Enhancement of optical birefringence in tellurite glasses containing silver nanoparticles induced via thermal poling

Wavelength-selective enhancement of optical birefringence has been observed in a tellurite glass containing silver nanoparticles (Ag NPs) induced via thermal poling. The birefringence appears as an optical rotation of linearly polarized light; a large optical rotation is observed at around the wavelength of localized surface plasmon resonance (LSPR) of Ag NPs. The optic axis is oriented along the electric field applied during the thermal poling, suggesting that birefringence induced in the glass matrix through the thermal poling is drastically enhanced by the NPs at around the LSPR. Because of the birefringence of the matrix, the wavelength of LSPR shifts depending on the polarization state of the incident light, which in turn induces the polarization dependence of the real part of the refractive index via the Kramers–Kronig relation.     

Channel-selective independent sorption and collection of hydrophilic and hydrophobic molecules by Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40] ionic crystal

An ionic crystal of Cs2[Cr3O(OOCC2H5)6(H2O)3]2[alpha-SiW12O40].4H2O 1a with hydrophilic and hydrophobic channels has been designed and successfully synthesized. The guest-free phase 1b sorbs dichloromethane and water in the hydrophobic and hydrophilic channels, respectively. The rate and equilibrium amount of the dichloromethane sorption into the hydrophobic channel and those of water into the hydrophilic channel were independent of each other. The sorption properties can be applied to the channel-selective sorption and collection of hydrophobic (dichloromethane) and hydrophilic (water) molecules from the mixture.     

Synthesis of hydrosilylboronates via the monoborylation of a dihydrosilane Si–H bond and their application for the generation of dialkylhydrosilyl anions

The synthesis of a series of hydrosilylboronates via the selective iridium- or nickel-catalyzed monoborylation of dihydrosilane Si–H bonds is described. The synthesized silylboronates, which bear a single Si–H bond, can be used as novel silicon nucleophiles in the presence of transition-metal catalysts or bases. The first ²⁹Si{¹H} NMR spectroscopic evidence for the formation of (t-Bu)₂HSiLi, generated by the reaction of (t-Bu)₂HSi–B(pin) with MeLi, is reported as the first example of a dialkylhydorosilyl lithium species.

Monoborylation of a dihydrosilane Si–H bond can be achieved in the presence of iridium- or nickel-based catalysts, yielding novel hydrosilylboronates that bear a hydrogen atom at the silicon center.     

Sugar Binding Effects on the Enzymatic Reaction and Conformation Near the Active Site of Pokeweed Antiviral Protein Revealed by Fluorescence Spectroscopy

In various trials for elucidating the physiological function of pokeweed antiviral protein (PAP), studies on the interaction with sugar are essential. The fluorescence titration curves showed that PAP retained the strong affinity against N-acetylglucosamine (NAG) and two sites in one PAP molecule co-operatively participated in the binding. In the complex of PAP with NAG, Trp208 located at the entrance lid site of substrate came closer to Tyr72 about 0.3 Å. Furthermore, the fluorescence anisotropy decay measurement demonstrated that the segmental rotation of Trp208 was enlarged by the binding of PAP with NAG. Such conformational changes around the active site closely correlate with the enzymatic activity of PAP. The N-glycosidase activity of PAP was enhanced more than two times in the presence of NAG. The obtained results consistently suggested the enzymatic activity of PAP would be regulated through the conformation change near the active site induced by the binding with NAG.     

Crowd evacuation of pairs of pedestrians

The crowd evacuation of pairs of pedestrians (i.e. pairs consisting of a parent and a child) is numerically investigated. Here, it is assumed that all pedestrians have their own partners, and move randomly inside the bounded domain of the right-hand room as an initial state. All pedestrians start their evacuations after they contact their partners. The evacuations are completed by the transfer of all the pairs from the right-hand room to the left-hand room through an exit. A frozen swarm tends to appear in the right-hand room as the total number of pedestrians increases. The frozen swarm moves without changing its form, unless it is dissolved by a strong collision with a pair of pedestrians that comes back from the left-hand room by accident. Finally, the evacuation speed also depends on the area of the Escape Zone, whereas an obstacle placed in front of an exit also changes the speed of the evacuation in accordance with the type of motion of the children.     

Recognition of aromatic compounds by π pocket within a cage-shaped borate catalyst

Taking shape: the ability of a Lewis acid catalyst to distinguish between aromatic and aliphatic hydrocarbon moieties was accomplished by using cage-shaped borate catalysts B(OC(6)H(3)Aryl)(3)CH having a π pocket derived from aryl substituents surrounding the boron center. The catalyst predominantly activated aromatic aldehydes over aliphatic ones for reaction.     

First principles study of sulfuric acid anion adsorption on a Pt(111) electrode

A first principles theory combined with a continuum electrolyte theory is applied to adsorption of sulfuric acid anions on Pt(111) in 0.1 M H(2)SO(4) solution. The theoretical free energy diagram indicates that sulfuric acid anions adsorb as bisulfate in the potential range of 0.41 < U ≤ 0.48 V (RHE) and as sulfate in 0.48 V (RHE) < U. This diagram also indicates that sulfate inhibits formations of surface oxide and hydroxide. Charge analysis shows that the total charge transferred for the formation of the full coverage sulfate adlayer is 90 μC cm(-2), and that the electrosorption valency value is -0.45 to -0.95 in 0.41 < U ≤ 0.48 V (RHE) and -1.75 to -1.85 in U > 0.48 V (RHE) in good agreement with experiments reported in the literature. Vibration analysis indicates that the vibration frequencies observed experimentally at 1250 and 950 cm(-1) can be assigned, respectively, to the S-O (uncoordinated) and symmetric S-O stretching modes for sulfate, and that the higher frequency mode has a larger potential-dependence (58 cm(-1) V(-1)) than the lower one.     

(1)H NMR probe for in situ monitoring of dopamine metabolism and its application to inhibitor screening

Dopamine (DA) is a monoamine neurotransmitter that plays important roles in the brain, and whose levels in the brain are associated with several neurological and psychiatric disorders. Therefore, DA metabolism inhibitors have been used as therapeutic agents. Here, we report a (1)H NMR probe for the in situ analysis of DA metabolism, and its application to DA inhibitor screening. We designed doubly (13)C-labeled DA ((13)C(2)-DA) as the probe. The combination of the (13)C(2)-DA and (1)H-{(13)C-(13)C'} NMR technique allowed the selective and thus in situ monitoring of DA metabolism. Using (13)C(2)-DA, we successfully measured the efficacies of different inhibitors in a tissue sample, allowing us to improve the in situ inhibitory efficacy of the known DA metabolism inhibitor, clorgyline.     

Molecular Ionics in Supramolecular Assemblies with Channel Structures Containing Lithium Ions

A novel trilithium compound, Li₃[B(C₆H₄O₂){O(CH₂CH₂O)₃CH₃}₂][N(SO₂CF₃)₂]₂ ( 1 ‐2.0), with solid‐state ionic conductivity was synthesized. The crystal structure of 1 ‐2.0 consists of the one‐dimensional ionic conduction paths. The paths were afforded as a result of the self‐assembled stacking of the component molecules of 1 ‐2.0 with channel structures containing lithium ions. In this supramolecule, one lithium ion holds the component molecules in specific positions to construct a supramolecular structure with thermally stable ionic conduction paths and the others behave as carrier ions exhibiting selective lithium‐ion conductivity. Owing to the existence of both roles for the lithium ions, this electrolyte shows selective lithium‐ion conductivity.