first excited state above the p +¹⁹Ne threshold in²⁰Na has been identified at 2.637 MeV (± 15 keV) with J^π=0⁺ or 1⁺ from the²⁰Ne(³He, t)²⁰Na reaction, suggesting this state to be the s-wave resonance in the p +¹⁹Ne scattering at stellar energies.     

Influence of energetic ions on grafting to polyethylene

Li salts of acrylic acid were grafted to polyethylene, PE. It is known that li is mobile in this material at room temperature, and hence can act as a probe for newly introduced defects. After irradiation of PE(Li) with 100 keV He⁺ ions at different fluences the Li depth distributions were measured by NDP. Changes in the Li distributions are observed which are ascribed to bonding at oxygen, the latter one preferentially penetrating into the PE via the irradiation-damaged sample surface. With increasing sample age, i.e. after exposure to ambient atmosphere for more than half a year, Li appears to lose its original mobility.