Asymmetric 1,3-dipolar cycloaddition of chiral sulphinylethenes with 1-methyl-3-oxido-pyridinium and some nitrones

1,3-Dipolar cycloaddition of (R)-(+)-p-tolyl vinyl sulphoxide 1 with 1-methyl-3-oxidopyridinium 6 proceeded in a diastereoselective manner to afford the exo and endo cycloadducts 11a,b and 12a in 36%, 7% and 29% yield, respectively. The absolute configuration of 11a was determined by its transformation to (1S)-(−)-2-tropanol (−)-15. Attempts to the cycloaddition of the sulphinylethenes 17–19 with the pyridinium 6 were nsuccessful under several conditions. The reaction of the sulphoxide 20 with pyrroline 1-oxide 21 gave an inseparable mixture of products. The cycloaddition of 20 with 3,4,5,6-tetrahydropyridine 1-oxide22 afforded a mixture of four adducts in ca. 90% yield. High level of diastereoselectivity was achieved for the endo cycloaddition affording the adduct 23 in 33% isolated yield. The absolute configuration of 23 was confirmed by a single-crystal X-ray diffraction study. The stereochemical course of the reaction was discussed based on the absolute configuration of the products.     

Nanoparticulate BaTiO<Subscript>3</Subscript> film produced by aerosol-type nanoparticle deposition

Aerosol-type nanoparticle deposition (NPD) is a magical method to form a dense electroceramic film with a fine, nanoscale structure on a substrate surface by depositing ceramic particles through a nozzle at room temperature. This film has the potential to be applied to various electronic, environmental, and energy devices. However, the deposition mechanism and the nanostructure in the film are not understood sufficiently. This study aimed at investigating the crystal structure of an NPD as-deposited film, and compared the crystal structures of the NPD as-deposited film, annealed film, and the raw powders consisting of particles with diameters of 200 and 50 nm, respectively, using barium titanium oxide (BaTiO₃). We found that the crystal in BaTiO₃ with a disordered phase due to the Ba displacement within the BaTiO₃ was responsible for the adhesion between the BaTiO₃ crystalline particles having a diameter of approximately 10 nm, as well as with the substrate.     

Si(111) surface modified with alpha,beta-unsaturated carboxyl groups studied by MIR-FTIR

A Si(111) surface modified with alpha,beta-unsaturated carboxyl groups was fabricated using activated alkynes such as propiolic acid and propiolic acid methyl ester via hydrosilylation reaction. The obtained coverage of carboxyl groups was roughly estimated to be 55-60% in both cases from the Si-2p and C-1s X-ray photoelectron specroscopy (XPS) peak intensities. The detailed surface structures were investigated by multiple internal reflection Fourier transform infrared (MIR-FTIR) measurement. It was revealed that this reaction was promoted by visible light irradiation at room temperature. The Si surface modified with functional groups prepared under such a moderate condition is adaptable to functional devices which are easily damaged under UV irradiation or high temperature conditions.     

Switching the selectivity of a polyglycerol dendrimer monomolecularly imprinted with d-(−)-fructose

A polyglycerol dendrimer monomolecularly imprinted with d-(−)-fructose (Fru) was synthesized. The dendrimer formed adducts with several monosaccharides, Fru, d-(+)-galactose, d-(+)-glucose, d-(+)-mannose, and methyl-α-d-mannopyranoside (MMan), by removal of four water molecules. The dendrimer preferred Fru in the absence of N,N,N′,N′-tetramethyldiaminomethane (TMDAM), whereas it preferred MMan in the presence of TMDAM.     

Gel‐to‐Sol and Sol‐to‐Gel Transitions Utilizing the Interaction of α‐Cyclodextrin with Dodecyl Side Chains Attached to a Poly(acrylic acid) Backbone

Summary: By utilizing the interaction of α‐cyclodextrin (α‐CD) with dodecyl side chains in polymers of x mol‐% dodecyl‐modified poly(acrylic acid) (p(AA/C₁₂(x))), systems that undergo gel‐to‐sol and sol‐to‐gel transitions were successfully constructed. Rheological experiments indicated that addition of α‐CD to the hydrogel of p(AA/C₁₂(5)) caused a drastic decrease in the viscosity, while addition of oligo(α‐CD) to the solution of p(AA/C₁₂(2)) led to a remarkable increase in the viscosity.

Photographs for a gel‐to‐sol transition upon addition of α‐CD to 5.0 g · L⁻¹ p(AA/C₁₂(5)).     

The strong Lefschetz property for complete intersections defined by products of linear forms

We prove the strong Lefschetz property for certain complete intersections defined by products of linear forms, using a characterization of the strong Lefschetz property in terms of central simple modules.

     

Promotion of low-humidity proton conduction by controlling hydrophilicity in layered metal-organic frameworks

We controlled the hydrophilicity of metal-organic frameworks (MOFs) to achieve high proton conductivity and high adsorption of water under low humidity conditions, by employing novel class of MOFs, {NR(3)(CH(2)COOH)}[MCr(ox)(3)]·nH(2)O (abbreviated as R-MCr, where R = Me (methyl), Et (ethyl), or Bu (n-butyl), and M = Mn or Fe): Me-FeCr, Et-MnCr, Bu-MnCr, and Bu-FeCr. The cationic components have a carboxyl group that functions as the proton carrier. The hydrophilicity of the cationic ions was tuned by the NR(3) residue to decrease with increasing bulkiness of the residue: {NMe(3)(CH(2)COOH)}(+) > {NEt(3)(CH(2)COOH)}(+) > {NBu(3)(CH(2)COOH)}(+). The proton conduction of the MOFs increased with increasing hydrophilicity of the cationic ions. The most hydrophilic sample, Me-FeCr, adsorbed a large number of water molecules and showed a high proton conductivity of ~10(-4) S cm(-1), even at a low humidity of 65% relative humidity (RH), at ambient temperature. Notably, this is the highest conductivity among the previously reported proton-conducting MOFs that operate under low RH conditions.     

Development of a New Distyrylbenzene-Derivative Amyloid-β-aggregation and Fibril Formation Inhibitor

Several new amyloid-β (Aβ) aggregation inhibitors were synthesized according to our theory that a hydrophilic moiety could be attached to the Aβ-recognition unit for the purpose of preventing amyloid plaque formation. A distyrylbenzene-derivative, DSB(EEX)(3), which consider the Aβ recognition unit (DSB, 1,4-distyrylbenzene) and expected to bind to amyloid fibrils (β-sheet structure), was combined with the hydrophilic aggregation disrupting element (EEX) (E, Glu; X, 2-(2-(2-aminoethoxy)ethoxy)acetic acid). This DSB(EEX)(3) compound, compared to several others synthesized similarly, was found to be the most active for reducing Aβ toxicity toward IMR-32 human neuroblastoma cells. Moreover, its inhibition of Aβ-aggregation or fibril formation was directly confirmed by transmission electron microscopy and atomic force microscopy. These results suggest that the Aβ aggregation inhibitor DSB(EEX)(3) disrupts clumps of Aβ protein and is a likely candidate for drug development to treat Alzheimer's disease.