The theoretical study for the perovskite-type manganese fluorides of KMnF3, RbMnF3 and K1−xLixMnF3

We performed the hybrid-density functional theory (DFT) calculations for the strongly correlated perovskite-type manganese fluorides of KMnF₃, RbMnF₃ and K_1?xLi_xMnF₃ In both solids, UBHHLYP, which contains 50% Hartree–Fock exchange term, provided the reasonable effective exchange integral (J_ab) values, in comparison with the experimental ones. In order to investigate the intrinsic roles of counter cations precisely, we examined the variations of the total energy and J_ab value, assuming the displacement of counter cation toward <1 0 0> direction. In KMnF₃ (RbMnF₃), it was found that the steric repulsion between potassium (rubidium) and bottleneck is large, while that between lithium and bottleneck is negligible in K_1?xLi_xMnF₃. Finally, we also showed the possibility of the lithium ion conduction in the antiferromagnetic K_1?xLi_xMnF₃. It was concluded that the lithium ion conduction in RMnF₃ is possible, if the vacancy at R site exists.     

Large-scale forcing with less communication in finite-difference simulations of stationary isotropic turbulence

This study proposes a new forcing scheme suitable for massively-parallel finite-difference simulations of stationary isotropic turbulence. The proposed forcing scheme, named reduced-communication forcing (RCF), is based on the same idea as the conventional large-scale forcing scheme, but requires much less data communication, leading to a high parallel efficiency. It has been confirmed that the RCF scheme works intrinsically in the same manner as the conventional large-scale forcing scheme. Comparisons have revealed that a fourth-order finite-difference model run in combination with the RCF scheme (FDM-RCF) is as good as a spectral model, while requiring less computational costs. For the range 80 < Re_λ < 540, where Re_λ is the Taylor microscale-based Reynolds number, large computations using the FDM-RCF scheme show that the Reynolds dependences of skewness and flatness factors have similar power-laws as found in previous studies.     

The role of spin-orbit potential in nuclear prolate-shape dominance

It is confirmed, in terms of the Woods-Saxon-Strutinsky method, that the spin-orbit potential plays a decisive role in the predominance of prolate deformation, which has been a long standing problem in nuclear physics. It is originated from the combined effects of the spin-orbit coupling and the diffused surface of the potential, in agreement with the previous work based on a more schematic Nilsson-Strutinsky method. The degree of prolate-shape dominance exhibits an oscillatory behavior with respect to the strength of spin-orbit potential and, the prolate-shape dominance is realized at the proper strength of the spin-orbit potential together with the standard surface diffuseness; this oscillatory behavior disappears in case of small diffuseness corresponding to ellipsoidal cavity. The calculated energy differences between oblate and prolate minima in this Letter are consistent with those of our extensive self-consistent calculations of the Hartree-Fock + BCS method with the Skyrme interaction.     

Synthesis of end‐functionalized poly(phenylacetylene)s with well‐characterized palladium catalysts

End‐functionalized poly(phenylacetylene)s were synthesized by the polymerization of phenylacetylene (PA) using the well‐defined palladium catalysts represented as [(dppf)PdBr(R)] {dppf = 1,1′‐bis(diphenylphosphino)ferrocene}. The Pd catalysts having a series of R groups such as o‐tolyl, mesityl, C(Ph)?CPh₂, C₆H₄‐o‐CH₂OH, C₆H₄‐p‐CN, and C₆H₄‐p‐NO₂ in conjunction with silver triflate polymerized PA to give end‐functionalized poly(PA)s bearing the corresponding R groups in high yields. The results of IR and NMR spectroscopies and MALDI‐TOF mass analyses proved the introduction of these R groups at one end of each polymer chain. The poly(PA) bearing a hydroxy end group was applied as a macroinitiator to the synthesis of a block copolymer composed of poly(PA) and poly(β‐propiolactone) moieties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Accurate and sensitive high-performance liquid chromatographic method for geometrical and structural photoisomers of bilirubin IX alpha using the relative molar absorptivity values.

It has been reported that considerable differences exist between the relative molar absorptivity values of the geometrical and structural photoisomers of bilirubin. We have devised an accurate HPLC method for photoisomer quantification based on the following principle: the sum of both the integrated peak areas corrected by each factor for each photoisomer, and the integrated peak area of unchanged (ZZ)-bilirubin [(ZZ)-B] after an anaerobic photoirradiation, should be constant and equal to the integrated peak area of initial (ZZ)-bilirubin [(ZZ)-Bi] before photoirradiation. On this basis, the following equation can be used to determine each factor. [equation: see text] alpha, beta, gamma and delta represent the factors used to correct the integrated peak areas of individual bilirubin photoisomers, and they are arranged in the order of the formula. It was demonstrated that the relative 455 nm molar absorptivity values for (ZZ)-bilirubin and all its geometrical and structural photoisomers, i.e., (ZZ)-bilirubin, (ZE)-bilirubin (EZ)-bilirubin, (EZ)-cyclobilirubin (= lumirubin) and (EE)-cyclobilirubin in the HPLC eluent, are, respectively, 1.0, 0.81 (= alpha), 0.54 (= beta), 0.47 (= gamma) and 0.39 (= delta).     

