Sequential SNAr Reaction/Suzuki–Miyaura Coupling/C−H Direct Arylations Approach for the Rapid Synthesis of Tetraaryl‐Substituted Pyrazoles

A rapid synthesis of 1,3,4,5‐tetraaryl‐substituted pyrazoles has been achieved through a sequence of S_NAr reaction/Suzuki–Miyaura coupling/Pd‐catalyzed direct arylations that used 3‐iodo‐1H‐pyrazole as a scaffold. Pyrazoles with four different aryl groups were synthesized in a straightforward manner with no extra synthetic steps, such as protection/deprotection or the introduction of activating/directing groups, using readily available substrates and reagents. The developed synthetic approach enabled the structurally diverse synthesis of multiaryl‐substituted pyrazoles without using a glovebox technique.     

Mass spectrometric measurements of driver gas arrival in the T4 free-piston shock-tunnel

Available test time is an important issue for ground-based flow research, particularly for impulse facilities such as shock tunnels, where test times of the order of several ms are typical. The early contamination of the test flow by the driver gas in such tunnels restricts the test time. This paper reports measurements of the driver gas arrival time in the test section of the T4 free-piston shock-tunnel over the total enthalpy range 3–17 MJ/kg, using a time-of-flight mass spectrometer. The results confirm measurements made by previous investigators using a choked duct driver gas detector at these conditions, and extend the range of previous mass spectrometer measurements to that of 3–20 MJ/kg. Comparisons of the contamination behaviour of various piston-driven reflected shock tunnels are also made. PACS 07.75.th; 47.40.-x     

Nonlinear Ergodic Theorem for Positively Homogeneous Nonexpansive Mappings in Banach Spaces

Recently, two retractions (projections), which are different from the metric projection and the sunny nonexpansive retraction in a Banach space, were found. In this article, using nonlinear analytic methods and new retractions, we prove a nonlinear ergodic theorem for positively homogeneous and nonexpansive mappings in a uniformly convex Banach space. The limit points are characterized by using new retractions.     

Estimated effects of silicone glue on protein crystal growth

Silicone glue (modified silicone polymer) is widely used for both experiments involving inorganic crystal growth and those involving organic materials like proteins. This material is very useful for building a hand-made experiment setup or for fixing protein crystals to specific locations. Though silicone glue is regarded as harmful to proteins, no systematic verification was performed to investigate its impurity effects on protein crystal growth. We focused on and estimated the impurity effects of silicone glue on protein crystal growth.     

Characterization and solventless growth of salicylic acid macro‐crystals involving a nitrogen gas flow

We report an original solventless thermal crystallisation method to grow large needle‐like salicylic acid (SA) crystals of 10‐12 mm in length. The method is based on the utilization of nitrogen gaz flow on salicylic acid powder during heating just below melting point temperature for 24 h. Salicylic acid provides one of the best examples of a pharmaceutical substance used for cosmetics whose physical and chemical properties indicate hydrogen‐bond formation between the hydroxyl group and an adjacent oxygen atom of the same molecule. The structure of the crystals is confirmed by single crystal X‐ray diffraction; it is monoclinic, a = 4.93(2) Å, b = 11.23(5) Å, c = 11.56(6) Å, β = 90.77(4)° with the space group P 2₁/c. The macrocrystals formation using this method is new and represents an interesting finding for a wide range of applications to be developed in the fields of biotechnology and photonics (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemical constituents in the leaves of Vateria indica

Comprehensive re-investigation of the chemical constituents in the leaves of Vateria indica (Dipterocarpaceae) resulted in the isolation of a novel resveratrol dimeric dimer having a C(2)-symmetric structure, vateriaphenol F (1), and two new O-glucosides of resveratrol oligomers, vateriosides A (2) (resveratrol dimer) and B (4) (resveratrol tetramer), along with a new natural compound (3) and 33 known compounds including 26 resveratrol derivatives. The absolute structures were elucidated by spectroscopic analysis, including two dimensional NMR and circular dichroism (CD) spectra.     

Self-accumulation of aromatics at the oil-water interface through weak hydrogen bonding

It is well-known that the amphiphilic solutes are surface-active and can accumulate at the oil-water interface. Here, we have investigated the water and a light-oil model interface by using molecular dynamic simulations. It was found that aromatics concentrated in the interfacial region, whereas the other hydrocarbons were uniformly distributed throughout the oil phase. Similar to previous studies, such concentrations were not observed at pure aromatics-water interfaces. We show that the self-accumulation of aromatics at the oil-water interface is driven by differences in the interfacial tension, which is lower for aromatics-water than between the others. The weak hydrogen bonding between the aromatic rings and the water protons provides the mechanism for lowering the interfacial tension.     

Enantioselective total synthesis of (-)- and (+)-petrosin

The enantioselective total synthesis of (-)- and (+)-petrosin is described. The union of two key segments was executed by Suzuki-Miyaura coupling. The quinolizidine rings were stereoselectively constructed via a diastereoselective Mannich reaction and an aza-Michael reaction. The 16-membered ring was constructed by ring-closing metathesis with the second-generation Grubbs catalyst.     

Palladium-catalyzed asymmetric synthesis of axially chiral allenylsilanes and their application to SE2' chirality transfer reactions

Stepwise application of the Pd-catalyzed S(N)2' reaction and the desilylative S(E)2' reaction to the ambivalent 2-bromo-1-silyl-1,3-dienes provides a novel route to the highly enantioselective construction of tertiary and quaternary propargylic stereogenic centers via axially chiral allenylsilanes.     

Influence of exchange coupling on current-driven domain wall motion in a nanowire

In this study, the effect of exchange stiffness constant on current-driven domain wall motion in nanowires with in-plane magnetic anisotropy (IMA) and perpendicular magnetic anisotropy (PMA) has been investigated using micromagnetic simulation. The critical current density in a nanowire with IMA decreases as the exchange stiffness constant decreases because the domain wall width at the upper edge of the nanowire narrows according to the decrease of the exchange stiffness constant. On the other hand, the critical current density in a nanowire with PMA slightly decreases contrary to that of IMA although the domain wall width reasonably decreases as the exchange stiffness constant decreases. The slight reduction rate of the critical current density is due to the increase of the effective hard-axis anisotropy of PMA nanowire.