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.     

Selective oxidation of benzene to phenol with molecular oxygen on rhenium/zeolite catalysts

Zeolite-supported rhenium catalysts are active for selective oxidation of benzene with molecular oxygen, where coexisting ammonia is prerequisite to the direct phenol synthesis.     

Synthesis of surface organopalladium intermediates in coupling reactions: the mechanistic insight

The design and synthesis of surface transient organometallic intermediates on nanopalladium supported on layered double hydroxides is conceived and developed for the first time. The formation of only one STO intermediate in all the Heck-, Suzuki-, Sonogashira-, and Stille-type coupling reactions during their reaction sequences and the excellent isolated yields of each of the coupling products from the corresponding organometallic complexes not only validate the mechanism but also demonstrate the evolution of the single-site heterogeneous catalyst.     

Synthesis of 1-haloethenamides from ynamide through halotrimethylsilane-mediated hydrohalogenation

A convenient synthesis of 1-haloethenamides has been achieved by utilizing halotrimethylsilane (TMSX, X = Cl, Br, I) and water. Halotrimethylsilane in 1 M CH₂Cl₂ solution functions as a halogen source of the in situ generated HX, and the HX added to the terminal triple bonds of ynamides in Markovnikov fashion.     

Rhodium(I)-catalyzed direct carboxylation of arenes with CO2 via chelation-assisted C-H bond activation

Rh-catalyzed direct carboxylation of unactivated aryl C-H bond under atmospheric pressure of carbon dioxide was realized via chelation-assisted C-H activation for the first time. Variously substituted and functionalized 2-arylpyridines and 1-arylpyrazoles underwent the carboxylation in the presence of the rhodium catalyst and a stoichiometric methylating reagent, AlMe(2)(OMe), to give carboxylated products in good yields. The catalysis is proposed to consist of methylrhodium(I) species as the key intermediate, which undergoes C-H activation to afford rhodium(III), followed by reductive elimination of methane to give nucleophilic arylrhodium(I). This approach demonstrates promising application of C-H bond activation strategy in the field of carbon dioxide fixation.