Volume 89, Issue 7, July 2016

The activation process of the coupled dinuclear copper proteins such as tyrosinase remained to be clarified until lately. Thorough understanding of its molecular mechanism as well as the phenolase reaction mechanism is provided on the basis of the crystal structures.

Visible light sensitive heterogeneous photocatalyst for generation of H₂ was successfully designed by utilization of 4-sulfocalix[4]arene as a linker molecule for stable immobilization of 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrinatozinc(II) ion on Pt-loaded TiO₂.

The moment theory was developed to analytically determine association and dissociation rate constants from elution peaks measured by affinity capillary electrophoresis (ACE). Ample ACE data previously published can be used as a source for kinetic study of intermolecular interactions.

A fluorescent probe RO is fruitfully explored for the turn “off–on” recognition of Cu²⁺ and Cys in aqueous media with high sensitivity. The spectral observations were translated into an IMP molecular logic system. The RO also exhibited efficient bio-imaging of Cu²⁺ and Cys in E. coli cells.

We report the results of an experimental and computational study of adamantylideneadamantane (1). Calorimetric experiments provided the standard enthalpy of formation of 1. FT-ICR spectroscopy allowed the determination of the gas phase basicity of 1. These properties and the ionization potentials of 1 were computationally studied at the MP2/6-311+G(d,p) and/or G3 levels. Comparison with the reactivity of simple alkenes is given.

Coupled-cluster calculations were performed for cyclobutane-1,3-diylidene dicarbenes. The closed-shell singlet state with a bicyclo[1.1.0]but-1(3)-ene (BBE) structure found to be the ground-state was much lower in energy than other spin states.

DOPO–Mg changed the thermal degradation process of the PIR–PUR foam and prevented a kind of highly toxic flammable gas from being generated. DOPO–Mg can effectively produce spherical material covering the surface of the char to hinder flame and energy transmission in the condensed phase. The FTIR spectra of the pyrolytic gas products at 540 °C.

We demonstrated that demolding in ultraviolet (UV) nanoimprinting was assisted by a nanoscale lubricating fluid layer of a liquefied 1,1,1,3,3-pentafluoropropane (PFP) gas. UV-curable Resin A composed of glycerol 1,3-diglycerolate diacrylate with low PFP absorption showed low surface roughness of 22-nm line-and-space imprint patterns with the smallest line edge roughness (LER) value of 3σ = 1.8 nm.

A reusable ionic liquid 1-butyl-3-methylimidazolium bromide/Cu(II) system was proven to be a reusable catalyst for the homocoupling of terminal alkynes at mild temperature using air as oxidant in aqueous phase or under solvent-limited conditions. In most cases, good to excellent yields can be achieved. Furthermore, this reaction can be easily scaled up to gram level.

Mesolysis profiles due to the C–O bond cleavage in benzyl phenyl ether radical anions generated during electron pulse radiolysis in DMF were investigated based on transient absorption measurements at various temperatures and DFT calculations. The Arrhenius parameters for the mesolysis were determined. The mesolysis was shown to proceed via a stepwise mechanism.

The dynamically calculated lifetime distributeon contains a large number of short lifetime trajectories at t < 50 fs. By analyzing the nature of these short lifetime trajectories, we found that a transferred proton can be trapped between two carbon atoms. Based on these analysis, the concept of “dynamically stable trapped state” is proposed.

The first example of abnormal Michael reaction of an active methylene compound, 2-acylmethyl-4,4-dimethyl-2-oxazoline, with acetylenic ketone in acetonitrile is reported. Selectivity of the reaction depends on bulkiness of all the substituents of both the substrate and the reagent.

(3-Aminopropyl)trimethoxysilane (APS)-silica gels were prepared by a one-pot process using sodium silicate as a low-cost source of silica. After introducing several surfactants, the adsorption properties of gels were improved. By comparison of the pore and CO₂ uptake properties, we confirmed that P123 was a suitable surfactant for the preparation of APS-silica gel by a one-pot process using sodium silicate as the silica source.

The microwave specific effect on the catalytic atropo-enantioselective ring-opening reaction of biaryl lactones was investigated. Under strictly controlled temperature conditions, the reaction was accelerated by microwave irradiation without any loss of the enantioselectivity. Also, it was revealed that the racemization rate of the atropo-optically active biaryl lactone was enhanced by the microwave irradiation.

We have found out that the near-IR spectroscopic behavior of [Ni(iPr₂timdt)₂] depends on the properties (coordination property, relative permittivity) of organic solvents.