Complexes of Dichlorogermylene with Phosphine/Sulfoxide-Supported Carbone as Ligand

Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L₂C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 °C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide.     

Labile Base-Stabilized Silyliumylidene Ions. Non-Metallic Species Capable of Activating Multiple Small Molecules

Several base-stabilized silyliumylidene ions ( 2 and 3 ) with different ligands were synthesized. Their behaviour appeared strongly dependent on the nature of ligand. Indeed, in contrast to the poorly reactive silyliumylidene ions 3 c,d stabilized by strongly donating ligands (DMAP, NHC), the silylene- and sulfide-supported one ( 2-H and 3 a ) exhibits higher reactivity toward various small molecules. Furthermore, their capability to successively activate multiple small molecules was clearly demonstrated by processes involving successive reactions with silane/formamide, CO₂ and H₂. Moreover, HBPin adduct of 3 a ( 8-C ) catalyzes the hydroboration of pyridine. Of particular interest, silylene-supported silyliumylidene complex 2-H is one of the rare species able to activate two H₂ molecules.     

A penalization method applied to the wave equation

In this Note we investigate the mathematical properties of the volume penalization method applied to the one-dimensional wave equation. Generally speaking, the penalization method allows one to handle complex geometries by simply adding a term to the equation to impose the boundary conditions. We study the convergence of the method with regards to the penalization parameter and we present error and stability analyses for the wave equation. Numerical simulations using a finite difference scheme illustrate the results. To cite this article: A. Paccou et al., C. R. Mecanique 333 (2005).     

Flexible Wiper System Dynamic Instabilities: Modelling and Experimental Validation

The optimization of wiper systems under various conditions and the creation of a product which is as robust as possible are the main objectives for an equipment supplier. However, in certain conditions, instabilities can appear and generate wiping defects due to the rubber-glass contact. To improve wiping quality and to reduce the number of test stages for design, this study proposes a wiper system modeling method. The wiper system is represented by a rigid blade holder on which a rubber blade is fitted. This rigid blade system is used on a flat test bench at constant wiping velocity. The model is based on modal synthesis methods and will be validated through comparison with experimental tests under various conditions. The right correlation obtained allows the same modelling method to be applied to the new generation of flexible wiper blades which take account of the degree of freedom of the wiper blade flexions. So, a new computation tool will be developed and validated through experimentation on a specific test bench.     

Marine Exopolysaccharide Complexed With Scandium Aimed as Theranostic Agents

(1) Background: Exopolysaccharide (EPS) derivatives, produced by Alteromonas infernus bacterium, showed anti-metastatic properties. They may represent a new class of ligands to be combined with theranostic radionuclides, such as ⁴⁷Sc/⁴⁴Sc. The goal of this work was to investigate the feasibility of such coupling. (2) Methods: EPSs, as well as heparin used as a drug reference, were characterized in terms of molar mass and dispersity using Asymmetrical Flow Field-Flow Fractionation coupled to Multi-Angle Light Scattering (AF4-MALS). The intrinsic viscosity of EPSs at different ionic strengths were measured in order to establish the conformation. To determine the stability constants of Sc with EPS and heparin, a Free-ion selective radiotracer extraction (FISRE) method has been used. (3) Results: AF4-MALS showed that radical depolymerization produces monodisperse EPSs, suitable for therapeutic use. EPS conformation exhibited a lower hydrodynamic volume for the highest ionic strengths. The resulting random-coiled conformation could affect the complexation with metal for high concentration. The LogK of Sc-EPS complexes have been determined and showing that they are comparable to the Sc-Hep. (4) Conclusions: EPSs are very promising to be coupled with the theranostic pair of scandium for Nuclear Medicine.     

Advances on the Determination of the Astatine Pourbaix Diagram: Predomination of AtO(OH)2− over At− in Basic Conditions

It is generally assumed that astatide (At^?) is the predominant astatine species in basic aqueous media. This assumption is questioned in non‐complexing and non‐reductive aqueous solutions by means of high‐pressure anion‐exchange chromatography. Contrary to what is usually believed, astatide is found to be a minor species at pH=11. A different species, which also bears a single negative charge, becomes predominant when the pH is increased beyond 7. Using competition experiments, an equilibrium constant value of 10^?6.9 has been determined for the formation of this species from AtO(OH) with the exchange of one proton. The identification of this species, AtO(OH)₂^?, is achieved through relativistic quantum mechanical calculations, which rule out the significant formation of the AtO₂^? species, while leading to a hydrolysis constant of AtO(OH) in excellent agreement with experiment when the AtO(OH)₂^? species is considered. Beyond the completion of the Pourbaix diagram of astatine, this new information is of interest for the development of ²¹¹At radiolabeling protocols.     

Visualizing Microglia with a Fluorescence Turn‐On Ugt1a7c Substrate

Microglia, the brain‐resident macrophage, are involved in brain development and contribute to the progression of neural disorders. Despite the importance of microglia, imaging of live microglia at a cellular resolution has been limited to transgenic mice. Efforts have therefore been dedicated to developing new methods for microglia detection and imaging. Using a thorough structure–activity relationships study, we developed CDr20, a high‐performance fluorogenic chemical probe that enables the visualization of microglia both in vitro and in vivo. Using a genome‐scale CRISPR‐Cas9 knockout screen, the UDP‐glucuronosyltransferase Ugt1a7c was identified as the target of CDr20. The glucuronidation of CDr20 by Ugt1a7c in microglia produces fluorescence.     

A study on the limitations of a vane rheometer for mineral suspensions using image processing

This study presents the results from the rheological measurement of clay suspensions using vane geometry in a wide gap configuration. It focuses on how measurement of viscosity cannot be effective for two reasons: the limits of the vane geometry itself and the limits of the material depending on its content of solid particles. Image analysis of the flow while shearing the material is carried out to relate the flow behavior. Several approaches to compute the shear flow curve from torque-rotational velocity data are used. The results demonstrate that the applied setpoint while applying a logarithmic shear rate ramp can be very different from the calculated shear rate from existing theories. Depending on the solid volume fraction of the particles in the mixture, we relate the macroscopic behavior using image analysis and the shear flow curves to the rheophysical regime of the flow of the suspensions. Therefore, this paper has two simultaneous goals: the first one is to describe the physical phenomena which control macroscopic behavior and the second one is to highlight the limits of the vane geometry for viscosity measurement of mineral suspensions like kaolinite pastes.     

Analysis of high molecular mass proteins larger than 150 kDa using cyanogen bromide cleavage and conventional 2-DE

Proteomic approaches including high-resolution 2-DE are providing the tools needed to discover disease-associated biomarkers in complex biological samples. Although 2-DE is an extremely powerful approach to analyze the proteome, the separation of proteins with extreme molecular masses still remains an issue requiring improvement. Because high molecular mass (HMM) proteins larger than 150 kDa have already been observed to be differentially expressed in several pathologies such as cancer, we developed an original strategy to analyze this part of the proteome that is not easily separated by 2-DE in polyacrylamide gels. This strategy is based on the 2-DE separation of cyanogen bromide (CNBr) fragments of purified HMM protein fractions, and combines techniques including SEC fractionation, TCA precipitation, CNBr cleavage, 2-DE and MS analysis. The method was first tested on a model protein, the BSA. Preliminary results obtained using colonic tissues led to the identification of six HMM proteins with M(r) comprised between 163 and 533 kDa in their reduced state. These results demonstrated that our CNBr/2-DE approach should provide a powerful tool for identification of new biomarkers larger than 150 kDa.