Reaction Intermediates on TiO2(110) Identified by Time-Lapse Scanning Tunneling Microscopy

The present account describes first time examples of scanning tunneling microscope (STM) visualization of reaction intermediates on a metal oxide surface. The topographic response of reactant-adsorbed TiO₂(110) surfaces to a temperature increment or to a pressure increment was monitored as a sequence of STM images. Acetates thermally decomposing to ketene were resolved in a temperature-jump STM observation. The kinetics of the acetate consumption was determined on the number of acetates resolved in the microscope images and agreed with the macroscopic rate law of ketene production. A pressure-jump study revealed how a chemisorbed carboxylate (RCOO^-) is exchanged by another carboxylate (R'COO^-) supplied from the ambient vapor phase. An impinging R'COOH was immobilized on the top of a RCOO^- and then squeezed itself into the monolayer of the RCOO^-. One of the carboxylates in the squeezed state returned to the vapor phase via the immobilized state.     

Mechanistic Studies of the Radical S‐Adenosylmethionine Enzyme DesII with TDP‐D‐Fucose

DesII is a radical S‐adenosylmethionine (SAM) enzyme that catalyzes the C4‐deamination of TDP‐4‐amino‐4,6‐dideoxyglucose through a C3 radical intermediate. However, if the C4 amino group is replaced with a hydroxy group (to give TDP‐quinovose), the hydroxy group at C3 is oxidized to a ketone with no C4‐dehydration. It is hypothesized that hyperconjugation between the C4 C? N/O bond and the partially filled p orbital at C3 of the radical intermediate modulates the degree to which elimination competes with dehydrogenation. To investigate this hypothesis, the reaction of DesII with the C4‐epimer of TDP‐quinovose (TDP‐fucose) was examined. The reaction primarily results in the formation of TDP‐6‐deoxygulose and likely regeneration of TDP‐fucose. The remainder of the substrate radical partitions roughly equally between C3‐dehydrogenation and C4‐dehydration. Thus, changing the stereochemistry at C4 permits a more balanced competition between elimination and dehydrogenation.     

Fabrication of high-aspect-ratio polymer microstructures and hierarchical textures using carbon nanotube composite master molds

Scalable and cost effective patterning of polymer structures and their surface textures is essential to engineer material properties such as liquid wetting and dry adhesion, and to design artificial biological interfaces. Further, fabrication of high-aspect-ratio microstructures often requires controlled deep-etching methods or high-intensity exposure. We demonstrate that carbon nanotube (CNT) composites can be used as master molds for fabrication of high-aspect-ratio polymer microstructures having anisotropic nanoscale textures. The master molds are made by growth of vertically aligned CNT patterns, capillary densification of the CNTs using organic solvents, and capillary-driven infiltration of the CNT structures with SU-8. The composite master structures are then replicated in SU-8 using standard PDMS transfer molding methods. By this process, we fabricated a library of replicas including vertical micro-pillars, honeycomb lattices with sub-micron wall thickness and aspect ratios exceeding 50:1, and microwells with sloped sidewalls. This process enables batch manufacturing of polymer features that capture complex nanoscale shapes and textures, while requiring only optical lithography and conventional thermal processing.     

Synthesis and drug-release characteristics of the conjugates of mitomycin C with N-succinyl-chitosan and carboxymethyl-chitin.

By condensation of mitomycin C (MMC) with N-succinyl-chitosan (Suc-chitosan) and carboxymethyl-chitin (CM-chitin) using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, Suc-chitosan-MMC conjugate (Suc-chitosan-MMC) and CM-chitin-MMC conjugate (CM-chitin-MMC) were prepared, respectively. The reaction conditions for 45 min at pH 5 and for 2 h at pH 5 were selected as the most appropriate for the preparations of Suc-chitosan-MMC and CM-chitin-MMC, respectively. Suc-chitosan-MMC was obtained as a water-insoluble product, while CM-chitin-MMC was partially water-soluble. When the ratio of MMC to the polymer supports changed in the conjugation reaction, the conjugates with 33% (w/w) and 23% (w/w) MMC contents were obtained as those most highly drug-loaded for Suc-chitosan-MMC and CM-chitin-MMC, respectively. At pH 7.4 at 37 degrees C, Suc-chitosan-MMC regenerated MMC very slowly, while the release of MMC from CM-chitin-MMC was relatively fast. Each drug release followed very nearly pseudo-first order kinetics, in which the apparent drug release rate constants (k(apps)) of Suc-chitosan-MMC and CM-chitin-MMC were 3.9 x 10(-3) and 1.1 x 10(-1) (h-1), respectively.