[IrCl(cod)]2-catalyzed direct oxidative esterification of aldehydes with alcohols

[IrCl(cod)]₂ catalyzed the oxidative esterification of a variety of aldehydes with methanol as a solvent in combination with K₂CO₃ under mild conditions (rt, 12 h). The oxidative esterification reaction of aliphatic aldehydes also took place with olefinic alcohols as reagents in toluene under similar conditions.     

Efficient oxidation of alcohols electrochemically mediated by azabicyclo-N-oxyls

Preparation of azabicyclo-N-oxyls and the electrochemical oxidation of alcohols using them as mediators have been exploited. This oxidation was applicable to a transformation of sterically hindered secondary alcohols into the corresponding ketones in high yields.     

Effective procedure for selective ammonolysis of monosubstituted oxiranes: application to E7389 synthesis

A highly effective procedure is reported to synthesize 1,2-aminoalcohols by regio- and chemo-selective ammonolysis of mono-substituted epoxides. Additive- and concentration-effects were studied, revealing that (1) methanesulfonic acid is most effective among the additives tested and (2) formation of bis-adducts is practically eliminated at [C] ? 40 mM. The optimum condition thus identified was successfully applied to the final step of the synthesis of potent anti-tumor compound E7389.     

First-principles study of benzene on noble metal surfaces: Adsorption states and vacuum level shifts

We have studied the interaction of benzene with Cu(1 1 1), Ag(1 1 1) and Au(1 1 1) surfaces using density functional theory (DFT) within a generalized gradient approximation (GGA) and the van der Waals density functional [vdW-DF; M. Dion, H. Rydberg, E. Schröder, D.C. Langreth, B.I. Lundqvist, Phys. Rev. Lett. 92 (2004) 246401]. The adsorption energies using vdW-DF are significantly more accurate than those using GGA, while the equilibrium adsorption distances between benzene and metal substrates () calculated by both GGA and vdW-DF are almost identical. The work function changes induced by the adsorption of benzene are significantly underestimated compared with the experimental values, as a result of the overestimation of by both GGA and vdW-DF. Instead of determining the values from first-principles calculations, we deduced the most probable adsorption distances in such a way as to reproduce the experimentally-observed work function changes. The deduced adsorption distance () is shortest on Cu(1 1 1) while it is longest on Ag(1 1 1), reflecting the strength of the interactions between benzene and the metal surfaces. It turns out that the substrate dependence of the work function change is mainly ascribed to the difference in the benzene–metal distance (Z_C). Charge transfer and work function changes by the adsorption of benzene were analyzed by means of the induced density of interface states (IDIS) model [H. Vázquez, R. Qszwaldowski, P. Pou, J. Ortega, R. Pérez, F. Flores, A. Kahn, Europhys. Lett. 65 (2004) 802], and compared with the self-consistent GGA calculations. The vacuum level shifts estimated by the IDIS model agree with the GGA results for . On the other hand, the discrepancy between the two methods becomes larger for , where the back donation from the metal substrates to the adsorbate becomes significant. We show that the IDIS model reasonably works well for benzene on Cu(1 1 1), Ag(1 1 1) and Au(1 1 1) surfaces because on all surfaces. However, our analysis reveals that the actual charge density redistribution induced by the adsorption of benzene is more complicated than that assumed in the IDIS model.     

Validation of practical diffusion approximation for virtual near infrared spectroscopy using a digital head phantom

Light propagation in the digital head phantom for virtual near infrared spectroscopy and imaging is calculated by diffusion theory. In theory, diffusion approximation is not valid in a low-scattering cerebrospinal fluid (CSF) layer around the brain. The optical path length and spatial sensitivity profile predicted by the finite element method based upon the diffusion theory are compared with those predicted by the Monte Carlo method to validate a practical implementation of diffusion approximation to light propagation in an adult head. The transport scattering coefficient of the CSF layer is varied from 0.01 to 1.0 mm⁻¹ to evaluate the influence of that layer on the error caused by diffusion approximation. The error is practically ignored and the geometry of the brain surface such as the sulcus structure in the digital head phantom scarcely affects the error when the transport scattering coefficient of the CSF layer is greater than 0.3 mm⁻¹.     

