Recognition of dicarboxylates in aqueous acetonitrile by a dinuclear zinc(II) complex of 2,2’-binaphthalene-based receptor

Molecular recognition of dicarboxylates by a dinuclear zinc(II) complex of 2,2?-binaphthalene bearing di(2-pyridyl)aminomethyl groups at 8- and 8?-positions ([Zn₂L]⁴⁺) by UV-vis and fluorescence spectral titrations in an aqueous solvent was investigated. In a series of α,ω-dicarboxylate, receptor [Zn₂L]⁴⁺ showed the highest binding affinity for succinate and UV-vis and fluorescence changes were also largest upon the addition of this guest. In a series of phthalate derivatives, phthalate was strongly bound by [Zn₂L]⁴⁺. The characteristic UV-vis and fluorescence changes strongly depend on the dihedral angle of two naphthyl groups of the complex [Zn₂L]⁴⁺· dicarboxylate estimated by spectral titrations and DFT calculations.     

Edge-defined film-fed growth of Yb:YVO4 single crystal plates

The applicability of the edge-defined film-fed growth (EFG) technique for Yb_xY_(1−x)VO₄ (x=0.05, 0.1 and 1) was approved by successful growth of crystals up to 80 mm in length as the thin plates. Low-angle grain boundaries and the crystal coloration as main defects were found. Optimal seed orientation was suggested on the strength of vanadate crystal plate morphology. Optical properties, chemical composition and the crystalline quality were investigated.     

Optical anisotropy and columnar structure of obliquely deposited thin films containing fine metal particles ag]

Anisotropic optical properties and nanostructures of thin films prepared by oblique co-deposition of Ag and SiO₂ were studied. At low concentrations of Ag, a columnar structure grew towards the direction of the incident SiO₂ vapor and small Ag particles were embedded in that structure. An inhomogeneous distribution of Ag was observed in cases where the Ag was deposited from the opposite side of the surface normal to the direction of the incident SiO₂ vapor. This inhomogeneous distribution of Ag particles gives rise to optical anisotropy, i.e., the optical transmittance of p-polarized light varies drastically depending on the angle of incidence, while that of s-polarized light remains unchanged. A possible application of the anisotropic optical absorption properties of Ag---SiO₂ hybrid films is in the manufactur of an inorganic thin film polarizer.     

A non‐volatile,bistable, and rewritable memory device fabricated with poly(nitroxide radical) and silver salt layers

A non‐volatile, bistable, and rewritable organic memory device was successfully fabricated with the layers of poly(2,2,6,6‐tetramethylpiperidine‐1‐oxyl methacrylate) (PTMA) and poly(methyl methacrylate) (PMMA) containing silver salt. The PTMA layer was employed as a p‐dopable material, while the silver salt‐dispersed PMMA layer acted as an n‐dopable material. The ON–OFF ratio between low‐conductivity and high‐conductivity states amounted to more than four orders of magnitude, and the retention time was longer than 10³ sec. The device was characterized by excellent rewritability. Copyright © 2007 John Wiley & Sons, Ltd.     

Annulation of Alkynyl Aryl Ethers with Allyl Pivalates To Give 2,3‐Bismethylenechromanes through Double C−H Bond Cleavage

The treatment of silylethynyloxyarenes with allylic pivalates in the presence of a palladium catalyst led to efficient C?H bond cleavage in both substrates and a novel annulation reaction to give 2,3‐bismethylenechromanes. When ortho‐allylated silylethynyloxybenzenes were used as the substrates, the same products were obtained. This result shows that site‐selective intramolecular hydrovinylation is involved in the annulation reaction. The synthetic utility of the products was demonstrated by the construction of condensed polycycles.     

Highly beta-selective O-glucosidation due to the restricted twist-boat conformation

[reaction: see text] Ethyl 1-thio-2,3,4,6-tetrakis-O-triisopropylsilyl-beta-d-glucopyranoside, ethyl 6-O-benzyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-d-glucopyranoside, and ethyl 6-O-pivaloyl-1-thio-2,3,4-tris-O-triisopropylsilyl-beta-d-glucopyranoside induced highly beta-selective O-glucosidations. Among them, the 6-O-pivaloylated substrate provided the best selectivity up to alpha/beta = 3:97 with cyclohexylmethanol, and the substrate was used for glucosidations with secondary and tertiary alcohols in a highly beta-selective manner. The selectivity would be caused by the twist-boat conformation of the pyranose; this is the first beta-selective O-glucosidation based on conformational control of the pyranose ring.     

A B3LYP study on counterpoise-corrected geometry optimizations for hydrated complexes of [K(H2O)n] and [Na(H2O)n]

We report the basis set dependencies and the basis set superposition errors for the hydrated complexes of K⁺ and Na⁺ ions in relation to the recent studies of the KcsA potassium channel. The basis set superposition errors are estimated by the geometry optimizations at the counterpoise-corrected B3LYP level. The counterpoise optimizations alter the hydration distances by about 0.02–0.03 Å. The enthalpies and free energies for K⁺ + n(H₂O) → [K(H₂O)_n]⁺ and Na⁺ + n(H₂O) → [Na(H₂O)_n]⁺ (n = 1–6) are compared between the theoretical and experimental values. The results show that the addition of diffuse functions to K, Na, and O species are effective. However, it is also found that the counterpoise corrections using diffuse functions work so as to underestimate the free energies for the complexes with increasing the hydration number. The stabilization energies in aqueous solution are larger for a Na⁺ ion than for a K⁺ ion, suggesting the contributions of their dehydration processes to the ion selectivity of the KcsA potassium channel. The changes in coordination distance between the isolated [K(H₂O)₈]⁺ and the [K(H₂O)₈]⁺ in the KcsA potassium channel indicate the importance of hydrogen bondings between the first hydration shell and the outer hydration shells.     

Three New Monoterpene Glucosides from Lamium amplexicaule

Three new monoterpene glucosides, lamiuamplexosides A–C ( 1 – 3 ), along with thirteen known glucosides, were isolated from the whole plant of Lamium amplexicaule L. The structures of 1 – 3 were elucidated on the basis of spectroscopic, chemical, and physicochemical evidence.     

Me‐bipam for Enantioselective Ruthenium(II)‐Catalyzed Arylation of Aldehydes with Arylboronic Acids

Ligand design by‐pam : A ruthenium‐catalyzed asymmetric arylation of aldehydes with arylboronic acids has been developed, giving chiral diarylmethanols in good yields. The use of a chiral bidentate phosphoramidite ligand ((R,R)‐Me‐bipam) led to excellent enantioselectivities.