Luminescence of GaN single crystals prepared by heating a Ga melt in Na–N2 atmosphere

Colorless transparent prismatic crystals (0.5‐2.0 mm long) and hopper crystals (1.0‐2.5 mm long) of GaN were prepared by heating a Ga melt at 800°C in Na vapor under N₂ pressures of 7.0 MPa for 300 h. The photoluminescence (PL) spectrum of a prismatic crystal at 4 K showed the emission peaks of neutral donor‐bound exciton (D⁰‐X) and free exciton (X_A) at 3.472 eV and 3.478 eV, respectively, in the near band edge region. The full‐width at half‐maximum (FWHM) of (D⁰‐X) peak was 1.9 meV. The emission peaks of a donor–acceptor pair transition (D⁰‐A⁰) and its phonon replicas were observed in a lower energy range (2.9‐3.3 eV). The emission peaks of the D⁰‐A⁰ and phonon replicas were also observed in the cathodoluminescence (CL) spectrum at 20 K. The (D⁰‐X) PL peak of a hopper crystal at 4 K was at 3.474 eV (2.1 meV higher), having a FWHM of 6.1 meV which was over 3 times larger than that of the prismatic crystal. A strong broad band with a maximum intensity around 1.96 eV was observed for the hopper crystals in the CL spectrum at room temperature. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of GaN crystals by heating a Li3N‐added Ga melt in Na vapor and their photoluminescence

GaN crystals were prepared by heating a Ga melt with 1 at% Li₃N against Ga at 750 °C in Na vapor under N₂ pressures of 0.4–1.0 MPa. The GaN crystals grown at 1.0 MPa of N₂ were colorless and transparent prismatic, having a size of approximately 0.7 mm in length. A secondary ion mass spectrometry (SIMS) showed the contaminant of lithium in the obtained crystals. A large broad yellow band emission peak of 2.28 eV was observed at room temperature in the photoluminescence spectrum in addition to the near band emission peak of GaN at 3.39 eV and a small broad satellite emission at 3.24 eV. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

High-resolution laser ablation inductively coupled plasma mass spectrometry used to study transport of metallic nanoparticles through collagen-rich microstructures in fibroblast multicellular spheroids

We have efficiently produced collagen-rich microstructures in fibroblast multicellular spheroids (MCSs) as a three-dimensional in vitro tissue analog to investigate silver (Ag) nanoparticle (NP) penetration. The MCS production was examined by changing the seeding cell number (500 to 40,000 cells) and the growth period (1 to 10 days). MCSs were incubated with Ag NP suspensions with a concentration of 5 μg mL⁻¹ for 24 h. For this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to visualize Ag NP localization quantitatively. Thin sections of MCSs were analyzed by LA-ICP-MS with a laser spot size of 8 μm to image distributions of ¹⁰⁹Ag, ³¹P, ⁶³Cu, ⁶⁶Zn, and ⁷⁹Br. A calibration using a NP suspension was applied to convert the measured Ag intensity into the number of NPs present. The determined numbers of NPs ranged from 30 to 7200 particles in an outer rim of MCS. The particle distribution was clearly correlated with the presence of ³¹P and ⁶⁶Zn and was localized in the outer rim of proliferating cells with a width that was equal to about twice the diameter of single cells. Moreover, abundant collagens were found in the outer rim of MCSs. For only the highest seeding cell number, NPs were completely captured at the outer rim, in a natural barrier reducing particle transport, whereas Eosin (⁷⁹Br) used as a probe of small molecules penetrated into the core of MCSs already after 1 min of exposure.

Fibroblast MCS could build up the barrier only for nanoparticles

     

Morphology control of polypropylene by crystallization under carbon dioxide

We investigated the crystalline morphology of isotactic polypropylene obtained by melt crystallization under carbon dioxide (CO₂) at various pressures. Spherulites consisting of regularly arranged fibrils without subsidiary lamellae were obtained by crystallization under CO₂ below 2 MPa, whereas large spherulites consisting of irregularly arranged fibrils with subsidiary lamellae were obtained under ambient pressure. Distorted domain crystals with uniform optical anisotropy consisting of α‐form were found to be obtained under CO₂ above 2 MPa, and needle crystals consisting of γ‐form were obtained above 12 MPa. Transmission electron micrographs showed that straight and thick lamellae are regularly arranged in both the distorted domain crystals and the needle crystals. The uniformly thick lamellae were confirmed by differential scanning calorimetry thermograms; that is, the melting temperature is higher and the melting peak is sharper than those obtained under ambient pressure. Such characteristic crystalline morphologies obtained under CO₂ may be attributed to local ordering in the melt state. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2738–2746, 2004     

Millimeter and Submillimeter Wave ESR System: Using 30 T Pulsed Magnetic Field

New systems for millimeter and submillimeter wave ESR have been developed in Kobe University. In the previous system the pulsed magnetic field was limited up to 17 T in the temperature range from 1.8 to 86 K. Using the new systems, we can measure in the field range up to 30 T in the temperature range from 1.8 K to 4.2 K and from 18 K to room temperature. The resolution of the magnetic field has been also improved in the new ESR system. The details of our new ESR systems are presented. In addition, the measurements of Yb₂Cu₂O₅ using these new systems are presented.     

