Intermolecular propargyl/allenyl group transfer from Pd(II) to Pt(0) and Pt(II) to Pd(0). Key reaction in metal-catalyzed isomerization between propargyl and allenyl metal complexes

Isomerization of phenyl-substituted propargylplatinum(II) complex, trans-Pt(CH₂CCPh)(Cl)(PPh₃)₂ (1) to allenyl complex, trans-Pt(CPh=C=CH₂)(Cl)(PPh₃)₂ (2) was found to be catalyzed by zerovalent complex Pd(PPh₃)₄. The reaction was proposed to proceed through the transfer of the propargyl/allenyl ligand both from Pt(II) to Pd(0) and Pd(II) to Pt(0). The former transfer, which seemingly has a thermodynamic disadvantage, has unambiguously been confirmed to take place; treatment of 1 with Pd(PPh₃)₄ or a mixture of Pd₂(dba)₃ and PPh₃ resulted in the formation of Pd(I) complex, Pd₂(μ-PhCCCH₂)(μ-Cl)(PPh₃)₂ which lies in equilibrium with a mixture of propargyl/allenylpalladium(II) and Pd(0) complexes.     

Improvement in interactive remote in situ visualization using SIMD-aware function parser and asynchronous data I/O

Journal of Visualization - An in situ visualization system based on the particle-based volume rendering offers a highly scalable and flexible visual analytics environment based on multivariate...     

On the a posteriori estimates for inverse operators of linear parabolic equations with applications to the numerical enclosure of solutions for nonlinear problems

We consider the guaranteed a posteriori estimates for the inverse parabolic operators with homogeneous initial-boundary conditions. Our estimation technique uses a full-discrete numerical scheme, which is based on the Galerkin method with an interpolation in time by using the fundamental solution for semidiscretization in space. In our technique, the constructive a priori error estimates for a full discretization of solutions for the heat equation play an essential role. Combining these estimates with an argument for the discretized inverse operator and a contraction property of the Newton-type formulation, we derive an a posteriori estimate of the norm for the infinite-dimensional operator. In numerical examples, we show that the proposed method should be more efficient than the existing method. Moreover, as an application, we give some prototype results for numerical verification of solutions of nonlinear parabolic problems, which confirm the actual usefulness of our technique.     

Truxene‐Based Columnar Liquid Crystals: Self‐Assembled Structures and Electro‐Active Properties

Columnar liquid‐crystalline (LC) truxene derivatives containing branched flexible alkyl chains have been designed and synthesized. The dicyanomethylene and dithiafulvene substituents have been introduced into the π‐conjugated truxene framework to tune their electronic and redox properties as well as the molecular assembled structures. The π‐conjugated cores of dicyanomethylene‐ and dithiafulvene‐appended truxenes adopt bowl‐shaped conformations, giving rise to a large intrinsic dipole moment perpendicular to the aromatic framework. These molecules form stable columnar LC structures through intermolecular dipole–dipole interactions. The redox properties of LC truxene derivatives have been examined by cyclic voltammetry. The dicyanomethylene‐appended truxene shows the reversible four‐step electrochemical reductions, whereas the dithiafulvene‐appended truxene undergoes three‐step oxidations.     

Autothermal reforming of biogas over a monolithic catalyst

This study focused on measurement of the autothermal reforming of biogas over a Ni based monolithic catalyst. The effects of the steam/CH₄ (S/C) ratio, O₂/CH₄ (O₂/C) ratio and temperature were investigated. The CH₄ conversions were higher under all examined temperatures than the equilibrium conversion calculated using the blank outlet temperature, because the catalyst layer was heated by the exothermic catalytic partial oxidation reaction. The CH₄ conversion increased with increasing O₂/C ratio. Moreover, the CH₄ conversion was higher than the equilibrium conversion calculated using the blank outlet temperature for O₂/C>0.42 and reached about 100% at O₂/C=0.55. However, the hydrogen concentration decreased for O₂/C>0.45 because hydrogen was combusted to steam in the presence of excess oxygen. On the other hand, the hydrogen and CO₂ concentrations increased and the CO concentration decreased with increasing S/C ratio. As a result, it was found that the highest hydrogen concentrations and CH₄ conversions were attained at the O₂/C ratios of 0.45-0.55 and the S/C ratios of 1.5-2.5. Moreover, the H₂/CO ratio could also be controlled in the range from about 2 to 3.5 to give at least 90% CH₄ conversion, by regulating the O₂/C or S/C ratios.     

