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.     

On Potentially Abelian Geometric Representations

The finiteness is proved of the set of isomorphism classes of potentially abelian geometric Galois representations with a given set of data. This is a special case of the finiteness conjecture of Fontaine and Mazur.     

Achievement of laser fusion of biological cells using UV pulsed dye laser beams

This paper reports a successful achievement of laser-induced biological cell fusion using an excimer laser excited dye laser. To our knowledge, we examined for the first time the dependence of fusion rate on laser pulse energy, number of laser pulses, and laser wavelength. Maximum fusion rate of approximately 50% was obtained by this laser fusion technology.     

Micro-phase sorbent extraction for trace analysis via in situ sorbent formation: application to the spectrophotometric determination of nitrite in environmental waters.

A micro-phase sorbent in situ formation from an aqueous solution was proposed for the sensitive spectrophotometric determination of nitrite in environmental waters. Nitrite in a 10 mL sample solution was converted into a cationic azo dye by the reaction with 4-trifluoromethylanilinium ion and N-1-naphthylethylenediammonium ion in an acidic medium. Addition of dodecylbenzenesulfonate ion caused the formation of a suspension of ion associate in the solution. Centrifugation of the solution led to the isolation of a liquid organic phase that extracted the azo dye at the bottom of the centrifuge tube. The volume of the new phase was ca. 5 microL. After the aqueous phase was discarded, the organic phase was dissolved with 1 mL of 2-methoxyethanol to measure the absorbance. Nitrogen as NO2- at concentrations from 1.5 to 30 microg L(-1) was determined with sufficient precision. When 0.2 mL of 2-methoxyethanol was applied to dissolve the organic phase, 0.3-4.8 microg NO2--N L(-1) was determined. The recovery tests for nitrite added to some river water and seawater were satisfactory. This method is very simple and rapid. It takes only 30 min from the dye formation to the measurement of the absorbance.     

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.     

Lewis acid promoted reactions of γ,γ-dialkoxyallylic zirconium species with various carbonyl compounds

The reactions of γ,γ-dialkoxyallylic zirconium species with carbonyl compounds in the presence of Lewis acid are reported. The reactivity of γ,γ-dialkoxyallylic zirconium species and reaction pathway were strongly dependent on the structure and electrostatic nature of the carbonyl compounds.