Synthesis of poly(vinylene-arsine)s: alternating radical copolymerization of arsenic atomic biradical equivalent and phenylacetylene

Novel organoarsenic polymers, poly(vinylene-arsine)s, were synthesized by a free-radical alternating copolymerization of phenylacetylene with cyclooligoarsines as an atomic biradical equivalent. The polymerization between pentamethylpentacycloarsine (1a) or hexaphenylhexacycloarsine (1b) with phenylacetylene (2) in the presence of a catalytic amount of AIBN (in benzene; refluxing; for 12 h) gave the corresponding poly(vinylene-arsine)s. The obtained polymers were soluble in common organic solvents such as THF, chloroform, and benzene. From gel permeation chromatographic analysis (chloroform, PSt standards), the number-average molecular weights of the polymers from 1a and 1b were found to be 11500 and 3900, respectively. The structures of the polymers were supported by 1H and 13C NMR spectroscopies. The corresponding polymer was also obtained by irradiation of a benzene solution of 1a and 2 with xenon lamp at room temperature. After the polymer from 1a was stirred vigorously with 30% H2O2, the 1H NMR spectrum of the polymer showed the methyl proton that was assigned to As(III)-Me, suggesting the insensitivity of the trivalent state arsenic in the main chain to the oxidation. The structures and the molecular weights of the polymers were insensitive to the feed ratio of the monomers. This result indicates that the addition of the arsenic radical to phenylacetylene was a rate-determining step in the copolymerization.     

Effects of various thiol molecules added on morphology of dendrimer-gold nanocomposites

Interactions between poly(amidoamine) dendrimer (PAMAM)-gold nanocomposites and alkanethiols and between the former nanocomposites and thiol-modified poly(amidoamine) dendrons in ethyl acetate were investigated by adding alkanethiols, such as 1-propanethiol and 1,3-propanedithiol, and thiol-modified poly(amidoamine) dendrons, generations 0.5 and 2.5 (G0.5-SH and G2.5-SH). The PAMAM dendrimers with surface methyl ester groups used were generations 1.5 and 5.5 (G1.5 and G5.5). The mean particle sizes of PAMAM-gold nanocomposites were about 2.1 for G1.5 and 2.4 nm for G5.5. In both nanocomposite systems where 1-propanethiol and 1,3-propanedithiol were added, the mean particle size was about 4 nm, twice that of the systems where these thiols were not added. Increasing the addition of 1,3-propanedithiol made the average particle size smaller for both nanocomposites systems. To compare with alkanethiol, thiol-modified poly(amidoamine) dendron with a highly branched structure on one side was synthesized. Using G2.5-SH as a protective agent, dendron-gold nanocomposites with mean diameters of 3 to 4 nm were obtained. The difference in particle size was seen only when the combination of PAMAM-gold nanocomposites and thiol-modified dendron was less sterically dense, modified dendron (G0.5-SH). The mechanisms for morphology changes in the dendrimer-gold nanocomposites by the addition of these thiols are discussed.     

Cross-metathesis of vinyl aromatic heterocycles with 1-octene in the presence of a Schrock catalyst

Metathesis of 2-vinyl aromatic heterocycles such as furan, thiophene, pyrrole and pyridine in the presence of a molybdenum-based Schrock catalyst has been investigated from a synthetic point of view. The self-metathesis of 2-vinyl aromatic heterocycles was not successful. However, in cross-metathesis of thiophene, furan and styrene with 1-octene, the cross-metathesis product, heterodimer, was readily obtained selectively, together with only small amounts of the two corresponding self-metathesis products. The origin of the surprisingly high selectivity of heterodimer formation was elucidated through metallacyclobutane intermediate mechanism, observations of carbenes by in situ ¹H NMR, and reaction products.     

Key aspects of crystalline Mo-V-O-based catalysts active in the selective oxidation of propane

Mo-V-O-based complex metal oxide catalysts were synthesized hydrothermally for the first time, characterized structurally and tested in the selective oxidation of propane to acrylic acid, and the results obtained were compared on the basis of catalyst crystal structures in order to clarify key aspects of alkane selective oxidation over multifunctional metal oxide catalysts. The catalysts tested were black solids of rod-shaped crystals, which had a layer structure in the direction of fiber axis and various high dimensional arrangements of metal octahedra in the cross-section plane. A strong dependency on the octahedra arrangements and a facet dependency were observed, and the roles of metal elements in the course of selective oxidation of propane were clarified by comparing the catalytic performance of various Mo-V-O-based catalysts. We discuss the multi-functional character derived from high dimensional structures of the catalysts and mechanism of the selective oxidation of propane.     

Synthesis and properties of bowl‐shaped homotriazacalix[3 and 6] arenes and the acyclic analogues

Bowl‐shaped chiral homotriazacalixarenes were prepared by the cyclization reactions of chiral triamines with three equimolar amounts of bis(chloromethyl) phenols or bis(chloromethyl) phenol‐formaldehyde dimers in moderate yields. The corresponding acyclic phenol‐formaldehyde oligomers were also synthesized. The structural analysis of the macrocycles by nmr and circular dichroism spectra imply the existence of chiral transmission from the point chirality of the cysteine bridge to the cyclophane moiety. Their cyclic and acyclic compounds have a π‐base cavity large enough to include the ammonium ion.     

Comparison of PAMAM-Au and PPI-Au nanocomposites and their catalytic activity for reduction of 4-nitrophenol

Dendrimer-Au nanocomposites are prepared in aqueous solutions using poly(amidoammine)dendrimers (PAMAM) (generation 2, 3, and 5) and poly(propyleneimine)dendrimers (PPI)(generation 2, 3, and 4) by wet chemical NaBH(4) method. The Au nanoparticles thus obtained are 2-4 nm in diameter for both dendrimers and no generation dependence on the particle size is observed, whereas the generations of the dendrimers are increased as stabilization of Au-nanoparticles is achieved with lower dendrimer concentrations. Studies of the reduction reaction of 4-nitrophenol using these nanocomposites show that the rate constants for the PAMAM dendrimers (generations 2 and 3) are higher than those for the PPI dendrimers (generations 2 and 3), while a distinct difference in the rate constants is not seen for the PAMAM dendrimer (generation 5) or the PPI dendrimer (generation 4). In addition, the rate constants for the reduction of 4-nitrophenol involving all the dendrimers decrease with increases in dendrimer concentrations.     

Kinetic study of the electron-transfer oxidation of the phenolate anion of a vitamin E model by molecular oxygen generating superoxide anion in an aprotic medium

Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger.     

Aqueous Titanate Sols from Ti Alkoxide-α-Hydroxycarboxylic Acid System and Preparation of Titania Films from the Sols

Aqueous titanate sols were prepared by reactions of titanium tetraisopropoxide (TIP) with -hydroxycarboxylic acids in water. IR and Raman spectra, and elemental analyses of the precipitates obtained from the sols revealed that the carboxylates were chelated to titanium but the Ti species were polymerized to form a cluster that had a colloidal nature. Spin-coating of titania (TiO₂) thin films from these sols was also examined. Interestingly, it was found that (004) preferentially oriented anatase films with refractive index of 2.54 were obtained from TIP-lactic acid-NH₃ (1:1:1, molar ratio) aqueous sol. This crystallographic orientation was characteristic of the TIP-lactic acid-NH₃ (1:1:1) system, and was not affected by the kinds of substrates used and the heating rate of the film. TEM observation indicated that small anatase grains had already formed at 200°C. Therefore, the crystallographic orientation might depend strongly on the structure of the chemical species of the precursor solutions.