Evaluation of additives required for periodontal disease formulation using basic fibroblast growth factor

To design a suitable periodontal disease formulation using basic fibroblast growth factor (bFGF), legally available thickeners were evaluated focusing on their viscosity, extrusive force from a syringe, flow property and inertness to bFGF. Thirteen candidate thickeners showed appropriate viscosity (about 1×10? mPa·s), and further evaluations were conducted on them. Flow property was evaluated by the tilting test tube method. As a result, most thickener solutions with the optimum viscosity showed appropriate flow time (about 100 s) and the flow time did not depend on thickener concentration, whereas the extrusive force from a syringe depended on thickener concentration despite the thickener type and grade. Thickener solutions of 2-3% showed ideal result (10-20 N) and thickener solutions prepared outside of the concentration range (2-3%) were found to show unsuitable extrusive force. Consequently, to obtain required properties for a dental drug formulation, thickener solutions needed to show adequate viscosity (about 1×10? mPa·s) at 2-3% thickener concentration. In addition, several types of cellulose derivatives showed inertness to the bFGF because of their structure, without strong ionic dissociable groups, and neutral pH. Overall, the present work demonstrates that some water-soluble cellulose derivatives, such as hydroxypropylcellulose (HPC) and hydroxyethylcellulose (HEC), were suggested to have required properties for a dental drug formulation including bFGF.     

Columnar liquid crystalline pi-conjugated oligothiophenes

Polycatenar oligothiophenes possessing three alkoxy chains at each terminal self-organise into columnar liquid crystalline phases, and one-dimensional columnar stacks can be oriented uniaxially by mechanical shearing in the mesophases.     

Cobalt-catalyzed trimethylsilylmethylmagnesium-promoted radical alkenylation of alkyl halides: a complement to the Heck reaction

A cobalt complex, [CoCl2(dpph)] (DPPH = [1,6-bis(diphenylphosphino)hexane]), catalyzes an intermolecular styrylation reaction of alkyl halides in the presence of Me3SiCH2MgCl in ether to yield beta-alkylstyrenes. A variety of alkyl halides including alkyl chlorides can participate in the styrylation. A radical mechanism is strongly suggested for the styrylation reaction. The sequential isomerization/styrylation reactions of cyclopropylmethyl bromide and 6-bromo-1-hexene provide evidence of the radical mechanism. Crystallographic and spectroscopic investigations on cobalt complexes reveal that the reaction would begin with single electron transfer from an electron-rich (diphosphine)bis(trimethylsilylmethyl)cobalt(II) complex followed by reductive elimination to yield 1,2-bis(trimethylsilyl)ethane and a (diphosphine)cobalt(I) complex. The combination of [CoCl2(dppb)] (DPPB = [1,4-bis(diphenylphosphino)butane]) catalyst and Me3SiCH2MgCl induces intramolecular Heck-type cyclization reactions of 6-halo-1-hexenes via a radical process. On the other hand, the intramolecular cyclization of the prenyl ether of 2-iodophenol would proceed in a fashion similar to the conventional palladium-catalyzed transformation. The nonradical oxidative addition of carbon(sp2)-halogen bonds to cobalt is separately verified by a cobalt-catalyzed cross-coupling reaction of alkenyl halides with Me3SiCH2MgCl with retention of configuration of the starting vinyl halides. The cobalt-catalyzed intermolecular radical styrylation reaction of alkyl halides is applied to stereoselective variants. Styrylations of 1-alkoxy-2-bromocyclopentane derivatives provide trans-1-alkoxy-2-styrylcyclopentane skeletons, one of which is optically pure.