Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions

We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone^® in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.     

Saturation transfer ratio imaging in invasive ductal carcinomas of the breast

A prospective study was performed to investigate the correlations between saturation transfer ratio (STR) and histologic parameters of invasive ductal carcinomas in human breast. The histologic parameters investigated were the extent of fibrosis in the intercellular matrix, dysplastic changes of nuclei, and mitotic index. Twenty-seven patients with breast carcinoma were examined using an off-resonance saturation pulse in conjunction with conventional field-echo T(1)-weighted imaging at frequency offsets of 448 Hz and 1200 Hz from water resonance. The values of STR at frequency offset of 1200 Hz (STR(1200)) increased from non-scirrhous carcinoma to scirrhous carcinoma. Although STR(1200) showed correlation with the extent of fibrosis in the intercellular matrix (p<0.01, n = 27), they did not correlate with the dysplastic changes of nuclei or mitotic index. On the other hand, the values of STR at frequency offset of 448 Hz (STR(448)) demonstrated close correlation to dysplastic changes of nuclei and mitotic index (p<0.01, n = 27). STR(1200) correlates with the structural characteristics and STR(448) correlates with the nature of malignant cells with regard to nuclear dysplasia and mitotic potential.     

Photocarrier injection and the I-V characteristics of La0.8Sr0.2MnO3/SrTiO3:Nb heterojunctions

Oxide heterojunctions made of p-type La_0.8Sr_0.2MnO₃ (LSMO) and niobium-doped n-type SrTiO₃ (STO:Nb) have been fabricated by the pulsed laser deposition (PLD) technique and characterized under UV light irradiation by measuring the current-voltage, photovoltaic properties and the junction capacitance. It is shown that the heterojunctions work as an efficient UV photodiode, in which photogenerated holes in the STO:Nb substrate are injected to the LSMO film. The maximum surface hole density Q/e and external quantum efficiency γ are estimated to be 8.3×10¹² cm⁻² and 11% at room temperature, respectively. They are improved significantly in a p-i-n junction of LSMO/STO/STO:Nb, where Q/e and γ are 3.0×10¹³ cm⁻² and 27%, respectively.     

Epitaxial strain effects on the metal-insulator transition in V2O3 thin films

Effects of epitaxial stress on the metal-insulator transition of V₂O₃ have been studied for in the form of epitaxial thin films grown on α-Al₂O₃ (0001) and LiTaO₃ (0001) substrates. A metallic phase is stabilized down to 2 K in the V₂O₃ thin film on α-Al₂O₃ (0001), where the a-axis is compressed by 4% owing to large epitaxial stress. On the other hand, the transition temperature T_MI is raised by 20 K from the value of 170 K in bulk samples in the film on LiTaO₃ (0001), where the a-axis is expanded. These results suggest an intimate relationship between the a-axis length and T_MI in V₂O₃. The conductivity of the metallic ultrathin films shows logarithmic temperature dependence below 20 K, probably due to the Anderson localization in two-dimensional systems.     

Analytical electron microscopy study of diffusion-bonded multiphase system

This study presents diffusion experiments of NiAl coupled with pure Ni (Ni/NiAl). The couple produces the Ni₃Al-based intermetallic phase ( phase) as an intermediate layer at the interface during diffusion annealing. Analytical electron microscopy is used to examine microstructural features, crystallographic orientation and compositional variations across the interface. Interdiffusivities are measured from the compositional variations. It is shown that the growing behavior of the phase changes between higher and lower annealing temperatures. The growth kinetics of the phase is also discussed.     

群链R3i-D4d-C2v及dN体系在C2v对称性场中的能量矩阵

R_(3i)—D_(4d)—C_(2v)是一条群链。本文讨论如何应用D_(4d)群的标准基函作为C_(2v)群的基函来写出d~N体系在C_(2v)对称性场中各配场谱项的能量矩阵H_1。H_1中的H_(el)。部分完全可以应用D_(4d)的H_1中的H_(el)。,因而简化了计算。所得能量矩阵H_1与前文列出的H_1等价。     

Synthesis of Enkephalin analogs via asymmetric hydrogenation of dehydropeptide building blocks

[Ac-D-Tyr¹, D-Ala², Leu⁵-OMe]Enkephalin and [Ac-Tyr¹, D-Ala², Leu⁵-OMe]Enkephalin were successfully synthesized by the coupling of dipeptide units and tripeptide units which were readily obtained by the asymmetric hydrogenation of the corresponding dehydropeptide building blocks.     

Crystal structure of the pyrochlore oxide superconductor KOs2O6

We report the single-crystal X-ray analysis of the structure of the pyrochlore oxide superconductor KOs₂O₆. The structure was identified as the β-pyrochlore structure with space group and lattice constant at : the K atom is located at the 8b site, not at the 16d site as in conventional pyrochlore oxides. We found an anomalously large atomic displacement parameter at for the K cation, which suggests that the K cation weakly bound to an oversized Os₁₂O₁₈ cage exhibits intensive rattling, as recently observed for clathrate compounds. The rattling of A cations is a common feature in the series of β-pyrochlore oxide superconductors AOs₂O₆ (A=Cs, Rb and K), and is greatest for the smallest K cation.     

Molecular orientation of aromatic polycarbonates containing fluorene side chains by polarized infrared spectroscopy and birefringence analysis

The molecular orientation of an aromatic polycarbonate containing fluorene side chains was investigated by polarized infrared spectroscopy and birefringence analyses. The copolymers were synthesized from 2,2‐bis(4‐hydroxyphenyl)propane (BPA), 9,9‐bis(4‐hydroxy‐3‐methylpheny)fluorene (BMPF), and phosgene by interfacial polycondensation. The 1449‐cm^?1 band of the uniaxially oriented films, stretched at the glass‐transition temperature (T_g) plus 5 °C, was assigned to various combinations of CC stretching and CH in‐plane bending vibrations in the fluorene ring, and the transition moment angle was estimated to be 90°. The intrinsic birefringence of aromatic polycarbonate films with BMPF molar ratios ranging from 0.5 to 1 was obtained with the 1449‐cm^?1 band. The copolymer was estimated to show zero intrinsic birefringence at the BMPF molar ratio of 0.75, and the BMPF homopolymer showed negative intrinsic birefringence. A linear relationship between the volume fraction of BMPF units and the intrinsic birefringence indicated that the two monomer units of BPA and BMPF in each copolymer were not independent, and an intrinsic birefringence could be defined even in the copolymer. The sign of the photoelastic coefficient in the homopolymer with BMPF units was positive. The different signs of the photoelastic coefficient and the intrinsic birefringence suggest that the fluorene side‐chain orientation induced by stress in the glass state is quite different from the orientation of the uniaxially oriented films stretched at T_g + 5 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1554–1562, 2003