Artificial photochemical nitrogen cycle to produce nitrogen and hydrogen from ammonia by platinized TiO2 and its application to a photofuel cell

Photochemical artificial nitrogen cycle was reported to produce dinitrogen and dihydrogen by photodecomposing ammonia with platinized TiO2, and its application to a photofuel cell with a nanoporous TiO2 film electrode, a new concept of a fuel cell to photochemically produce electricity and H2 from ammonia, was proposed.     

Formal total synthesis of (±)-magellanine

Formal total synthesis of magellanine is described. Key features in the synthesis were stereoselective Ireland-Claisen rearrangement and intramolecular Pauson-Khand reaction of exo-cyclic enynes.     

Fission product separation from seawater by electrocoagulation method

At the Fukushima Daiichi nuclear power station, seawater was urgently injected into the reactor core. Therefore a large amount of seawater containing highly radioactive fission products (FP) accumulated and its treatment has been a serious problem. FP such as Cs, Sr and I in water are generally removed by an ion exchanger such as zeolite and separated with column or chemical precipitation methods. An alternative electrocoagulation method, which efficiently separates fine particles from the liquid phase without a chemical reagent is expected to be part of a useful separation system that can reduce the amount of waste, decrease processing time and simplify the process. In this study, powdered adsorbents, such as ferrocyanide and zeolite, were added to seawater containing simulated FP, and the electrocoagulation effect with Al alloy electrodes were investigated. More than 99 % of Cs and 90 % of I were removed by potassium nickel hexacyanoferrate(II) and silver zeolite, respectively. Sedimentation was promoted by electrocoagulation and addition of an inorganic cohesion promoter further increased the sedimentation rate. Moreover, rapid dissolution reaction with heating of the aggregation substance was not observed, so the thermal risk of aqueous processing of it would be low. In addition, thermal analyses showed that the electrocoagulation process did not lead to thermal decomposition. Therefore, if the electrocoagulation method is applied to a decontamination system, it has the potential to thermally stabilize and reduce waste.     

First EMC3-EIRENE modelling of JT-60SA edge plasmas with/without resonant magnetic perturbation field

The first EMC3-EIRENE modelling for the JT-60SA edge plasmas with/without the resonant magnetic perturbation field (RMP) was conducted. Both core degradation in the vacuum approximation and strike-point splitting were observed due to the application of the RMP, as in previous studies in other devices. Toroidally averaged divertor heat fluxes with and without the RMP were fitted by using a one-dimensional diffusive model function, showing similar profiles. To extract the modulation components of the divertor heat flux profile, the proper orthogonal decomposition (POD) method was applied. By using the POD outputs, a modulation ratio with respect to the toroidally averaged profile was quantitatively calculated.     

The use of water structure breakers, urea and guanidium chloride, new mobile phase modifiers in reversed-phase partition high-performance liquid chromatography.

Organic solvent-free mobile-phase systems in ion-pair reversed-phase partition high-performance liquid chromatography (IPRP-HPLC) are demonstrated; using urea at 3.0-7.0 molal (mol kg-1) as a modifier in a mobile phase on an octadecylsilanized silica column, four nitrophenolates and metal 4-(2-pyridilazo)resorcinol (PAR) chelates (in PAR chelates system an aqueous mobile phase with 15 wt% methanol was used) were separated rapidly within 6 min at no sacrifice to the separation efficiency. On the addition of urea in the mobile phase, reduced retention times of nitrophenolates and naphthalenesulfonates and also diminution of the height equivalent to a theoretical plate were observed. The addition of urea and guanidium chloride (GuCl) in the mobile phase gave rise to a decrease in the mobile phase volume; in turn, this meant an increased volume of the stationary phase. As the concentration of urea and GuCl in the mobile phase increased, the volume of the mobile phase in the column decreased within about 70% and 40% at 7.0 molal of urea and GuCl, respectively. A decrease in the mobile phase volume suggests an increase in the extent of solvation of the bonded hydrocarbon chain of the stationary phase. The possible explanations for the LC behavior with the urea and GuCl are turned into reduction of hydrophobic interaction in LC processes, solute partitioning and entangling of alkyl chain brushes, with the addition of urea. The water structure breakers, urea and GuCl, most likely affect the solvation states of both solute molecules and the hydrocarboneous stationary phase by changing the nature of the water solvent, which provides a new technique for fine tuning of the LC resolution of the analytes.     

Highly Regioselective 5-endo-tet Cyclization of 3,4-Epoxy Amines into 3-Hydroxypyrrolidines Catalyzed by La(OTf)3

Highly regioselective intramolecular aminolysis of 3,4-epoxy amines has been achieved. Key features of this reaction are (1) chemoselective activation of epoxides in the presence of unprotected aliphatic amines in the same molecules by a La(OTf)₃ catalyst and (2) excellent regioselectivity for anti-Baldwin 5-endo-tet cyclization. This reaction affords 3-hydroxy-2-alkylpyrrolidines stereospecifically in high yields. DFT calculations revealed that the regioselectivity might be attributed to distortion energies of epoxy amine substrates. The use of this reaction was demonstrated by the first enantioselective synthesis of an antispasmodic agent prifinium bromide.