The phase diagram of the lyotropic nematic mesophase in the TTAB/NaBr/water system

The phase diagram of the nematic mesophase present in the tetradecyltrimethylammonium bromide/sodium bromide/water ternary system was determined. A calamitic nematic mesophase (N_C) was observed which extends to very high concentrations of electrolyte. The order parameters of the surfactant head group in the mesophases were studied by the NMR quadrupolar splitting of the deuterated surfactant. On increasing the temperature of nematic mesophases with low electrolyte concentrations, a phase separation occurs with the formation of a more highly ordered hexagonal phase and an isotropic phase. Diffusion measurements of the isotropic micellar solution by the NMR PFG method were used to estimate hydrodynamic radii at low surfactant concentrations and to study micelle diffusion as the concentration of the surfactant was increased to the liquid crystalline region. At higher surfactant concentrations, the diffusion coefficient reached a limiting value. The calamitic nematic mesophase in this surfactant/electrolyte/water system appears to be formed by long wormlike micelles.     

Asymmetric hydrogenation of alkyl(vinyl)thioethers: a promising approach to α-chiral thioethers

This paper describes the enantioselective hydrogenation of vinylthioethers. We show that thioether derivatives of maleic esters can be hydrogenated with full conversion and up to 60% ee, and that α-thioether cinnamic acids can be hydrogenated in 51% ee with modest conversion.     

Synthesis and characterization of functional gradient copolymers of allyl methacrylate and butyl acrylate

Functional spontaneous gradient copolymers of allyl methacrylate (A) and butyl acrylate (B) were synthesized via atom transfer radical polymerization. The copolymerization reactions were carried out in toluene solutions at 100 °C with methyl 2‐bromopropionate as the initiator and copper bromide with N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst system. Different aspects of the statistical reaction copolymerizations, such as the kinetic behavior, crosslinking density, and gel fraction, were studied. The gel data were compared with Flory's gelation theory, and the sol fractions of the synthesized copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance spectroscopy. The copolymer composition, demonstrating the gradient character of the copolymers, and the microstructure were analyzed. The experimental data agreed well with data calculated with the Mayo–Lewis terminal model and Bernoullian statistics, with monomer reactivity ratios of 2.58 ± 0.37 and 0.51 ± 0.05 for A and B, respectively, an isotacticity parameter for A of 0.24, and a coisotacticity parameter of 0.33. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5304–5315, 2006     

The Hard Lefschetz Theorem and the topology of semismall maps

A line bundle on a complex projective manifold is said to be lef if one of its powers is globally generated and defines a semismall map in the sense of Goresky-MacPherson. As in the case of ample bundles the first Chern class of lef line bundles satisfies the Hard Lefschetz Theorem and the Hodge-Riemann Bilinear Relations. As a consequence, we prove a generalization of the Grauert contractibility criterion: the Hodge Index Theorem for semismall maps, Theorem 2.4.1. For these maps the Decomposition Theorem of Beilinson, Bernstein and Deligne is equivalent to the non-degeneracy of certain intersection forms associated with a stratification. This observation, joint with the Hodge Index Theorem for semismall maps gives a new proof of the Decomposition Theorem for the direct image of the constant sheaf. A new feature uncovered by our proof is that the intersection forms involved are definite.     

Infrared and Raman spectroscopic investigation of Eu3+-doped mono and Di-urethanesil hybrid siliceous materials

The general features of two series of sol-gel derived materials, designatedurethanesils (Ut), have been investigated by infrared and Raman spectroscopies with the goal of elucidating the chemical environment of the Eu³⁺ cations. The host frameworks of the two families of ormolytes studied have been represented by m-Ut(350) and d-Ut(300), where m stands for mono, d stands for di, 350 and 300 are the average molecular weights of the organic precursors (poly(ethylene glycol) methyl ether, PEGME, and poly(ethylene glycol), PEG, respectively). The hybrid matrix of the mono-xerogels is composed by a siliceous backbone bonded by means of urethane linkages (-NHC (=O)O-) to pendant methyl end capped oligopolymer chains with approximately 7 oxyethylene units, whereas that of the di-xerogels is based on a siliceous network grafted through urethane groups to both ends of poly(oxyethylene) segments containing about 6 (OCH₂CH₂) repeat units. Both classes of materials have been doped with europium triflate (Eu(CF₃SO₃)₃). The doped samples have been identified by m-Ut(350)_nEu(CF₃SO₃)₃ and d-Ut(300)_nEu(CF₃SO₃), where n is the molar ratio of (OCH₂CH₂) repeat units per Eu³⁺ ion. Materials with n ranging from ∞ to 5 have been analyzed. The spectral data obtained provide evidence that the cations begin to coordinate to the ether oxygen atoms of the oligopolymer chains at n=40 in the mono-urethanesils and at n=10 in the di-urethanesils. In mono-urethanesils samples with n>40 and in di-urethanesils materials with n>10, the Eu³⁺ coordinate exclusively to the carbonyl oxygen atoms of the urethane linkages. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Γ-type-invariants associated toPU(2)-bundles and the differentiable structure of Barlow's surface

Supported by a Heisenberg-scholarship of the DFG