Reaction of an Introverted Carboxylic Acid with Carbodiimide

The reaction of carboxylic acids with carbodiimides is reviewed, and an ‘introverted’ carboxylic acid is proposed as a means of trapping reactive intermediates along the reaction pathway. The introverted acid is a cavitand with the carboxylic function directed toward the floor of the cavity. Its reaction with diisopropyl carbodiimide gives a covalent adduct that is either the elusive O-acylisourea or the commonly encountered N-acylurea.     

High resolution images of Mo2C(0001)- structure by scanning tunneling microscopy

A C-terminated structure on Mo₂C(0001) was observed by scanning tunneling microscopy. The structure was observed as a honeycomb structure with dark depressions corresponding to C atoms which make up the lattice. High resolution imaging was possible at low tunneling resistance less than 1 MΩ. Each C atom appears as a shallow sombrero protrusion predicted by theoretical calculations of C atoms on a metal substrates. It is concluded that the C atoms occupied threefold hollow sites of the (1×1) Mo layer of the substrate and a model for the structure is proposed.     

Imaging of atomic-scale structure of oxide surfaces and adsorbed molecules by noncontact atomic force microscopy

Atom-resolved images of a TiO₂(110)-(1×1) surface and individual formate and acetate ions adsorbed on the surface were obtained by noncontact atomic force microscopy (NC-AFM) in ultrahigh vacuum. In contrast to previous scanning tunneling microscopic studies imaging five-fold coordinated Ti atoms, outermost atoms of bridge-bound oxygen ridges of the surface were resolved as protruding rows by NC-AFM. High-resolution image of the surface revealed that the bridging oxygen atoms on terraces ordered in a (1×1) periodicity. Randomly distributed point and multiple defects of oxygen atoms were also imaged as dark spots. The (2×1) overlayer of formate and acetate ions were resolved as ordered bright spots. Dispersed formate ions at a low coverage were also observed as bright spots between the bridging oxygen ridges along the [001] direction.     

Highly sodium-selective fluoroionophore based on conformational restriction of oligoethyleneglycol-bridged biaryl boron-dipyrromethene

A non-PET and non-PCT fluoroionophore has been designed and synthesized based on the combination of a biaryl boron-dipyrromethene fluorophore with an oligoethyleneglycol bridge. A specific red-shift response of absorption for NaClO4 in acetonitrile was demonstrated based on conformational restriction triggered by cation recognition at the bridge. The concentration of Na+ can be determined accurately using fluorescence due to a high extinction coefficient (epsilon = 50 000), a high fluorescence quantum yield (Phif = 0.68), and the sharpness of absorption and emission peaks of the boron-dipyrromethene derivative.     

Preparation,characteristics, and application of an asparaginase tube

Conditions for the preparation of an asparaginase (L-asparagine amidohydrolase, EC 3.5.1.1) tube using polyacrylamide gel were investigated. The apparent yield of activity of the asparaginase tube was about 20%; the activity of the tube was dependent on inner surface area. The optimum pH of the asparaginase tube shifted by 1 pH unit to the acid side in comparison with that of native enzyme. The apparent Michaelis constant of the tube was about 200 times higher than that of the native enzyme. The half-life of the asparaginase tube in continuous operation was estimated to be 16 days at 37°C. The tube was found to be resistant to attack by proteolytic enzyme. The L-asparagine level in blood plasma of a dog was lowered to 1/4 by the performance of an extracorporeal shunt using the asparaginase tube.     

Bidentate amidine ligands for nickel(0)-mediated coupling of carbon dioxide with unsaturated hydrocarbons

Novel bidentate amidines were designed and synthesized as easily available electron-donating N-ligands for Ni0-mediated coupling of carbon dioxide with alkynes or allenes, and high regioselectivity was achieved even for the carboxylation of aryl substituted internal alkynes.