Nematic liquid crystal droplets with an enhanced quasi-linear electro-optical response

Nematic liquid crystal droplets dispersed in a thermoplastic matrix with a built-in d.c. electric field exhibit a quasi-linear response to an electric field. In this work we show a device characterized by a large light modulation. The device can store fields up to several V μm^-1 and operates well from d.c. to several kHz. In addition, we found that the experimental results are in agreement with a simple theoretical model for light scattering by a dispersion of liquid crystal droplets. This device allows us to overcome possible drawbacks, due to a reduced light modulation, in applications where polarity detection is required.     

Benzoyl Group Migrations in Methyl 2,3,6-Trio-O-Benzoyl-4-deoxy-4-(N-Hydroxyamino)-α-D-Gluco and α-D-Galacto-Pyranosides

Abstract

Deoxy-N-hydroxyaminosugars constitute a novel family of sugars. The interest in them is mainly due to their close structural similarity to natural sugars, coupled, with their easy oxidation to nitroxide free radicals, enabling their study by ESR spectroscopy.¹ From the point of view of their chemical reactivity, the hydroxyamino group is an ambident nucleophile possessing complex orbital and topographical factors, which direct its reactivity to either of its heteroatoms.     

Boundary value problems with nonhomogeneous Neumann conditions on a fractal boundary

This note deals with some boundary value problems in a self-similar ramified domain of ${\mathbb{R}}^2$, with a fractal boundary. The partial differential equation is Laplace's equation, and there are nonhomogeneous generalized Neumann boundary conditions on the fractal boundary. We propose a multiscale strategy for approximating the restriction of the solutions to simple subdomains. This strategy is based on transparent boundary conditions and on a wavelet expansion of the Neumann datum. To cite this article: Y. Achdou, N. Tchou, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Study of conformational properties of a biologically active peptide of fibronectin by circular dichroism, NMR and molecular dynamics simulation

Circular dichroism (CD), and NMR spectra have been recorded and molecular dynamics (MD) simulations have been performed in water and water-trifluoroethanol (TFE) mixed solvent for a synthetic biologically active 13-amino-acid fragment of human fibronectin and two related peptides. The CD results are interpreted on the basis of statistical analyses of MD trajectories and of ensuing calculations of CD spectra based on Schellman's matrix method. It is observed that the peptide conformation is quite variable in water and loses its mobility with the addition of TFE. (1)H-NOE data were found to be consistent with the most abundant calculated conformation.     

Alpha-cyclodextrin functionalized CdS nanocrystals for fabrication of 2/3 D assemblies

Different types of cyclodextrins (CDs) have been tested as mediators for the water phase transfer of organic-capped CdS nanocrystals (NCs), and alphaCD has been demonstrated to be the most effective system. The formation of a complex based on alphaCDs and colloidal NCs has been considered to be responsible for the phase transfer process and extensively investigated by optical, structural, and calorimetric measurements, as a function of the experimental parameters (pH and NC and CD concentration). A mechanism for the complexation phenomena has been suggested. The fabrication of 2/3 D supramolecular architectures has been proposed according to two different strategies. First, a layer-by-layer procedure has been used to obtain multilayered structures where polyelectrolyte layers have been intercalated with negatively charged alphaCD-CdS NC complexes by exploiting electrostatic interaction between polyelectrolyte and cyclodextrin OH groups. Second, a monolayer of CdS NCs has been deposited onto a self-assembled monolayer of sulfated CDs, thus combining the use of an electrostatic-force-based approach and host-guest chemistry. The important role played by host-guest interactions has then been revealed.     

α-chymotrypsin superactivity in cetyltrialkylammonium bromide-rich media

α-Chymotrypsin (α-CT) activity was tested with N-glutaryl-l-phenylalanine p-nitroanilide in buffered media with added cationic surfactants. The effect of the commercial cetyltrimethylammonium bromide (CTABr) was compared with that of three other surfactants with ethyl (CTEABr), propyl (CTPABr), and butyl (CTBABr) head groups. These were synthesized and purified in this laboratory. Surfactant head groups provided distinct environments that largely modulated the catalytic performance. Larger alkyl head group hydrophobicity led to a marked enhancement of α-CT activity. CTBABr-rich media induced the highest superactivity. Kinetic measurements were performed in Tris-HCl buffer at a surfactant concentration either below or above CMC, and α-CT superactivity occurred in both media. Positive interactions between the enzyme and surfactants happened independently of thesupramolecular organization of the medium. The reaction followed the Michaelis-Menten kinetics. The substrate to micelle aggregates binding constant was used to calculate the substrate concentration available for catalysis. The k _cat to k _m ratio was in CTBABr-rich media always higher than in pure buffer and depended on the surfactant concentration. α-CT superactivity depended on the pH value of buffer solution. Enzyme inactivation followed a single-step mechanism in pure buffer and a series mechanism in the presence of a surfactant. The rate of activity decay obeyed a first-order kinetics.     

Hydrosilylation of aromatic nitriles promoted by solvated rhodium atom-derived catalysts

Rhodium metal particles, isolated as supported or unsupported powder starting from mesitylene solvated rhodium atoms, catalyse the hydrosilylation of aromatic nitriles to N,N-disilylamines in high conversion at 100°C. Different hydrosilanes (HSiMe₃, HSi(OEt)₃) can be employed. In the case of cinnamonitrile, the chemoselectivity of the reaction to 2-trimethylsilyl-3-phenylpropionitrile and (E)- and (Z)-1-di(trimethylsilyl)amino-3-phenyl-1-propene is strongly dependent on the reaction temperature. The commercial rhodium on γ-Al₂O₃ catalyst is considerably less active and selective than the analogous catalyst prepared via Metal Vapour Synthesis (MVS) probably owing to the different dimension and distribution of the metal particles in the two samples as shown by HRTEM analysis.     

Synthesis and NMR characterization of a novel class of thienomorphinans

[formula: see text] Synthesis of four novel thieno derivatives 4-7 featuring the codeine skeletal backbone is reported. Characterization by 1H and 13C NMR is also discussed, along with binding profile for opioid receptors.