Extensions of nilpotent blocks

Oblatum 16-IX-1988 &; 27-XII-1989     

Sur un théorème de Green

Sans résumé     

Identification of peptides that neutralize bacterial endotoxins using β-hairpin conformationally restricted libraries

Bacterial endotoxins are the major mediator of septic shock; therefore, endotoxin-neutralizing molecules could have biomedical applications. The septic shock cascade relies in a series of molecular recognition processes. The large contact-surface described for the interacting macromolecules, in most cases, prevents the identification of small molecules that could modulate such recognition events. Here we report on a beta-hairpin conformationally restricted combinatorial library that has been generated and screened towards the identification of new peptides that neutralize bacterial endotoxins. Starting with a de novo designed linear peptide that shows a beta-hairpin structure population of around 30%, (Ramirez-Alvarado, M., Blanco, F. J. and Serrano, L. Nat. Struc. Biol., 7, 604-612 (1996)), we selected four positions to build up a combinatorial library of 20(4) sequences. Deconvolution of the library reduced such a sequence complexity to 8 defined sequences. The newly identified peptides have a biological activity equivalent to that reported for peptides derived from natural endotoxin-binding proteins.     

Anisotropic vortex plasticity in the liquid state of YBa2Cu3O7: evidence for quenched c-axis vortex correlation length

A generalized methodology, based on anisotropic angular dependent magnetoresistance measurements, is presented to deconvolute the contributions to the vortex activation energy (i.e., plastic and pinning energies) in the vortex liquid state of high temperature superconductors. Experimental evidence is given for the appearance of a partially entangled liquid vortex state in YBa 2Cu 3O (7) when random quenched and correlated disorders compete, as in twinned melt textured YBa 2Cu 3O (7) quasisingle crystals with Y 2BaCuO (5) precipitates. The hallmark of this new phase is a quench of the c-axis vortex correla-tion length.     

Phase and rheological behavior of the polymerizable surfactant CTAVB and water

The phase and rheological behaviors of the polymerizable surfactant, cetyltrimethylammonium benzoate (CTAVB), and water as a function of surfactant concentration and temperature are investigated here. The critical micelle concentration (cmc) and the (cmc(2)), as well as the Krafft temperature (T(K)), are reported. A large highly viscous micellar solution region and hexagonal- and lamellar-phase regions were identified. The micellar solutions exhibit shear thickening in the dilute regime, below the overlapping or entanglement concentration. At higher concentrations, wormlike micelles form and the solutions show strong viscoelasticity and Maxwell behavior in the linear regime and shear banding flow in the nonlinear regime. The linear viscoelastic regime is analyzed with the Granek-Cates model, showing that the relaxation is controlled by the kinetics of reformation and scission of the micelles. The steady and unsteady responses in the nonlinear regime are compared with the predictions of the Bautista-Manero-Puig (BMP) model. Model predictions follow the experimental data closely.     

Resonance Tongues and Spectral Gaps in Quasi-Periodic Schrödinger Operators with One or More Frequencies. A Numerical Exploration

In this article we investigate numerically the spectrum of some representative examples of discrete one-dimensional Schrödinger operators with quasi-periodic potential in terms of a perturbative constant b and the spectral parameter a. Our examples include the well-known Almost Mathieu model, other trigonometric potentials with a single quasi-periodic frequency and generalisations with two and three frequencies. We computed numerically the rotation number and the Lyapunov exponent to detect open and collapsed gaps, resonance tongues and the measure of the spectrum. We found that the case with one frequency was significantly different from the case of several frequencies because the latter has all gaps collapsed for a sufficiently large value of the perturbative constant and thus the spectrum is a single spectral band with positive Lyapunov exponent. In contrast, in the cases with one frequency considered, gaps are always dense in the spectrum, although some gaps may collapse either for a single value of the perturbative constant or for a range of values. In all cases we found that there is a curve in the (a, b)-plane which separates the regions where the Lyapunov exponent is zero in the spectrum and where it is positive. Along this curve, which is b = 2 in the Almost Mathieu case, the measure of the spectrum is zero.     

