Photo‐capacitance spectroscopy investigation of deep‐level defects in AlGaN/GaN hetero‐structures with different current collapses

We have investigated electronic deep levels in two AlGaN/GaN hetero‐structures with different current collapses grown at 1150 and 1100 °C by a photo‐capacitance spectroscopy technique, using Schottky barrier diodes. Three specific deep levels located at ～2.07, ～2.80, and ～3.23 eV below the conduction band were found to be significantly enhanced for severe current collapse, being in reasonable agreement with photoluminescence and capacitance–voltage characteristics. These levels probably originate in Ga vacancies and residual C impurities and are probably responsible for the current collapse phenomena of the AlGaN/GaN hetero‐structures. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microwave-assisted synthesis of (tris-acetylacetonato)(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline)terbium(III) complex with outstanding high green luminescence

Microwave-assisted synthesis method enabled the preparation of the (tris-acetylacetonate)(2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinate) terbium(III) (Tb(acac)₃(dmdpphen)) complex with outstanding high green luminescence. This method is appropriate for green chemistry and energy-saving processes. The Tb(acac)₃(dmdpphen) complex has good thermal stability. Emission peaks are assigned to the f-f transitions of the Tb³⁺. The Tb(acac)₃(dmdpphen) complex is expected to be used in functional materials of electronic products.     

Synthesis and healing properties of poly(arylether sulfone)–poly(alkylthioether) multiblock copolymers containing disulfide bonds

Thermoplastic elastomers composed of soft and hard segments are important elastic and processable synthetic polymers. The microphase‐separated soft domains show low glass transition temperature and possess sufficient chain mobility at room temperature. In this study, we report the synthesis and healing properties of multiblock copolymers containing disulfide bonds as dynamic covalent bonds. The multiblock copolymers composed of poly(arylether sulfone) and poly(alkylthioether) segments were synthesized by oxidative coupling polymerization of the corresponding thiol‐terminated oligomers. Atomic force microscopy phase images, differential scanning calorimetry, and dynamic mechanical analysis curves indicated the microphase‐separated morphology of the multiblock copolymer. Self‐healing properties of the polymer were evaluated by changes in the elongation at break of the cut/adhered samples. The elongation recovery increased with UV irradiation time, and the multiblock copolymer showed a 93% recovery after UV irradiation for 5 h. The healing efficiency induced by UV irradiation, determined by subtracting the recovery without UV irradiation, was calculated to be 51%. According to the UV spectra and solubility changes after UV irradiation, the main healing factor in this study was the crosslinking reactions caused by thiyl radicals generated from UV irradiation instead of disulfide exchange reactions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3545–3553     

On computational proofs of the existence of solutions to nonlinear parabolic problems

This paper is an extension of the preceding study (Nakao, this journal, 1991) in which we described a numerical verification method of the solution for one-space dimensional parabolic problems, to the several-space dimensional case. Here, numerical verification means the automatic proof of the existence of solutions to the problems by some numerical techniques on a computer. We reformulate the verification condition for nonlinear parabolic initial boundary value problems using the fixed-point problem of a compact operator on certain function spaces. As in the preceding study based upon a simple C⁰ finite-element approximation and its constructive a priori error estimates, a numerical verification procedure is presented with some numerical examples.     

Numerical study of free-piston shock tunnel performance

A free-piston shock tunnel (FPST) is one of the most useful ground testing facilities for hypervelocity flow research of re-entry vehicles and scramjet engines. For an efficient operation with tuned piston motion, the design of facility and the comprehension of the physical phenomena in a FPST, a numerical simulation which can properly predicts the flow with actual losses is required. But there are few successful numerical methods which can simulate its overall performance. In the present study, numerical method was developed by using the KRC shock capturing scheme and by modeling the flow losses in suitable forms for a quasi-1D numerical computation. The present numerical results were compared with the data obtained in two different facilities, T4 and T5. The applicability of the present numerical method as a design tool is discussed briefly.This article was processed using Springer-Verlag T_EX Shock Waves macro package 1.0 and the AMS fonts, developed by the American Mathematical Society.     

