Effect of adsorbed water on the electrorheology of silica suspensions

Monodisperse silica particles were formed by hydrolyzing tetraethylorthosilicate in an ethanol solution and the silica suspensions dispersed in a silicone oil were prepared by a different procedure. The effects of adsorbed water on the electrorheological (ER) behavior were studied under oscillatory shear. The amounts of adsorbed water and surface silanol groups were determined by thermogravimetric analysis. The magnitude of the complex viscosity, |η^*|, increases with the application of electric fields. The physically adsorbed water is primarily responsible for the ER effect. However, the fluids containing large amounts of adsorbed water do not always show excellent ER performance. The surface silanol groups have an important role in promoting the ER effect. Not only the amount but also the situation of silanol groups determines the ER activity of adsorbed water.     

Regioselective synthesis of virazole using benzyl cyanoformate as a synthon

An antiviral nucleoside or virazole was synthesized efficiently and regioselectively starting with benzyl cyanoformate.     

Novel type of heterogenized CuCl2 catalytic systems for oxidative carbonylation of methanol

A novel type of heterogenized CuCl₂ catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl^– while keeping the catalytic activity of the homogeneous CuCl₂ catalyst, we adopted, as supports (or ligands) of CuCl₂, four polymers, bearing a 2,2-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2-bipyridine-5,5-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N-bisphenylene-2,2-bipyridine-4,4-dicarboxylic amide) (Bpya), and poly(4-methyl-4-vinyl-2,2-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl₂ and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl₂ and Ppy-CuCl₂ catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl₂ catalyst. This high activity appears to be associated with the presence of the -conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl₂ catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl₂ leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system.     

A new strategy for construction of eight-membered carbocycles by Brook rearrangement mediated [6 + 2] annulation

[reaction: see text] A newly developed strategy for construction of eight-membered carbocycles via [6 + 2] annulation that involves the combination of beta-alkenoyl acylsilanes and a vinyllithium derivative is described. A unique feature of this annulative approach is that it enables in one operation and a stereoselective manner construction of eight-membered ring systems containing useful functionalities for further synthetic elaboration from readily available six- and two-carbon components.     

Drug-plasma protein binding assay by electrokinetic chromatography-frontal analysis

We developed a rapid, microscale and reliable analytical method for binding of drugs to plasma proteins using capillary electrophoresis (CE) with ionic cyclodextrins (CD) combined with frontal analysis. These CDs were used as pseudostationary phases of electrokinetic chromatography (EKC). The CD-modified EKC (CDEKC) approach allowed us to separate anionic drugs from plasma proteins, whereas CZE could not separate these drugs from plasma proteins because they had a similar mobility like plasma proteins. CDs uniquely interact with these drugs but not with plasma proteins. Therefore, CDEKC could be coupled with frontal analysis to measure the binding of anionic drugs to plasma proteins. The binding values obtained by CDEKC were highly consistent with those determined by the ultrafiltration method. Our CDEKC approach should expand the applicability of CE to protein binding analysis.     

Stereospecific synthesis of new 2,3,4,5-piperidinetetracarboxylic acids and 2,3,5-piperidinetricarboxylic acids

Diels-Alder adducts of 1,2-dihydropyridine with maleic and acrylic acid derivatives were stereospecifically converted by way of RuO₄ oxidation into new r-2,c-3,c-4,c-5-piperidinetetracarboxylic acid, r-2,t-3,t-4,c-5-piperidinetetracarboxylic acid, r-2,c-3,c-5-piperidinetricarboxylic acid, and r-2,t-3,c-5-piperidinetricarboxylic acid.     

Manganese(II) o ctacyanotungstate(V)-based magnet containing a noncoordinated aromatic molecule

We have prepared a pillared layer magnetic material containing a noncoordinated aromatic molecule, [{MnII(pyrimidine)(H2O)}2{MnII(H2O)2}{WV(CN)8}2](pyrimidine)2.2H2O. This compound has one-dimensional channels (6.2 x 2.1 A) that are occupied by noncoordinated pyrimidine. The magnetization versus temperature plots showed the magnetic phased transition temperature (TC) was 47 K. The magnetization versus external magnetic field plots showed that the saturation magnetization (MS) value was 13.0 muB at 2 K. This MS value indicates that an antiferromagnetic interaction operates between the WV (S = 1/2) and MnII (S = 5/2) ions. The magnetic hysteresis loop showed that the coercive field (HC) was 17 G at 2 K.