A modifier that enables the easy dispersion of alkyl-coated nanoparticles in an epoxy network

Nanoparticles (NPs) coated with alkyl chains cannot be dissolved in diglycidylether of bisphenol A (DGEBA), which is a typical monomer used in the synthesis of epoxy networks. We show that adding small amounts of the linear amphiphilic polymer obtained by reaction of DGEBA with dodecylamine, produced a stable dispersion of dodecanethiol-coated gold NPs in DGEBA. The anionic homopolymerization of this blend initiated by a tertiary amine led to a nanocomposite with a uniform dispersion of gold NPs. The selected crosslinking chemistry allowed covalent bonding of the modifier to the matrix, avoiding phase separation and enabling easy tuning of the thermal properties of the matrix.     

Decomposition processes and structural transformations of cerium propionate into nanocrystalline ceria at different oxygen partial pressures

The structural transformations that occur when thermal treatments turn cerium propionate into nanocrystalline ceria have been analysed with thermoanalytical techniques (TG, DTA and MS) and with structural and magnetic characterization (HRTEM, SQUID and XRD) of the final and intermediate products. Attention has been paid to what occurs during the decomposition of propionate and how the process is affected by the furnace atmosphere (oxidizing or inert). In an oxidizing atmosphere, the decomposition of cerium propionate is triggered by the oxidation of Ce³⁺ to Ce⁴⁺. This reaction entails the loss of large unoxidized propionate fragments of the propionate ligands. As decomposition proceeds, the carbonaceous residue makes the oxygen transport inside the material more difficult and decomposition becomes diffusion limited. At this point, extensive oxidation of the residue begins until it is completely removed. Crystallization of CeO₂ occurs simultaneously with decomposition. In these conditions, crystalline nanoparticles (diameter of 3–5 nm) can be obtained at a temperature as low as 300 °C. In an inert atmosphere, decomposition occurs in three steps. During the first step, one of the three propionate ligands is lost, with little oxidation of Ce³⁺, and is substituted by a hydroxyl group. The second step entails the loss of the remaining ligands with a substantial oxidation of Ce³⁺ to Ce⁴⁺. After this step, the intermediate product is, proposed as, a mixture of amorphous Ce(OH)₃ and Ce(OH)₄. Finally, the third step leads to conversion of the Ce hydroxide into crystalline CeO₂. In an inert atmosphere, the process is less reproducible than in air and a carbonaceous residue remains in the product.     

Improving the sensitivity of the determination of ceftiofur by capillary electrophoresis in environmental water samples: in-line solid phase extraction and sample stacking techniques

This paper describes two different approaches for increasing the sensitivity for the analysis of ceftiofur by capillary electrophoresis (CE). Two different techniques based on the introduction of an enlarged volume of sample, namely large volume sample stacking (LVSS) and in-line solid phase extraction (SPE) were studied and compared. LVSS allowed the on-column electrophoretic preconcentration of ceftiofur without modification of the separation capillary. In-line SPE-CE was developed by using a home-made microcartridge that was filled with a reversed-phase sorbent (C₁₈). The microcartridge was coupled in-line near the inlet of the separation capillary. LVSS and in-line SPE-CE allowed automated operation and improved sensitivity for the analysis of ceftiofur with respect to conventional CE. When environmental water samples were analyzed, an additional pretreatment step based on off-line SPE was necessary in both cases to further decrease the detection limits. In terms of sensitivity for the determination of ceftiofur in river water samples, the combination of off-line SPE with in-line SPE-CE was found the most sensitive with a detection limit of 10 ng L⁻¹, whereas the method based on the use of off-line SPE with LVSS presented a detection limit of 100 ng L⁻¹.     

Distribution of emulsified monomers with different water solubility

The location and distribution of acrylic acid and styrene in emulsions made with a cationic surfactant, cetyltrimethylammonium bromide (CTAB), or an anionic surfactant, sodium dodecylsulfate (SDS), were determined with ultra-violet spectroscopy, conductivity, and potentiometry. In these systems, the acrylic acid remains in the aqueous phase near the micelle surface, whereas the styrene is located in the micelles or in emulsified droplets. In the absence of acrylic acid, some of the styrene is solubilized in the micelle interior and some is adsorbed at the micelle inner surface. Upon addition of acrylic acid, all the styrene is displaced to the center of the micelles. The interaction between acrylic acid and CTAB micelles is stronger than that between acrylic acid and SDS micelles. With CTAB, acrylic acid is adsorbed at the micelle surface, whereas with SDS, acrylic acid remains in the intermicellar solution. These differences can account for the differences reported in the emulsion copolymerization of acrylic acid and styrene using CTAB or SDS.