Nuclear resonance vibrational spectroscopy reveals the FeS cluster composition and active site vibrational properties of an O2-tolerant NAD+-reducing [NiFe] hydrogenase

Hydrogenases are complex metalloenzymes that catalyze the reversible splitting of molecular hydrogen into protons and electrons essentially without overpotential. The NAD⁺-reducing soluble hydrogenase (SH) from Ralstonia eutropha is capable of H₂ conversion even in the presence of usually toxic dioxygen. The molecular details of the underlying reactions are largely unknown, mainly because of limited knowledge of the structure and function of the various metal cofactors present in the enzyme. Here, all iron-containing cofactors of the SH were investigated by ⁵⁷Fe specific nuclear resonance vibrational spectroscopy (NRVS). Our data provide experimental evidence for one [2Fe2S] center and four [4Fe4S] clusters, which is consistent with the amino acid sequence composition. Only the [2Fe2S] cluster and one of the four [4Fe4S] clusters were reduced upon incubation of the SH with NADH. This finding explains the discrepancy between the large number of FeS clusters and the small amount of FeS cluster-related signals as detected by electron paramagnetic resonance spectroscopic analysis of several NAD⁺-reducing hydrogenases. For the first time, Fe–CO and Fe–CN modes derived from the [NiFe] active site could be distinguished by NRVS through selective ¹³C labeling of the CO ligand. This strategy also revealed the molecular coordinates that dominate the individual Fe–CO modes. The present approach explores the complex vibrational signature of the Fe–S clusters and the hydrogenase active site, thereby showing that NRVS represents a powerful tool for the elucidation of complex biocatalysts containing multiple cofactors.     

Solid‐Phase Combinatorial Synthesis and Biological Evaluation of Destruxin E Analogues

The solid‐phase combinatorial synthesis of cyclodepsipeptide destruxin E has been demonstrated. The combinatorial synthesis of cyclization precursors 8 was achieved by using a split and pool method on SynPhase Lanterns. The products were successfully macrolactonized in parallel in the solution phase by using 2‐methyl‐6‐nitrobenzoic anhydride and 4‐(dimethylamino)pyridine N‐oxide to afford macrolactones 9 , and the subsequent formation of an epoxide in the side chain gave 18 member destruxin E analogues 6 . Biological evaluation of analogues 6 indicated that the N‐MeAla residue was crucial to the induction of morphological changes in osteoclast‐like multinuclear cells (OCLs). Based on structure–activity relationships, azido‐containing analogues 15 were then designed for use as a molecular probe. The synthesis and biological evaluation of analogues 15 revealed that 15 b , in which the Ile residue was replaced with a Lys(N₃) residue, induced morphological changes in OCLs at a sufficient concentration, and modification around the Ile residue would be tolerated for attachment of a chemical tag toward the target identification of destruxin E ( 1 ).     

Scrambled Self‐Assembly of Bacteriochlorophylls c and e in Aqueous Triton X‐100 Micelles

Bacteriochlorophyll (BChl) e was coassembled with BChl c in Triton X‐100 micelles in aqueous solutions. The Q_y absorption bands of the coaggregates were positioned between those of aggregates consisting solely of BChl c or e. The electronic absorption spectra of the coaggregates could not be reproduced by linear combinations of the spectra of the aggregates consisting solely of each pigment, but they were in line with the simulated spectra for the self‐aggregates in which both BChls were randomly distributed. These suggest that BChls c and e are not spatially separated; they are homogenously distributed over the self‐aggregates to give electronic spectra that are different from those of the aggregate consisting solely of each pigment. Deaggregation of the scrambled self‐aggregates by excess Triton X‐100 did not produce any spectral components assigned to an aggregate consisting solely of either BChl c or e. Acid‐induced decomposition of the scrambled aggregates showed different kinetics from those of the aggregates consisting solely of each pigment. These also support the homogeneous distribution of BChls c and e in the scrambled self‐aggregates. These results will be useful to investigate the major light‐harvesting antenna systems of green photosynthetic bacteria that contain two kinds of chlorosomal BChls.     

Magnetic ordering of divalent europium in double perovskites Eu2LnTaO6 (Ln=rare earths): Magnetic interactions of Eu ions determined by magnetic susceptibility, specific heat, and Eu Mössbauer spectrum measurements

Structures and magnetic properties of double perovskite-type oxides Eu₂LnTaO₆ (Ln=Eu, Dy-Lu) were investigated. These compounds adopt a distorted double perovskite structure with space group P2₁/n. Magnetic susceptibility, specific heat, and ¹⁵¹Eu Mössbauer spectrum measurements show that the Eu²⁺ ions at the 12-coordinate sites of the perovskite structure are antiferromagnetically ordered at ∼4 K, and that Ln³⁺ ions at the 6-coordinate site are in the paramagnetic state down to 1.8 K.