Direct synthesis of fluorescent 1,3a,6a-triazapentalene derivatives via click-cyclization-aromatization cascade reaction

An efficient and versatile method was established for the preparation of 1,3a,6a-triazapentalenes. The 1,3a,6a-triazapentalene skeleton without an additional fused ring system was discovered to be a compact and highly fluorescent chromophore, which exhibited various interesting fluorescent properties such as a noteworthy correlation of luminescent wavelength with the Hammett σ(p) value and a strongly positive solvatofluorochromism.     

A combined effective fragment potential-fragment molecular orbital method. II. Analytic gradient and application to the geometry optimization of solvated tetraglycine and chignolin

The gradient for the fragment molecular orbital (FMO) method interfaced with effective fragment potentials (EFP), denoted by FMO∕EFP, was developed and applied to polypeptides solvated in water. The structures of neutral and zwitterionic tetraglycine immersed in water layers of 2.0, 2.5, 3.0, 3.5, 4.0, and 4.5 A? are investigated by performing FMO∕EFP geometry optimizations at the RHF∕cc-pVDZ level of theory for the solutes. The geometries optimized with FMO-RHF∕EFP are compared to those from the conventional RHF∕EFP and are found to be in very close agreement. Using the optimized geometries, the stability of the hydrated zwitterionic and neutral structures is discussed structurally and in terms of energetics at the second-order M?ller-Plesset theory (MP2)∕cc-pVDZ level. To demonstrate the potential of the method for proteins, the geometry of hydrated chignolin (protein data bank ID: 1UAO) was optimized, and the importance of the inclusion of water was examined by comparing the solvated and gas phase structures of chignolin with the experimental NMR structure.     

Experimental evaluation and constitutive modeling of non-proportional deformation for asymmetric steels

Recently non-proportional deformation has received increased attention from researchers working in the area of experimental and computational modeling of metal deformation. However, most of them are numerical in nature with limited experimental data available, making it further difficult to model non-proportional deformation. In the present work, two-stage uniaxial tests, along with uniaxial cyclic and biaxial tests for different stress ratios, have been performed to evaluate deformation behavior of ultra-low carbon high strength automotive steel. Behaviors like cross-effect and hardening stagnation, which are attributed to the evolution of complex dislocation structures, were observed in this steel. It was also noticed that this steel exhibits tension-compression asymmetry. As for constitutive modeling, a modified asymmetric yield function is proposed to be used with a combined isotropic-kinematic hardening model. Also methods to account for the hardening stagnation during reverse loading and the cross-effect during two-stage deformation are proposed. The resulting constitutive model showed reasonably good agreement with experimental results.     

Optical characteristics of one-dimensional photonic crystals composed of high-aspect-ratio Si walls fabricated on V-grooved wafer

We demonstrate optical properties of one-dimensional photonic crystals (PC), which are fabricated using high-aspect-ratio etching on a V-grooved silicon wafer. The measured transmission spectrum has an obvious band gap; the suppression is over 30 dB. The quite small insertion loss of 1.9 dB is achieved by induced coupled plasma (ICP) cryogenic etching and direct coupling to the optical fiber aligned in the V-groove. We also successfully observed peaks originating from a localized cavity mode. Such a microcavity enables control of the light, which qualifies photonic crystal as a fundamental structure of optical functional devices. These results lead to achievement of integrated Si-based photonic circuits.     

Thin-layer chromatographic behaviour and separation of rare earths in silica gel-aqueous alkali metal chloride systems

Summary The thin-layer chromatographic behaviour of all the rare earths except Pm on silica gel in aqueous solutions of five alkali metal chlorides has been surveyed. The Rf-values and the logarithms of the separation factors relative to Gd vary in a regular and peculiar way with increasing atomic number, through a reflection of the strong tetrad effect. A discussion concerning the effects on the Rf-values of the solvent cations and the solvent anions, and typical chromatograms for the separations of multi-component mixtures containing adjacent lanthanoids are also presented.     

Copper(II) chloride as a new,efficient additive suppressing racemization in peptide synthesis by the carbodiimide method

Copper(II) chloride was found to be an extremely efficient additive suppressing racemization in the carbodiimide mediated couplings.     

Radical formation during tensile deformation of highly drawn crystalline poly[p-(2-hydroxyethoxy)benzoic acid] fibers

The micromechanism of tensile deformation of poly[p-(2-hydroxyethoxy)benzoic acid] fibers is discussed on the basis of a detailed esr study of radical formation. The concentration of primary phenoxy radicals, which were detected during deformation at room temperature as a direct indicator of main-chain rupture, was determined by extrapolating the radical decay curves at various strains to zero time. The relation between the initial radical concentration and the strain is well expressed by the cumulative normal distribution curve. By use of this relation and a model of fiber structure, the distribution of the contour length of tie chains was determined. No radicals were detected during a second stretching cycle until the maximum strain in the first run was exceeded. The deformation model which includes alternating crystalline and amorphous regions connected by tie chains, a distribution of contour lengths of tie chains, and a phase transformation of molecular chains in the crystalline region accounted fairly well for the observed stress–strain behavior of monofilaments in first and second stretching cycles. The comparison between the observed and the calculated radical concentration suggests that statistical factors and other deformation mechanisms have to be taken into account.