Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...     

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.     

Discrimination of carbonyl groups of meso-α-diketones with Horner-Wadsworth-Emmons reagent of chiral binaphthyl esters

Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described.     

FMS scheduling based on timed Petri Net model and reactive graph search

This paper presents a new scheduling method for manufacturing system based on the Timed Petri Net model and a reactive fast graph search algorithm. The following two typical problems are addressed in this paper. (1) Minimization of the maximum completion time. (2) Minimization of the total tardiness. As for the problem (1), a new search algorithm which combines the RTA^∗ and a rule-based supervisor is proposed. As for problem (2), the original Petri Net model is converted to its reverse model and the algorithm developed for the problem (1) is applied, regarding the due date as the starting time in the reverse model. Some numerical experiments are carried out to demonstrate usefulness of our algorithm.     

Application of novel SIMS technique for imaging the active sites of oxygen reduction at the SOFC cathode/electrolyte interfaces

The oxygen reduction active sites were visualized around the O₂/SOFC cathode/electrolyte triple phase boundaries (TPB) by the¹⁶O/¹⁸O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher¹⁸O concentration is observed on the cathode top surfaces (La_0.9Sr_0.1MnO₃-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode. The oxygen diffusion through the bulk of cathode occurred at the La_0.9Sr_0.1MnO₃-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La_0.9Sr_0.1MnO₃/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation is less than a few μm from the TPB lines. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Lattice path combinatorics and asymptotics of multiplicities of weights in tensor powers

We give asymptotic formulas for the multiplicities of weights and irreducible summands in high-tensor powers V_λ^⊗N of an irreducible representation V_λ of a compact connected Lie group G. The weights are allowed to depend on N, and we obtain several regimes of pointwise asymptotics, ranging from a central limit region to a large deviations region. We use a complex steepest descent method that applies to general asymptotic counting problems for lattice paths with steps in a convex polytope.     

Efficient synthesis of CCR5 antagonist, 2,3-dihydro-1-benzothiepine derivatives by improved intramolecular Claisen type reaction using dialkylcarbonate

The efficient synthesis of 2,3-dihydro-1-benzothiepine derivatives 4 has been developed. The intramolecular Claisen type reaction of the new products, 4-(o-formylphenylthio)butyrate 9, with alcoholate in dialkylcarbonate as a solvent afforded 4 in good yields. According to this new procedure, we have accomplished the practical preparation of CCR5 antagonist 1 as a candidate for oral HIV-1 therapy.     

Systematic enantiomeric separation of [60]fullerene bisadducts possessing an inherent chiral addition pattern

The optical resolution of trans-2 and trans-3 [60]fullerene bisadducts with an inherent chiral addition pattern, modified by Bingel reaction, cycloaddition by benzyne, Prato reaction, and cycloaddition by o-quinodimethane, was systematically investigated by using chiral HPLC columns (Chiralcel OD and Chiralpak AD). The chiroptical properties of enantiomers separated were also examined.