Corrected versions of cross-validation criteria for selecting multivariate regression and growth curve models

This paper is concerned with cross-validation (CV) criteria for choice of models, which can be regarded as approximately unbiased estimators for two types of risk functions. One is AIC type of risk or equivalently the expected Kullback-Leibler distance between the distributions of observations under a candidate model and the true model. The other is based on the expected mean squared error of prediction. In this paper we study asymptotic properties of CV criteria for selecting multivariate regression models and growth curve models under the assumption that a candidate model includes the true model. Based on the results, we propose their corrected versions which are more nearly unbiased for their risks. Through numerical experiments, some tendency of the CV criteria will be also pointed.     

Evaluation of the analytical capability of NIR femtosecond laser ablation-inductively coupled plasma mass spectrometry.

A laser ablation-inductively coupled plasma-mass spectrometric (LA-ICPMS) technique utilizing a titanium-sapphire (TiS) femtosecond laser (fs-laser) has been developed for elemental and isotopic analysis. The signal intensity profile, depth of the ablation pit and level of elemental fractionation were investigated in order to evaluate the analytical capability of the present fs-laser ablation-ICPMS technique. The signal intensity profile of (57)Fe, obtained from iron sulfide (FeS(2)), demonstrated that the resulting signal intensity of (57)Fe achieved by the fs-laser ablation was almost 4-times higher than that obtained by ArF excimer laser ablation under a similar energy fluence (5 J/cm(2)). In fs-laser ablation, there is no significant difference in a depth of the ablation pit between glass and zircon material, while in ArF laser ablation, the resulting crater depth on the zircon crystal was almost half the level than that obtained for glass material. Both the thermal-induced and particle size-related elemental fractionations, which have been thought to be main sources of analytical error in the LA-ICPMS analysis, were measured on a Harvard 91500 zircon crystal. The resulting fractionation indexes on the (206)Pb/(238)U (f(Pb/U)) and (238)U/(232)Th (f(U/Th)) ratios obtained by the present fs-laser ablation system were significantly smaller than those obtained by a conventional ArF excimer laser ablation system, demonstrative of smaller elemental fractionation. Using the present fs-laser ablation technique, the time profile of the signal intensity of (56)Fe and the isotopic ratios ((57)Fe/(54)Fe and (56)Fe/(54)Fe) have been measured on a natural pyrite (FeS(2)) sample. Repeatability in signal intensity of (56)Fe achieved by the fs-laser ablation system was significantly better than that obtained by ArF excimer laser ablation. Moreover, the resulting precision in (57)Fe/(54)Fe and (56)Fe/(54)Fe ratio measurements could be improved by the fs-laser ablation system. The data obtained here clearly demonstrate that, even with the fundamental wavelength (NIR operating at 780 nm), the fs-laser ablation system has the potential to become a significant tool for in-situ elemental and isotopic analysis of geochemical samples including heavy minerals and metallic materials.     

Asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones by rhodium-catalyzed 1,4-addition of arylzinc reagents in the presence of chlorotrimethylsilane

[reaction: see text] The first catalytic asymmetric synthesis of 2-aryl-2,3-dihydro-4-quinolones has been developed by way of a rhodium-catalyzed 1,4-addition of arylzinc reagents to 4-quinolones. These 1,4-adducts can be obtained with high enantioselectivity by the use of (R)-binap as a ligand, and high yields are realized by conducting the reactions in the presence of chlorotrimethylsilane.     

Angular dependence in the transmittance from self‐organized striped pattern of refractive indices in photopolymer

We report on a self‐organized striped pattern of refractive indices in a photopolymer and the resulting angular dependence in the transmittance as a result of the microstructure. The photopolymer plates were obtained by photoreaction of a monomer mixture placed in a space between two glass plates. The monomer mixture was prepared by mixing bifunctional methacrylate monomer, cyanoethylmethacrylate, and 2,4,6‐trimethylbenzoyldiphenylphosphine oxide as photoinitiator. After the photoreaction by uniform irradiation of UV light, the self‐organized striped pattern was observed in the crosslinked photopolymer plate by optical microscopy. Electron probe microanalysis of the cross section of the polymer plate confirms that a compositional inhomogeneity in the medium is quite small. The result suggests that the optically observed striped pattern is not due to the compositional and/or density modulation through the diffusion of monomers. We attribute the striped pattern to the crosslink density modulation and the resulting refractive‐index modulation. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 216–225, 2002     

Facile formation of chiral calixarene analogs incorporating cystine peptide into the macrocyclic ring

Chiral calixarene analogs incorporating cystine peptide into their macrocyclic ring were easily prepared by the cyclization reactions of bis(chloromethyl)phenol-formaldehyde oligomers with cystine peptides in moderate yields. Circular dichroism (CD) spectra indicated the existence of the transmission of the chirality from peptide unit to phenol-formaldehyde oligomer moiety.