Structural, textural, and electronic properties of a nanosized mesoporous ZnxTi1-xO2-) solid solution prepared by a supercritical drying route

Mesoporous nanosized TiO2 and Zn(x)Ti(1-x)O(2-x) solid solution having a Zn content below 10 mol % with a particles size between 13 and 17 nm are prepared by a template-free sol-gel method followed by high-temperature supercritical drying in 2-propanol. The structural, textural, and electronic properties of the obtained nanomaterials are methodically investigated by using XRD, SEM, TEM, ED, HREM, EDX, ICP-OES, N(2) adsorption-desorption, Raman spectroscopy, and diffuse reflectance UV-vis spectroscopy. It is shown that the proposed synthesis technique leads to the formation of a Zn(x)Ti(1-x)O(2-x) solid solution based on the anatase crystal structure rather than a two-phase sample. High-resolution electron microscopy and electron diffraction indicate that the distribution of zinc atoms over the anatase structure does not lead to a considerable deformation of the crystal structure.     

A highly regio- and stereoselective synthesis of internal olefins via an elimination of trimethylstannyl group

Internal reaction of secondary alkyltin(IV) compounds having thionium ion gave internal trans olefins with high yield and regio- and stereoselectivity via 1,5- or 1,6-transfer of a hydride β to the trialkylstannyl group.     

Synthesis of Ultrafine SiC Powders from Carbon-Silica Hybridized Precursors with Carbothermic Reduction

Inorganic-organic hybrid gels were prepared by simultaneous condensation of the liquid mixture of ethyl silicate, ethyl borate and water soluble phenol resin with low molecular weight. The liquid mixtures were changed into lightly colored transparent gels after a catalyst addition and stirring. The obtained gels were crushed, dried and fired in controlled conditions to yield the inorganic precursors. Since the tailored inorganic precursors mainly consisted of SiO2 and carbon, silicon carbide was formed with the heat treatments in an Ar atmosphere beyond 1773 K with carbothermic reduction. The properties and morphology of the formed silicon carbide powders in terms of the starting precursor compositions and the conditions of the carbothermic reduction were investigated with SEM, XRD and TG-DTA analysis.     

Synthetic studies on selective type 4 phosphodiesterase (PDE 4) inhibitors. 1. Structure-activity relationships and pharmacological evaluation of 1,8-naphthyridin-2(1H)-one derivatives

In order to develop novel and orally active phosphodiesterase (PDE) 4 inhibitors, random screening was performed using our chemical library to find YM-10335 possessing the 1,8-naphthyridin-2(1H)-one skeleton which is a completely different structure from rolipram. In this report, the syntheses and structure-activity relationships of the YM-10335 derivatives were described. Some compounds showed selective inhibitory activities for PDE 4 derived from human peripheral blood cells and no effect on the other PDE types (1, 2, 3, 5). The inhibition of the tumor necrosis factor-alpha (TNF-alpha) release in vitro and the carrageenan-induced pleurisy in rats were also described.     

First preparation of biotinylated gradient polyethylene surface to bind photoactive caged streptavidin

A gradient polyethylene (PE) surface was created through corona treatment, in which the corona power increased along the 5 cm length of the PE. The gradient surface was treated with polyethyleneimine and then biotin. Fluorescein-conjugated streptavidin (SAV) caged within 5-carboxymethoxy-2-nitrobenzyl (CMNB) adsorbed onto the biotinylated gradient PE surface following molecular recognition principles. Photoirradiation decomposed the CMNB cage and allowed the fluorescein-conjugated SAV to fluoresce, the intensity of which increased gradually along the PE surface.     

Heterometallic hexanuclear cluster with an S = 8 spin ground state: MnII[MnII(hfac)2]3[NiII(pao)3]2 (hfac- = hexafluoroacetylacetonate,pao- = pyridine-2-aldoximate)

The heterometallic Mn(II)(4)Ni(II)(2) title compound has been synthesized and characterized by X-ray crystallography. The compound consists of a Ni-Mn-Ni linear moiety, [[Ni-(mu-NO)(3)](2)-Mn], linked by oximate bridges and three Mn(II) hfac terminal units attached by oximate oxygens in a di-mu-oxo fashion, forming a novel heterometallic cluster: Mn[Mn(hfac)(2)](3)[Ni(pao)(3)](2) (1). Magnetic measurements reveal the antiferromagnetic nature of the oximate pathway between Mn(II) and Ni(II) metal ions, which imposes an unusual high-spin ground state (S = 8) for 1.     

Rhodium-catalyzed addition of arylboron compounds to nitriles, ketones, and imines

The rhodium-catalyzed addition reactions of sodium tetraphenylborate and arylboronic acids to nitriles, ketones, and imines were examined. The reaction of nitriles could be carried out efficiently in the presence of a catalyst system of [RhCl(cod)]₂-dppp and H₂O to give the corresponding monoarylated products selectively. Although unactivated ketones and imines are known to be poor electrophiles for rhodium-catalyzed arylation, the phenylation of them with use of sodium tetraphenylborate proceeded smoothly in the presence of [RhCl(cod)]₂ and Rh(acac)(cod) as catalysts, respectively. The addition of NH₄Cl was found to be crucial to effectively conduct the reaction of ketones and imines.     

Regioselective conjugate addition of sulfonylallyl carbanions to α, β-unsaturated ketones

Ambident lithium carbanions of allyl phenyl sulfones add 1,4-α to both acyclic and cyclic enones exclusively if HMPA is present in the medium; in contrast, 1,2-α addition to cyclic enone is the major kinetic course in the absence of HMPA, which is followed by rearrangement to the 1,4-γ adduct.     

Contrasteric stereochemical dictation of the cyclobutene ring-opening reaction by a vacant boron p orbital

Cyclobutene, having a pinacolatoboryl group at the 3-position, was prepared by the reaction of trimethyl borate with a cyclobutenyl anion, which was generated by reductive lithiation of 3-(phenylselenyl)cyclobutene. Its thermal ring-opening reaction provided (Z)-1-borylbuta-1,3-diene selectively despite the arising steric congestion. The contrasteric behavior was accounted for by assuming an electron-accepting interaction of the vacant boron p orbital with the distorted breaking sigma orbital in the inward transition state.     

Multifold curdlan gel formation by dialysis into aqueous solutions of metal salts

We have found that the dialysis of curdlan dissolved in alkaline solution into aqueous solutions of metal salts yielded multifold gel structures. Aqueous sodium chloride and potassium chloride as well as pure water induced isotropic gels. Aqueous calcium salts induced liquid crystalline gel with refractive index gradient/amorphous gel alternative structure. Aqueous salts of trivalent aluminum and ferric cations induced a rigid liquid crystalline gel, which shrank above a threshold concentration of each salt. On the other hand, Liesegang ring-like pattern was observed with aqueous solutions of mixed salts of calcium chloride and magnesium chloride. The patterns have been classified to discuss the mechanism of forming the variety of structures.