Diastereoselective cycloadditions of chiral homoallylic alcohols with benzonitrile oxide

The first diastereoselective cycloaddition of a nitrile oxide with a homoallylic alcohol is discussed. The reaction of benzonitrile oxide with the magnesium alkoxides of chiral homoallylic alcohols has been shown to proceed with good diastereoselectivity, favoring the syn isomer of the resulting 2-isoxazoline.     

Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.     

Synthesis, X-ray diffraction study, and ionic conductivity of new AB2O6 pyrochlores

The oxides A(Ti_0.5Te_1.5)O₆ (A = K, Rb, Cs, Tl), A(Ti_0.5W_1.5)O₆ (A = Rb, Cs, Tl), and Cs(B_0.5W_1.5)O₆ (B = Zr, Hf) have been obtained as polycrystalline powders giving X-ray diffraction patterns characteristic of defect cubic pyrochlores, space group (No. 227), Z = 8. The best discrepancy R factors, from 0.0265 for Rb(Ti_0.5Te_1.5)O₆ to 0.0554 for Cs(Zr_0.5W_1.5)O₆, were obtained for the B cations randomly distributed at 16(d), A ions at one quarter of 32(e), and oxygen atoms at 48(f) positions. A linear relationship is observed between the a unit cell parameters and the ionic radii of the A cations, as well as the average ionic radii of the B atoms. The results of electrical resistivity measurements for A(Ti_0.5Te_1.5)O₆ (A = K, Rb, Cs, Tl) are given.     

Characterization of thermal diffusion in polymer solutions by thermal field-flow fractionation: Dependence on polymer and solvent parameters

The thermal diffusion coefficient D_T has been obtained for 17 polymer-solvent combinations, each of them spanning a range of polymer molecular weights, using thermal field-flow fractionation. The polymers examined include polystyrene, poly(alpha-methyl)styrene, polymethylmethacrylate, and polysioprene. The solvents include benzene, toluene, ethylbenzene, tetrahydrofuran, methylethylketone, ethylacetate, and cyclohexane. Although D_T was confirmed as essentially independent of polymer molecular weight, it was found to vary substantially with the chemical composition of polymer and solvent. The results were used to evaluate several thermal diffusion theories; the agreement with theory was generally found to be unsatisfactory. Attempts were then made to correlate the measured thermal diffusion coefficients with various physicochemical parameters of the polymers and solvent. A good correlation was found in which D_T increases with the thermal conductivity difference of the polymer and solvent and varies inversely with the activation energy of viscous flow of the solvent.     

Dendrimers as scaffolds for multifunctional reversible addition–fragmentation chain transfer agents: Syntheses and polymerization

The synthesis and characterization of novel first‐ and second‐generation true dendritic reversible addition–fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3‐benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z‐group architecture based on 1,1,1‐hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free‐radical polymerization at 60 °C. The novel dendrimer‐based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number‐average molecular weight (M_n) with the monomer–polymer conversion, yielding star polymers with molecular weights of up to M_n = 160,000 g mol^?1 for PBA (based on a linear PBA calibration) and up to M_n = 70,000 g mol^?1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1‐hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star‐shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star‐shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877–5890, 2004     

Hollow latex particles as submicrometer reactors for polymerization in confined geometries

A method was developed for free‐radical polymerization in the confines of a hollow latex particle. Hollow particles were prepared via the dynamic swelling method from polystyrene seed and divinylbenzene and had hollows of 500–1000 nm. So that these hollow poly(divinylbenzene) particles could function as submicrometer reactors, the particles were filled with a monomer (N‐isopropylacrylamide) via the dispersion of the dried particles in the molten monomer. The monomer that was not contained in the hollows was removed by washing and gentle abrasion. Free‐radical polymerization was then initiated by γ radiolysis in the solid state. Transmission electron microscopy showed that poly(N‐isopropylacrylamide) formed in the hollow interior of the particles, which functioned as submicrometer reactors. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5706–5713, 2004     

Standardization of BSE rapid test performances and experiences gathered during the implementation of large-scale testing

The accumulation of pathological prion protein is used as a diagnostic marker for transmissible spongiform encephalopathies. According to European Union (EU) regulations cattle older than 30 months of age (Germany, France, Italy, and Spain by national law >24 months) and slaughtered for human consumption must be tested by using rapid tests for bovine spongiform encephalopathy (BSE). Likewise fallen stock and clinically affected animals must be tested. This article gives a short overview of the incidence of BSE in Europe. The diagnostic hierarchy, i.e., the officially approved methodology for the confirmation of suspect rapid test cases, and the organization of the numerous laboratories involved in this large-scale testing for BSE are described. Special emphasis is given to necessary quality control measures currently in place for BSE rapid testing laboratories and to measures intended to assure a consistent performance of the commercially available rapid test kits.Presented at BERM-9—Ninth International Symposium on Biological and Environmental Reference Materials, 15–19 June 2003, Berlin, Germany.     

Generating cryptographically strong Boolean functions using partial information

Periodica Mathematica Hungarica - In our paper we study the usage of partially defined Boolean functions (PDBFs) for generating cryptographically strong Boolean functions. A PDBF can be considered...     

Regioselective 1,4-trifluoromethylation of α,β-enones using ‘protect-in-situ’ methodology

In a convenient and efficient procedure, the nucleophilic 1,4-trifluoromethylation of several α,β-enones using (trifluoromethyl)trimethylsilane was achieved. The high regioselectivity of the reaction has been reached by blocking the carbonyl moiety of the electrophile with a bulky aluminum-centered Lewis acid.