Oxythallation of norbornene derivatives with thallium(III) acetate in methanol

Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis-exo-acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by ¹³C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2-endo-carboxylic acid, lactonization occurs to give a trans-oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. ¹H and/or ¹³C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo-alcohol.     

Vinyl polymerization. 413. Polymerization of vinyl monomer initiated by poly(vinylbenzyltrimethyl)-ammonium chloride

The polymerization of vinyl monomer initiated by an aqueous solution of poly(vinylbenzyltrimethyl)ammonium chloride (Q-PVBACI) was carried out at 85°C. Styrene, p-chlorostyrene, methyl methacrylate, and i-butyl methacrylate were polymerized, whereas acrylonitrile and vinyl acetate were not. The effects of the amounts of vinyl monomer, Q-PVBACI, and water on the conversion of vinyl monomer were studied. The overall activation energy in the polymerization of styrene was estimated as 79.1 kJ mol^?1. The polymerization proceeded through a radical mechanism. The selectivity of vinyl monomer was discussed by “a concept of hard and soft hydrophobic areas and monomers.”     

Diacetoxylation of conjugated dienes with thallium(III) acetate in acetic acid

The reaction of conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,5-dimethyl-2,4-hexadiene, 1,3-cyclopentadiene, and 1,3-cyclohexadiene, with thallium(III)acetate in acetic acid at 10–65° for 0.5–15 hr affords an isomeric mixture of the corresponding diacetoxyalkenes (1,2- and 1,4-addition products) in 10–92% yields. The 1,2-addition products are predominantly formed in all cases examined except the case of 1,3-cyclopentadiene. The reaction is assumed to proceed through acetoxythallation and dethallation steps, the latter step being accompanied and/or followed by an attack of acetoxyl group. An initial attack of thallium moiety is proposed to occur mainly at C-1 and C-2 carbons in the cases of linear terminal dienes and cyclic dienes, respectively.     

Radial breathing modes of single-walled carbon nanotubes in resonance Raman spectra at high temperature and their chiral index assignment

Radial breathing modes (RBMs) in resonance Raman spectra from single-walled carbon nanotubes (SWCNTs) on a SiO₂/Si (0 0 1) substrate are studied between 25 and 720 °C. A change in the relative intensity of each RBM peak with temperature is observed, which originates from the temperature dependence of the resonance condition of nanotubes. For 25 °C, each RBM peak is reasonably assigned on the basis of data in the literature [J. Maultzsch, H. Telg, S. Reich, F. Hennrich, C. Thomsen, Phys. Rev. B 72 (2005) 205438]. By taking into account the temperature-dependent behavior of the relative intensity of the RBM peaks, each RBM peak is successfully assigned even for 720 °C. It is found that most of the observed RBM peaks for a laser excitation energy of E_exc = 1.96 eV are from chiral SWCNTs. These results make it possible to discuss further details of the chirality-dependent growth behavior observed for in situ Raman spectroscopy.     

Statistics of reaction progress variable and mixture fraction gradients of a pulverised coal jet flame using Direct Numerical Simulation data

The statistical behaviour of the variances, covariance and gradients of the reaction progress variable (c), and the mixture fraction (ξ) have been analysed in a pulverised coal jet flame using a three-dimensional carrier phase direct numerical simulation (DNS) dataset. It has been observed that the Favre-probability density functions (PDFs) of c and ξ can be parametrised by the standard β function. Furthermore, the log-normal distribution has been found to accurately represent |?c| and |?ξ|. It is also found that ?c and ?ξ remain aligned throughout the flame brush. Finally the joint PDF of |?c| and |?ξ| has been compared with the product of the PDF of |?c| and PDF of |?ξ| extracted from carrier phase DNS, and it has been found that |?c| and |?ξ| are not statistically independent in the case investigated.The bivariate log-normal distributions with and without correlation have also been considered, and the former is found to be in better agreement with the carrier phase DNS data.     

A compact optical heterodyne interferometer by optical integration and its application

A compact high-resolution optical heterodyne interferometer combining a two-frequency light module and a minute optical system is described. The light module, which generates two independent frequencies of light, is fabricated by proton exchange method on LiNbO₃ substrate. We report an experiment evaluating measurement accuracy using a micro-displacement measurement system which incorporates this interferometer. Results of the experiment with a standard thickness sample show high thermal stability with maximum measurement error of 1.8 nm at a temperature from 19°C to 33°C. The system was used to measure the hysteresis of a piezoelectric element for displacements of several nm, thereby making it possible to analyze the system quantitatively in practice.     

A novel synthesis of half-protected 1,3-dicarbonyl compounds

It has been found that the reaction of enol silyl ethers with 2-ethoxy-1,3-dithiolane proceeds smoothly in the presence of zinc chloride catalyst to afford half-protected 1,3-dicarbony1 compounds in moderately good yields.     

A novel action of terpendole E on the motor activity of mitotic Kinesin Eg5

To reveal the mechanism of mitosis, the development of M phase-specific inhibitors is an important strategy. We have been screening microbial products to find specific M phase inhibitors that do not directly target tubulins, and rediscovered terpendole E (TerE) as a novel Eg5 inhibitor. TerE did not affect microtubule integrity in interphase, but induced formation of a monoastral spindle in M phase. TerE inhibited both motor and microtubule-stimulated ATPase activities of human Eg5, but did not affect conventional kinesin from either Drosophila or bovine brain. Although terpendoles have been reported as inhibitors of acyl-CoA:cholesterol O-acyltransferase (ACAT), the Eg5 inhibitory activity of TerE was independent of ACAT inhibition. Taken together, we demonstrate that TerE is a novel Eg5 inhibitor isolated from a fungal strain.     

Selective growth of ZnO nanodots prepared by metalorganic chemical vapor deposition on focused-ion beam-nanopatterned substrates

Selective formation of ZnO nanodots grown by metalorganic chemical vapor deposition (MOCVD) was achieved on focused-ion beam (FIB)-nanopatterned SiO₂ and Si substrates. The selective formation characteristics, dimension, and density of ZnO nanodots on FIB-nanopatterned substrates strongly depended on the FIB-patterning and MOCVD-growth conditions. The mechanism of the selective formation of ZnO nanodots on FIB-nanopatterned SiO₂ substrates is attributed to a surfactant effect of the implanted Ga which leads to the formation of the preferred nucleation sites for the growth of ZnO nanodots, while that of ZnO nanodots on nanopatterned Si substrates is mainly considered in terms of the generation of surface atomic steps and kinks, which are created by Ga⁺ ion sputtering, on the patterned Si areas.