Preparation and Regioselective Metalation of Bis(trimethylsilyl)methyl‐Substituted Aryl Derivatives

A range of bis(trimethylsilyl)methyl‐substituted aryl derivatives was prepared by using a Kumada–Corriu cross‐coupling reaction. The regioselective metalation of the resulting bis(trimethylsilyl)methyl‐substituted aryl derivatives bearing this bulky silyl group allowed the generation of functionalized aromatics. A regioselective switch in the presence or in the absence of the bis(trimethylsilyl)methyl group has been demonstrated. Furthermore, this silyl group was converted into a formyl group or a styryl group, enhancing the scope of application of such bis(trimethylsilyl)methyl‐substituted arenes.     

Emission Control by Molecular Manipulation of Double‐Paddled Binuclear PtII Complexes at the Air‐Water Interface

Molecular functions depend on conformations and motions of the corresponding molecular species. An air–water interface is a suitable asymmetric field for the control of molecular conformations and motions under a small applied force. In this work, double‐paddled binuclear Pt^II complexes containing pyrazole rings linked by alkyl spacers were synthesized and their orientations and emission properties dynamically manipulated at the air–water interface. The complexes emerge from water with concurrent variation of interface orientation of the planes of the Pt^II complexes from perpendicular to parallel during mechanical compression suggesting a unique ‘submarine emission‘. Phosphorescence of the complexes is quenched at the air–water interface prior to monolayer formation with intensities subsequently rapidly increasing during monolayer compression. These results indicate that asymmetric reactions and motions might be controlled by applying mechanical force at the air–water interface.     

The effect of various calcination treatments on the photocatalytic activity of a rod-type TiO<Subscript>2</Subscript> electrode for oxidation of ethanethiol

It was found that the photoelectrochemical performance and photocatalytic activity of rod-type TiO₂ electrodes were affected by various post-calcination treatments, for example, calcination in NH₃ or under vacuum. Post-calcination treatment in NH₃ at 773 K was particularly effective in increasing the photoelectrochemical performance and photocatalytic activity of rod-type TiO₂ electrodes. A unique photoelectrochemical circuit was constructed by connecting a rod-type TiO₂ electrode to a Pt electrode through a silicon solar cell in which the negative bias was applied on the rod-type TiO₂ electrode. It was found that the photoelectrochemical circuit can effectively oxidize ethanethiol in water into CO₂.     

Magnetic relaxations of antiferromagnetic nanoparticles in magnetic fields

We reexamine anomalous magnetic relaxations of ferritin in magnetic fields, the presence of which has been regarded as evidence suggesting the existence of thermally assisted macroscopic quantum tunneling in antiferromagnetic nanoparticles. In the present study, relaxation curves of ferritin are examined using an approach that is free from assumptions regarding distributions of various parameters of polydispersive particles. The results are not anomalous. In other words, the relaxation is accelerated by the field, as expected for classical superparamagnetic fluctuations.     

Membrane properties of archaeal macrocyclic diether phospholipids

Several biophysical properties of four synthetic archaeal phospholipids [one polyprenyl macrocyclic lipid A and three polyprenyl double-chain lipids (B, C, D) bearing zero, one or four double bonds in each chain] were studied using differential scanning calorimetry, electron and optical microscopies, stopped-flow/light scattering and solid-state 2H-NMR techniques. These phospholipids gave a variety of self-organized structures in water, in particular vesicles and tubules. These assemblies change in response to simple thermal convection. Some specific membrane properties of these archaeal phospholipids were observed: They are in a liquid-crystalline state over a wide temperature range; the dynamics of their polyprenyl chains is higher than that of n-acyl chains; the water permeability of the membranes is lower than that of n-acyl phospholipid membranes. It was also found that macrocyclization remarkably improves the barrier properties to water and the membrane stability. This may be related to the adaptation of Methanococcus jannaschii to the extreme conditions of the deep-sea hydrothermal vents.     

A novel synthesis of half-protected 1,3-dicarbonyl compounds

It has been found that the reaction of enol silyl ethers with 2-ethoxy-1,3-dithiolane proceeds smoothly in the presence of zinc chloride catalyst to afford half-protected 1,3-dicarbony1 compounds in moderately good yields.