Fluorescence studies on phenylene moieties embedded in a framework of periodic mesoporous organosilica

The excited state characteristics of phenylene (Ph)-bridged periodic mesoporous organosilica (PMO) powders with crystal-like and amorphous wall structures are investigated. Crystal-like Ph-PMO has a molecular ordering of the bridging organic moieties with intervals of 0.76 and 0.44 nm parallel and perpendicular to the mesochannel direction, respectively, whereas amorphous Ph-PMO has no molecular-level periodicity in the wall. Fluorescence from the exciton and excimer of the Ph moieties and the defect center in the silicate network were detected at room temperature, but fluorescence from the excimer and the defect center were not detected at 77 K for crystal-like Ph-PMO dispersed in a methanol/ethanol mixed solvent. The decay curve of the exciton fluorescence of crystal-like Ph-PMO at room temperature was analyzed successfully using a one-dimensional diffusion model quenched by the defect center and the excimer site. The results were discussed in comparison with those for the crystal-like biphenylene-bridged PMO reported in the preceding paper (Yamanaka et al., Phys. Chem. Chem. Phys., 2010, 12, 11688-11696). The existence of excited states with various conformations including ground state dimers or aggregates of the Ph moieties was suggested for amorphous Ph-PMO. It was clearly apparent that the differences in the excited state dynamics reflected the differences in the molecular-level structure in the wall.     

High-pressure and high-temperature generation using diamond/sic composite anvils prepared with hot isostatic pressing

Using a hot isostatic pressing (HIP) technique, we synthesized diamond/SiC composites from diamond and Si powders. At an HIP condition of 1450 °C and 100 MPa, a pressure much lower than that of the diamond stability field, diamond powders react with molten Si to form well-sintered diamond/SiC composites. Cubes of the composites with 15 mm edge length were thereby fabricated, and an application to the second stage anvils in a Kawai-type high-pressure apparatus was attempted. A hybrid anvils system using four cubes of the composites and four of the conventional WC was introduced and heating experiments up to 1600 °C became possible. Because the diamond/SiC composites are transparent to X-rays, the present system is applicable not only to diffraction studies but also to radiographic studies that need a larger window for an X-ray image.     

Complete selection of a self-assembling homo- or hetero-cavitand cage via metal coordination based on ligand tuning

Selective formation of a homo- or hetero-cavitand cage via metal-coordination, by using tetra(4-pyridyl)-cavitand (1), tetrakis(4-pyridylethynyl)-cavitand (2), or tetrakis(4-cyanophenyl)-cavitand (3) as deep cavitand ligands and Pd(dppp)(OTf)2 (4) as a connector, has been investigated by 1H NMR and CSI-MS. When the cavitand and 4 were mixed in CDCl3 in a 2:4 molar ratio, 1 gave a complicated mixture, whereas 2 or 3 formed a homo-cavitand cage {2(2).4[Pd(dppp)]}8+.8(TfO-) (5) or {2(3).4[Pd(dppp)]}8+.8(TfO-) (6), respectively, as a single species. In a 1:1:4 mixture of 2, 3, and 4, homo-cavitand cages 5 and 6 were observed in a 1:1 ratio. In marked contrast, a mixture of 1, 3, and 4 in a 1:1:4 ratio was exclusively self-assembled into a hetero-cavitand cage {1.3.4[Pd(dppp)]}8+.8(TfO-) (7). The selectivity for the self-assembly of the homo- or hetero-cavitand cage via metal coordination would arise from a combination of factors such as coordination ability and steric demand of cavitand ligands.     

Raman scattering in YBa2Cu3O7 single crystals: Anisotropy in normal and superconductivity states

Precise temperature and polarization dependences of Raman spectra have been investigated for fully oxygenated twin-free YBa₂Cu₃O₇ single crystals. We have found a striking superconductivity-induced x−y anisotropy in the temperature behavior of the 340 cm⁻¹ line: the magnitudes of the softening and broadening are quite different in the xx-and yy-polarizations. This anisotropy suggests a contribution of the CuO-chain superconductivity with a pairing symmetry different from that for the CuO₂ plane, or indicates that the superconducting gap amplitudes are different in the k _x and k _y directions. The d+s gap symmetry is the only realistic symmetry in the case of Δ_x≠Δ_y. Fiz. Tverd. Tela (St. Petersburg) 40, 403–412 (March 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Tunneling time based on the quantum diffusion process approach in multichannel and optical potential cases

We analyze the effects of inelastic scattering on the tunneling time theoretically, using generalized Nelson’s quantum mechanics. This generalization enables us to describe quantum system with channel couplings and optical potential in a real time stochastic approach, which seems to give us a new insight into quantum mechanics beyond Copenhagen interpretation     

Observation of field quenching of photo-induced effects in hydrogenated amorphous silicon

Field quenching phenomena were observed in the photo-induced changes in dark current—voltage and dark low frequency capacitance-voltage characteristics of hydrogenated amorphous silicon (a-Si:H) diodes. The photo-induced changes in photoconductivity of undoped a-Si:H measured in coplanar type samples also depended on the externally applied electric field. The mechanisms of the field quenching were discussed referring to trapping and/or recombination of photogenerated carriers in a-Si:H.     

Three dimensional gain analysis of free electron laser with focusing permanent magnet wiggler

A three dimensional simulation software system developed to estimate a free electron laser (FEL) gain has been applied to FEL using a standard plane polarized wiggler and an alternately shifted magnet wiggler. It is seen for the latter wiggler that a large filling factor could be selected and each maximum gain corresponding to each orbit of electron beam concentrates at a certain frequency region of FEL radiation. It is, therefore, implied that a proper shift between the adjacent magnets in the wiggler produces the improvement of the FEL gain.     

Hydrogen bond donors and acceptors are generally depolarized in α-helices as revealed by a molecular tailoring approach

Hydrogen-bond (H-bond) interaction energies in α-helices of short alanine peptides were systematically examined by precise density functional theory calculations, followed by a molecular tailoring approach. The contribution of each H-bond interaction in α-helices was estimated in detail from the entire conformation energies, and the results were compared with those in the minimal H-bond models, in which only H-bond donors and acceptors exist with the capping methyl groups. The former interaction energies were always significantly weaker than the latter energies, when the same geometries of the H-bond donors and acceptors were applied. The chemical origin of this phenomenon was investigated by analyzing the differences among the electronic structures of the local peptide backbones of the α-helices and those of the minimal H-bond models. Consequently, we found that the reduced H-bond energy originated from the depolarizations of both the H-bond donor and acceptor groups, due to the repulsive interactions with the neighboring polar peptide groups in the α-helix backbone. The classical force fields provide similar H-bond energies to those in the minimal H-bond models, which ignore the current depolarization effect, and thus they overestimate the actual H-bond energies in α-helices. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.