First-principles study of the pentacene/Cu(1 1 1) interface: Adsorption states and vacuum level shifts

We have studied the interaction of pentacene with a Cu(1 1 1) surface using density functional theory (DFT) within a generalized gradient approximation (GGA) and the van der Waals density functional [vdW-DF, M. Dion, H. Rydberg, E. Schröder, D.C. Langreth, B.I. Lundqvist, Phys. Rev. Lett. 92 (2004) 246401]. The adsorption energy is accurately predicted by vdW-DF, while the equilibrium distances between pentacene and the metal substrate (Z_C) are overestimated by both GGA and vdW-DF. The work function changes depend significantly on Z_C. The experimental work function change can be successfully reproduced by GGA if the experimentally reported adsorption geometry is used, whereas the magnitude of the work function change is underestimated if calculated adsorption geometries are applied. We examined the IDIS model [H. Vázquez, R. Qszwaldowski, P. Pou, J. Ortega, R. Pérez, F. Flores, A. Kahn, Europhys. Lett. 65 (2004) 802] to compare it with the GGA results. The interface dipoles estimated by the IDIS model fairly agree with the GGA results, provided that the adsorption distance is large. On the other hand, they tend to deviate from the GGA results as the adsorption distance becomes smaller, where back donation from the metal surface to the adsorbate occurs. Our analysis reveals that at experimentally reported metal–organic distance, back donation is significant enough to induce polarization of pentacene molecules perpendicular to the surface, which leads to a reduction of the work function. Thus, at the experimentally reported metal–organic distance, the work function change estimated by a simple IDIS model deviates from that calculated by self-consistent GGA calculations. We also found that at the experimentally reported metal–organic distance, the transferred electrons create weak chemical bonds between pentacene and the Cu(1 1 1) surface, illustrating the reactive nature of pentacene.     

Stabilization effects of carboxylate on pyrotechnic compositions including Mg powder in water

Magnesium powder is a common fuel in the field of pyrotechnics. The metal corrodes easily under wet conditions. This can lead to problems such as spontaneous ignition and deterioration of combustion performance when the powder is used in humid areas. For pyrotechnic compositions containing magnesium, harmful stabilizers are often used. In this study, we researched a less harmful replacement for the stabilizer and selected linseed oil, which is used as cooking oil. Experiments were conducted to examine linseed oil’s stabilization effects against magnesium corrosion when it is in contact with an oxidizer under humid conditions by coating magnesium powder and soaking it in aqueous oxidizer solutions. The oxidation of linseed oil led to its polymerization, because of which the stabilizing effect of linseed oil was lost. Stearic acid, which is a saturated fatty acid, was also examined for its stabilizing effects. Melted stearic acid was mixed with magnesium, and coating of stearic acid on magnesium particles was confirmed. The effect of stearic acid coating is more prominent than that of simple mixing of stearic acid with Mg. The stabilization effect of linseed oil and stearic acid coating shows that unharmful organic stabilizers can also be used in pyrotechnic compositions containing Mg.

     

Low-pass filtering effects of viscous sublayer on high Schmidt number mass transfer close to a solid wall

Numerical simulation of high Schmidt number turbulent mass transfer at a solid wall is carried out. Particular attention is paid to the response of the concentration field to the wall-normal velocity fluctuation inside the viscous sublayer. Spatio-temporal correlation shows that the high Schmidt number concentration field becomes insensitive to the wall-normal velocity fluctuation. In addition, there exists a significant time lag in the response of the concentration field to the wall-normal velocity fluctuation. As a result, the instantaneous distribution of the local mass transfer rate is drastically changed. These facts explain why the analogy between the momentum and mass transfer does not hold close to the wall. Based on a one-dimensional advection–diffusion equation, we derive a transfer function connecting the wall-normal velocity and the concentration fluctuations. It is shown that the present model can reproduce the fundamental dynamical features of high Schmidt number concentration field.     

Extraction mechanisms of charged organic dye molecules into silica-surfactant nanochannels in a porous alumina membrane

Extraction mechanisms of charged organic dye molecules are examined for an assembly of silica-surfactant nanochannels with a channel diameter of 3.4 nm, which is formed inside the pores of an anodic alumina membrane by a surfactant-template method. Experimental results confirm that the extraction mechanism depends on the sign of a charge of the dye molecules. The extraction of the cationic rhodamine 6G is predominantly caused by an ion-pair extraction process, whereas an anion-exchange process is mainly responsible for the extraction of the anionic sulforhodamine B. These extraction mechanisms are discussed by considering the microstructures of the silica-surfactant nanochannels.