Kinetic studies of specific solvent effect on the thermal isomerization of palladium dithizonate in toluene‐alcohol mixtures

The kinetics of the thermal isomerization of palladium dithizonate (Pd(HD_Z)₂) in the binary mixture of toluene and alcohols has been studied. In the solvent effects on the Pd(HD_Z)₂ isomerization rates, we found that the maximum lies in the range x = 0.02 ∼ 0.2 (x represents the mole fraction of alcohols). The experimental kinetic data for the specific solvent effect with maximum can be reproduced well by taking into account hydrogen bonding and coordination of alcohols with Pd(HD_Z)₂. The rate constants for the thermal isomerization of Pd(HD_Z)₂ involving hydrogen bonding and the coordinate interaction with 1‐butanol are evaluated. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 542–547, 2000     

Near-Infrared Imaging Using a High-Speed Monitoring Near Infrared Hyperspectral Camera(Compovision)

This review paper reports near-infrared (NIR) imaging studies using a newly-developed NIR camera, Compovision. Compovision can measure a significantly wide area of 150 mm×250 mm at high speed of between 2 and 5 s. It enables a wide spectral region measurement in the 1 000～2 350 nm range at 6 nm intervals. We investigated the potential of Compovision in the applications to industrial problems such as the evaluation of pharmaceutical tablets and polymers. Our studies have demonstrated that NIR imaging based on Compovision can solve several issues such as long acquisition times and relatively low sensitivity of detection. NIR imaging with Compovision is strongly expected to be applied not only to pharmaceutical tablet monitoring and polymer characterization but also to various applications such as those to food products, biomedical substances and organic and inorganic materials.     

Structural and electronic differences of copper(I) complexes with tris(pyrazolyl)methane and hydrotris(pyrazolyl)borate ligands

Copper(I) complexes with tripodal nitrogen-containing neutral ligands such as tris(3,5-diisopropyl-1-pyrazolyl)methane (L1') and tris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)methane (L3'), and with corresponding anionic ligands such as hydrotris(3,5-diisopropyl-1-pyrazolyl)borate (L1-) and hydrotris(3-tertiary-butyl-5-isopropyl-1-pyrazolyl)borate (L3-) were synthesized and structurally characterized. Copper(I) complexes [Cu(L1')Cl] (1), [Cu(L1')(OClO3)] (2), [Cu(L1')(NCMe)](PF6) (3a), [Cu(L1')(NCMe)](ClO4) (3b), [Cu(L1')(CO)](PF6) (4a), and [Cu(L1')(CO)](ClO4) (4b) were prepared using the ligand L1'. Copper(I) complexes [Cu(L3')Cl] (5) and [Cu(L3')(NCMe)](PF6) (6) with the ligand L3' were also synthesized. Copper(I) complexes [Cu(L1)(NCMe)] (7) and [Cu(L1)(CO)] (8) were prepared using the anionic ligand L1-. Finally, copper(I) complexes with anionic ligand L3- and acetonitrile (9) and carbon monoxide (10) were synthesized. The complexes obtained were fully characterized by IR, far-IR, 1H NMR, and 13C NMR spectroscopy. The structures of both ligands, L1' and L3', and of complexes 1, 2, 3a, 3b, 4a, 4b, 5, 6, 7, and 10 were determined by X-ray crystallography. The effects of the differences in (a) the fourth ligand and the counteranion, (b) the steric hindrance at the third position of the pyrazolyl rings, and most importantly, (c) the charge of the N3 type ligands, on the structures, spectroscopic properties, and reactivities of the copper(I) complexes are discussed. The observed differences in the reactivities toward O2 of the copper(I) acetonitrile complexes are traced back to differences in the oxidation potentials determined by cyclic voltammetry. A special focus is set on the carbonyl complexes, where the 13C NMR and vibrational data are presented. Density functional theory (DFT) calculations are used to shed light on the differences in CO bonding in the compounds with neutral and anionic N3 ligands. In correlation with the vibrational and electrochemical data of these complexes, it is demonstrated that the C-O stretching vibration is a sensitive probe for the "electron richness" of copper(I) in these compounds.     

