Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Microstructural stability and age-hardening behavior of Re-added dual two-phase Ni3Al and Ni3V intermetallic alloys

The effect of Re addition on the microstructure and hardening behaviour of the dual two-phase Ni₃Al (L1₂) and Ni₃V (D0₂₂) intermetallic alloy was investigated by scanning electron microscopy, transmission electron microscopy and Vickers hardness test. The two-phase eutectoid microstructure accompanying the Re-rich precipitates were observed in the channel region of the alloys in which Re substituted for Ni but not in those in which Re substituted for Al and V. The concomitant addition of Nb (or Ta) with Re more stabilized the two-phase eutectoid microstructure and consequently more induced the fine precipitates in the channel region. The annealing at temperatures below the eutectoid temperature was necessary to induce the fine precipitates in the channel region and thereby result in the precipitation hardening. The fine precipitation in the channel region and related hardening was attributed to the alloying feature so that Re is soluble in the A1 (fcc) phase at high temperatures and becomes less soluble in the two intermetallic phases decomposed from the A1 phase at low temperatures.     

Rational Molecular Design towards Vis/NIR Absorption and Fluorescence by using Pyrrolopyrrole aza‐BODIPY and its Highly Conjugated Structures for Organic Photovoltaics

Pyrrolopyrrole aza‐BODIPY (PPAB) developed in our recent study from diketopyrrolopyrrole by titanium tetrachloride‐mediated Schiff‐base formation reaction with heteroaromatic amines is a highly potential chromophore due to its intense absorption and fluorescence in the visible region and high fluorescence quantum yield, which is greater than 0.8. To control the absorption and fluorescence of PPAB, particularly in the near‐infrared (NIR) region, further molecular design was performed using DFT calculations. This results in the postulation that the HOMO–LUMO gap of PPAB is perturbed by the heteroaromatic moieties and the aryl‐substituents. Based on this molecular design, a series of new PPAB molecules was synthesized, in which the largest redshifts of the absorption and fluorescence maxima up to 803 and 850 nm, respectively, were achieved for a PPAB consisting of benzothiazole rings and terthienyl substituents. In contrast to the sharp absorption of PPAB, a PPAB dimer, which was prepared by a cross‐coupling reaction of PPAB monomers, exhibited panchromatic absorption across the UV/Vis/NIR regions. With this series of PPAB chromophores in hand, a potential application of PPAB as an optoelectronic material was investigated. After identifying a suitable PPAB molecule for application in organic photovoltaic cells based on evaluation using time‐resolved microwave conductivity measurements, a maximized power conversion efficiency of 1.27 % was achieved.     

Optical separation of racemic 5-(p-hydroxyphenyl)-5-phenylhydantoin by reversed phase high-performance liquid chromatography using eluents containing beta-cyclodextrin.

Both S-(-)- and R-(+)-enantiomers of 5-(p-hydroxyphenyl)-5-phenylhydantoin (p-HPPH), a main oxidative metabolite of the achiral antiepileptic drug phenytoin, could be determined simply, sensitively and accurately using reversed phase high-performance liquid chromatography by using a methanol-monopotassium phosphate eluent containing beta-cyclodextrin. Using this assay procedure, it was determined that an S-(-)-enantiomer was formed predominantly by the oxidation of phenytoin in isolated rat hepatocytes.     

Synthesis of 5-heteroarylazulenes: first selective electrophilic substitution at the 5-position of azulene

1,3-Di-tert-butylazulene reacted with highly electrophilic trifluoromethanesulfonate of N-containing heterocycles to give 5-(dihydroheteroaryl)azulene derivatives in good yield and treatment of the 5-(dihydroheteroaryl)azulene derivatives with KOH afforded 5-(heteroaryl)azulenes in excellent yield.     

The origin of enhanced photocatalytic decomposition of ATP on TiO2 powders as induced by surface modification with lanthanide ions: important roles of ATP adsorption to the modified surface

Surface modification of TiO₂ powders with lanthanide salts (EuCl₃ or YbCl₃) enhanced photocatalytic decomposition of ATP. In comparison with the unmodified catalyst, a 3-fold increase in the ATP decay rate was observed with TiO₂ powders as prepared in 5 mM EuCl₃ (or YbCl₃) solution. The reason was ascribed to enrichment of ATP to TiO₂ powder with the lanthanide ions. Evidence was obtained by adsorption experiments where ATP concentration was monitored after dispersing TiO₂ powders into the solution. The ATP molecules adsorbed faster to TiO₂ powder and strongly stabilized there in the presence of Yb³⁺ than otherwise.     

Pressure response of Raman spectra of water and its implication to the change in hydrogen bond interaction

In situ Raman spectroscopic measurements of water in the region of OH vibration were conducted up to 0.4 GPa at 23 and 52 degrees C. The frequencies of the decomposed OH stretching bands initially decreased with increasing pressure, reached a minimum at 0.15 GPa and increased up to 0.3 GPa and then decreased, which corresponds to the variations of the strength of hydrogen bonding. This variation was observed at 23 degrees C, but not at 52 degrees C, which suggests a change in pressure dependence on the hydrogen bond interaction between these two temperatures. Based on the equilibration model between hydrogen-bonded and nonhydrogen-bonded molecules, the present experimental results indicate that the pressure variation of the viscosity depends on the ratio of hydrogen-bonded molecules, rather than the strength of hydrogen bonding between molecules.     

Preparation of Layer Structure-Controlled Ru-Sn-Al2O3 Catalysts and Their Reactivity

In order to achieve functional group selective hydrogenation, the layer structure of Ru-Sn-Al2O3 catalysts was controlled by using sol-gel, powder impregnation and combined sol-gel impregnation methods. The properties of the catalysts and effectiveness in hydrogenation of dimethyl terephthalate were examined. The surface Sn contents of the catalysts characterized by X-ray photoelectron spectroscopy depended on the preparation method, in spite of almost the same bulk Ru and Sn compositions measured by X-ray fluorescence analyses. TPR and CO adsorption of the catalysts also depended on the preparation method. With regard to the conversion rate of dimethyl terephthalate and the rate of product conversion from methyl 4-hydroxy methylbenzoate to p-xylene via methyl p-toluate, Ru impregnation catalysts had higher rates than the other catalysts.