Convenient synthesis of alkoxyhalosilanes from hydrosilanes

Selective dehydrogenative coupling of di- and trihydrosilanes with alcohols catalyzed by PdCl₂ or NiCl₂ afforded alkoxyhydro- and dialkoxyhydrosilanes in good yield. Further treatment of the resulting alkoxyhydrosilanes with carbon tetrachloride or allyl bromide in the presence of the same catalyst led to the formation of alkoxychloro- and alkoxybromosilanes, respectively. Similar reactions of dialkoxyhydrosilanes with carbon tetrachloride afforded dialkoxychlorosilanes in good yield, although contamination of small amounts of trialkoxysilanes and alkoxydichlorosilanes was detected in the products. Selective substitution of the alkoxyhalosilanes with nucleophiles is also reported.     

Chiral discrimination of a helically organized crown ether array parallel to the helix axis of polyisocyanate

The asymmetric polymerization of 4′‐isocyanatobenzo‐18‐crown‐6 with the lithium amide of (S)‐(2‐methoxymethyl)pyrrolidine successfully proceeded to afford end‐functionalized poly(4′‐isocyanatobenzo‐18‐crown‐6) with (S)‐(2‐methoxymethyl)pyrrolidine (polymer 2 ). In the circular dichroism (CD) spectrum of 2 , a clear positive Cotton effect was observed in the range of 240–350 nm corresponding to the absorption of the polymer backbone, indicating that 2 partially formed a one‐handed helical structure, which was preserved by the chirality of (S)‐(2‐methoxymethyl)pyrrolidine bonding to the terminal end in 2 . In the titration experiments for the CD intensity of 2 in the presence of D ‐ and L ‐Phe·HClO₄ (where Phe is phenylalanine), a small but remarkable difference was observed in the amount of the chiral guest needed for saturation of the CD intensity and in the saturated CD intensity, indicating that the extremely stable, one‐handed helical part should exist in the main chain of 2 , which was not inverted even when the unfavorable chiral guest for the predominant helical sense, L ‐Phe·HClO₄, was added. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests; that is, the guests were extracted from the aqueous phase into the organic phase with enantiomeric excess. The driving force of the chiral discrimination ability of 2 should certainly be attributed to the one‐handed helical structure in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 325–334, 2006     

Preparation and characterization of mesoporous silica thin films from polyethoxysiloxanes

Tetraethoxysilane (TEOS) and polyethoxysiloxanes (PEOSs; prepared by the acid‐catalyzed hydrolytic polycondensation of TEOS) were subjected to the sol–gel process in the presence of cetyltrimethylammonium bromide (CTAB), respectively. The PEOSs with M_w 700–26,000, as prepared by sol–gel coating of TEOS and PEOS under various conditions, were used. Uniform and crack‐free thin films of thickness 276–613 nm were prepared by spin‐coating of a PEOS solution containing CTAB. When the coating films were sintered at 400 °C, the combustion of ethoxy groups and CTAB took place to provide porous silica thin films. The structure of the thin films was found to be dependent on the molecular weight of PEOS and the molar ratio of CTAB/Si: lamellar or hexagonal phase was observed for M_w less than 15,000 and for CTAB/Si molar ratios greater than 0.10. Honeycomb structures were observed for M_w less than 5000 and for CTAB/Si molar ratios of 0.15. The honeycomb structure was also observed by atomic force microscopy and transmission electron microscope. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2542–2550, 2006     

Synthesis of silicon nitride based ceramic nanoparticles by the pyrolysis of silazane block copolymer micelles

Diblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene (polyVSA‐b‐polySt) and triblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene‐block‐poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA‐b‐polySt‐b‐polyVSA), consisting of silazane and nonsilazane segments, were prepared by the living anionic polymerization of 1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane and styrene. PolyVSA‐b‐polySt formed micelles having a poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA) core in N,N‐dimethylformamide, whereas polyVSA‐b‐polySt and polyVSA‐b‐polySt‐b‐polyVSA formed micelles having a polyVSA shell in n‐heptane. The micelles with a polyVSA core were core‐crosslinked by UV irradiation in the presence of diethoxyacetophenone as a photosensitizer, and the micelles with a polyVSA shell were shell‐crosslinked by UV irradiation in the presence of diethoxyacetophenone and 1,6‐hexanedithiol. These crosslinked micelles were pyrolyzed at 600 °C in N₂ to give spherical ceramic particles. The pyrolysis process was examined by thermogravimetry and thermogravimetry/mass spectrometry. The morphologies of the particles were analyzed by atomic force microscopy and transmission electron microscopy. The chemical composition of the pyrolysis products was analyzed by X‐ray fluorescence spectroscopy and Raman scattering spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4696–4707, 2006     

Effective Hamiltonian method for environmental effects

Some novel physical ideas and mathematical techniques are described, useful in the development of effective Hamiltonian methods for studying molecular environmental effects.     

Development of dynamic compartment model for prediction of behavior of radioiodine in rice paddy field

For the assessment of a public impact caused by radionuclides released from nuclear facilities, a dynamic compartment model was developed for prediction of behavior of radioiodine in air, paddy field and rice plant system. The transfer coefficients among compartments were determined by some experimental data and assumptions for each chemical form of iodine. A verification of the model was carried out by some case studies.     

Structure of Sol-Gel-Derived Sodium Dititanate Glass

The sodium dititanate, Na₂O·2TiO₂ glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti⁴⁺ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti⁴⁺ ions are rather in five-fold coordination state, forming TiO₅ pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass.     

Catalytic,asymmetric Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen

[reaction: see text] Catalytic, enantioselective Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen are described. Several N-carbamate-protected alpha-imino esters, which are readily prepared from 2-bromoglycine esters using a polymer-supported amine, reacted with silicon enolates to afford the desired adducts in high yields with high enantioselectivity using a copper(II)-diamine complex. Easy deprotection of the product amine and transformation to free alpha-amino acid derivatives have also been demonstrated.