Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes

The industrial production of monosilanes Me_nSiCl_4−n (n=1–3) through the Müller–Rochow Direct Process generates disilanes Me_nSi₂Cl_6−n (n=2–6) as unwanted byproducts (“Direct Process Residue”, DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si−Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions.     

Synthesis of Highly Fluorinated Arene Complexes of [Rh(Chelating Phosphine)]+ Cations,and their use in Synthesis and Catalysis

The synthesis of rhodium complexes with weakly binding highly fluorinated benzene ligands is described: 1,2,3-F₃C₆H₃, 1,2,3,4-F₄C₆H₂ and 1,2,3,4,5-F₅C₆H are shown to bind with cationic [Rh(Cy₂P(CH₂)_xPCy₂)]⁺ fragments (x=1, 2). Their structures and reactivity with alkenes, and use in catalysis for promoting the Tishchenko reaction of a simple aldehyde, are demonstrated. Key to the synthesis of these complexes is the highly concentrated reaction conditions and use of the [Al{OC(CF₃)₃}₄]⁻ anion.     

Correlation Between Foam Flow Structure in Porous Media and Surfactant Formulation Properties

Transport in Porous Media - The optimization of foam injection in porous media for enhanced oil recovery or soil remediation requires a large screening of surfactant formulations. Tests of foam...     

Singlet Fission in Carbene-Derived Diradicaloids

Herein, we present a new class of singlet fission (SF) materials based on diradicaloids of carbene scaffolds, namely cyclic (alkyl)(amino)carbenes (CAACs). Our modular approach allows the tuning of two key SF criteria: the steric factor and the diradical character. In turn, we modified the energy landscapes of excited states in a systematic manner to accommodate the needs for SF. We report the first example of intermolecular SF in solution by dimer self-assembly at cryogenic temperatures.     

Targeted Photodynamic Therapy of Human Head and Neck Squamous Cell Carcinoma with Anti-epidermal Growth Factor Receptor Antibody Cetuximab and Photosensitizer IR700DX in the Mouse Skin-fold Window Chamber Model

Targeted photodynamic therapy (PDT) in head/neck cancer patients with a conjugate of the anti-epidermal growth factor receptor (EGFR) antibody, Cetuximab and a phthalocyanine photosensitizer IR700DX is under way, but the exact mechanisms of action are still not fully understood. In this study, the EGFR-overexpressing human head/neck OSC-19-luc2-cGFP tumor with transfected GFP gene was used in a skin-fold window chamber model in BALB/c nude mice. The uptake and localization of the conjugate in the tumor and its surrounding normal tissues were studied by an intravital confocal laser scanning microscopy with image analyses. The tumor was also irradiated with 690 nm laser light 24 h after conjugate administration. The vascular and tumor responses were examined by morphological evaluation and immunohistochemistry (IHC). The amount of conjugate in the tumor peaked at 24–48 h after injection. Image analyses of colocalization correlation parameters demonstrated a high fraction of the conjugate IR700DX colocalized in the GFP-expressing tumor cells. PDT-treated tumors showed extensive necrotic/apoptotic destruction with little vascular damage, while IHC showed no HIF-1α expression and decreased EGFR and Ki67 expression with activated caspase-3 overexpression, indicating a direct killing of tumor cells through both necrotic and apoptotic cell death.     

Coupled Models and Parallel Simulations for Three-Dimensional Full-Stokes Ice Sheet Modeling

A three-dimensional full-Stokes computational model is considered for determining the dynamics,temperature,and thickness of ice sheets.The goveming thermomechanical equations consist of the three-dimensional full-Stokes system with nonlinear rheology for the momentum,an advective-diffusion energy equation for temperature evolution,and a mass conservation equation for ice-thickness changes.Here,we discuss the variable resolution meshes,the finite element discretizations,and the parallel algorithms employed by the model components.The solvers are integrated through a well-designed coupler for the exchange of parametric data between components.The discretization utilizes high-quality,variable-resolution centroidal Voronoi Delaunay triangulation meshing and existing parallel solvers.We demonstrate the gridding technology,discretization schemes,and the efficiency and scalability of the parallel solvers through computational experiments using both simplified geometries arising from benchmark test problems and a realistic Greenland ice sheet geometry.     

Ends,tangles and critical vertex sets

We show that an arbitrary infinite graph G can be compactified by its ends plus its critical vertex sets, where a finite set X of vertices of an infinite graph is critical if its deletion leaves some infinitely many components each with neighbourhood precisely equal to X. We further provide a concrete separation system whose ?₀‐tangles are precisely the ends plus critical vertex sets. Our tangle compactification is a quotient of Diestel's (denoted by ), and both use tangles to compactify a graph in much the same way as the ends of a locally finite and connected graph compactify it in its Freudenthal compactification. Finally, generalising both Diestel's construction of and our construction of , we show that G can be compactified by every inverse limit of compactifications of the sets of components obtained by deleting a finite set of vertices. Diestel's is the finest such compactification, and our is the coarsest one. Both coincide if and only if all tangles are ends. This answers two questions of Diestel.     

Obstruction à la transversalité de lagrangiens

In this Note, we give a necessary and sufficient condition for Lagrangians in a symplectic vector bundle to be deformed stably into transversal Lagrangians. In the case of three Lagrangians, we show that the associated Grothendieck group can be identified with a Hermitian K-theory group. To cite this article: M. Karoubi, M.L. Lapa de Souza, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Recovering Invisible Signals by Two‐Field NMR Spectroscopy

Nuclear magnetic resonance (NMR) studies have benefited tremendously from the steady increase in the strength of magnetic fields. Spectacular improvements in both sensitivity and resolution have enabled the investigation of molecular systems of rising complexity. At very high fields, this progress may be jeopardized by line broadening, which is due to chemical exchange or relaxation by chemical shift anisotropy. In this work, we introduce a two‐field NMR spectrometer designed for both excitation and observation of nuclear spins in two distinct magnetic fields in a single experiment. NMR spectra of several small molecules as well as a protein were obtained, with two dimensions acquired at vastly different magnetic fields. Resonances of exchanging groups that are broadened beyond recognition at high field can be sharpened to narrow peaks in the low‐field dimension. Two‐field NMR spectroscopy enables the measurement of chemical shifts at optimal fields and the study of molecular systems that suffer from internal dynamics, and opens new avenues for NMR spectroscopy at very high magnetic fields.