Thermoresponsive shuttling of rotaxane containing trichloroacetate ion

A thermoresponsive rotaxane shuttling system was developed with a trichloroacetate counteranion of an ammonium/crown ether-type rotaxane. Chemoselective thermal decomposition of the ammonium trichloroacetate moiety on the rotaxane yielded the corresponding nonionic rotaxane accompanied by a positional change of the crown ether on the axle. The rotaxane skeleton facilitated effective dissociation of the acid, markedly lowering the thermal decomposition temperature.     

Improvement of the physical properties of poly(methyl methacrylate) by copolymerization with N-pentafluorophenyl maleimide; zero-orientational and photoelastic birefringence polymers with high glass transition temperatures

Copolymers of N-pentafluorophenyl maleimide (PFPMI) with methyl methacrylate (MMA) were synthesized by a free radical initiator, such as AIBN. The refractive indexes of the copolymers remained nearly constant (1.4970 at 532 nm) regardless of the polymer composition. These copolymers also showed high thermal stability. The orientational and photoelastic birefringence of the copolymers obtained were measured. Since both of the orientational and photoelastic birefringences of PMMA are negative whereas poly(PFPMI) exhibits positive, thus we have obtained nearly zero orientational and photoelastic birefringence polymers when the ratios of MMA/PFPMI were 91.8/8.2 and 97.0/3.0 mol%, respectively. Based on the experimental data, the ratios of MMA/PFPMI for zero birefringence were determined to be 88.9/11.1 and 93.8/6.2 mol% for orientational and photoelastic birefringence, respectively. The Tgs of corresponding copolymers were estimated to be 128 and 122 ℃.     

Cascade reactions in crystals through cation-π-controlled reorientation on exposure to HCl gas

Exposure of 4-azachalcones to HCl gas produced the corresponding HCl salts with a head-to-tail stacked alignment, irradiation of which produced the corresponding syn-HT dimers with high regio- and stereoselectivities, thus showing the effectiveness of the cascade process in crystals.     

Evaluating Optical Quality of a Bifocal Soft Contact Lens in Near Vision Using a Shack–Hartmann Wavefront Aberrometer

To assess optical characteristics of bifocal soft contact lenses (BCLs) in use, we measured wavefront aberrations of human eyes, of eyes with a monofocal soft contact lens (MCL), and of eyes with a BCL. Modulation transfer functions (MTFs), Strehl ratios, and simulated images for far and near vision were produced with the measured aberrations. High order aberrations of subject 1 were significantly smaller than those of subject 2 (t-test, P = 0.001). We found that wearing the BCL improved the optical quality of an eye in subject 1, expressed as the horizontal MTF from 2 to 48 cycles per degree (cpd) for near vision and the Strehl ratio (t-test, P = 0.009 for Strehl ratio). But we did not find the same effect in subject 2. This difference may be due to the difference in the aberrations of the eyes of the two subjects.     

Strain induced grain boundary premelting in bulk copper bicrystals

In bulk bicrystals strain induced grain boundary premelting (SIGBPM) occurs when heavy screw dislocation pileup can be held up to a certain high temperature, approximately 0.6T _M, where T _M is the melting point of bulk material in Kelvin. SIGBPM occurs at grain boundaries to which new twist component is added due to the rotation of both component crystals toward opposite direction about the axis perpendicular to the grain boundary plane. At the original grain boundary, grain boundary sliding takes place due to this relative rotation. In f.c.c. metals with relatively low stacking fault energies such as copper, nickel, brass(30Zn) and silver, dislocations dissociate into partials. Therefore high density tangled dislocations introduced during plastic deformation hardly loose. If these dislocations can be held to high temperatures, SIGBPM is promoted. Formation of static or dynamic recrystallized grains suppresses SIGBPM itself and the propagation of grain boundary cracks formed by SIGBPM.     

Surface modification of a TiO2 film electrode prepared by the sol-gel method and its effect on photoelectrochemical behavior

The surface of a TiO₂ film electrode, about 1 μm thick, prepared by the sol-gel method, was modified by being additionally coated with about 0.1 μm thick TiO₂---SiO₂, TiO₂---ZrO₂ or TiO₂---Al₂O₃ films. The effect of the additional coating on the photoelectrochemical properties of a TiO₂ film electrode was investigated in detail. On addition of the second additive to TiO₂, the flat band potential was shifted toward negative potential for SiO₂ and positive potential for ZrO₂ and Al₂O₃, which is attributed to the change in the point of zero zeta potential (pzzp), not in the electron affinity (EA). However, enhancement in photocurrent was not observed for all the cases.