On the Topology of Fibrations with Section and Free Loop Spaces

We relate the brace products of a fibration with section tothe differentials in its Serre spectral sequence. In the particularcase of free loop fibrations, we establish a link between thesedifferentials and Browder operations in the fiber. Applicationsand several calculations (for the particular cases of spheresand wedges of spheres) are given. 2000 Mathematical SubjectClassification: 55P35, 55Q15, 55R05, 55R20.     

Stationary Flow Past a Semi-Infinite Flat Plate: Analytical and Numerical Evidence for a Symmetry-Breaking Solution

We consider the question of the existence of stationary solutions for the Navier Stokes equations describing the flow of a incompressible fluid past a semi-infinite flat plate at zero incidence angle. By using ideas from the theory of dynamical systems we analyze the vorticity equation for this problem and show that a symmetry-breaking term fits naturally into the downstream asymptotic expansion of a solution. Finally, in order to check that our asymptotic expressions can be completed to a symmetry-breaking solution of the Navier–Stokes equations we solve the problem numerically by using our asymptotic results to prescribe artificial boundary conditions for a sequence of truncated domains. The results of these numerical computations a clearly compatible with the existence of such a solution. Mathematics Subject Classification (2000). 76D05, 76D25, 76M10, 41A60, 35Q35 Supported in part by the Fonds National Suisse.     

Hertzian fracture at unloading

Hertzian fracture through indentation of flat float glass specimens by steel balls has been examined experimentally. Initiation of cone cracks has been observed and failure loads together with contact and fracture radii determined at monotonically increasing load but also during unloading phases. Contact of dissimilar elastic solids under decreasing load may cause crack inception triggered by finite interface friction and accordingly the coefficient of friction was determined by two different methods. In order to make relevant predictions of experimental findings, a robust computational procedure has been developed to determine global and local field values in particular at unloading at finite friction. It was found that at continued loading it is possible to specify in advance how the contact domain divides into invariant regions of stick and slip. The maximum tensile stress was found to occur at the free surface just outside the contact contour, the relative distance depending on the different elastic compliance properties and the coefficient of friction. In contrast, at unloading invariance properties are lost and stick/slip regions proved to be severely history dependant and in particular with an opposed frictional shear stress at the contact boundary region. This causes an increase of the maximum tensile stress at the contour under progressive unloading. Predictions of loads to cause crack initiation during full cycles were made based on a critical stress fracture criterion and proved to be favourable as compared to the experimental results.     

SERF-filtered experiments: new enantio-selective tools for deciphering complex spectra of racemic mixtures dissolved in chiral oriented media

The use of chiral liquid crystals as NMR solvent is a powerful tool to visualize and quantify enantiomers. This technique is much more robust than traditional liquid state techniques. Recent developments have been performed to simplify proton spectra obtained in these solvents which are usually complex to analyze. In the different published sequences the enantiomeric differentiation can be visualized but none of them rely the different (1)H-(1)H couplings to have a coherent set for each enantiomer especially in cases of racemic mixtures. In this work to overcome such limitations, we present a new NMR pulse sequence using semi-selective pulses to assign for each enantiomer the different (1)H-(1)H couplings. The aim is to obtain the signal of only one enantiomer, through a first Selective ReFocussing (SERF) filtering block implemented for the enantio-selection followed by a second SERF block for measuring a chosen coupling. The whole sequence is called (1)H SERF-filtered-SERF. These techniques permit for the first time to assign all dipolar couplings to each enantiomer of racemic mixtures dissolved in chiral oriented media. We demonstrate that using this experiment it is possible to visualize enantio-differentiation even in the case where the multiplets are not resolved in the SERF experiments, pushing back the limits of the enantiomeric visualization.     

Dioxane and Dioxine Heterocycles Obtained Simultaneously on a Same Substrate from the Condensation Reaction Between p-Hydroxyacetophenone and Polymerised Formaldehyde

The condensation reaction between polymerised formaldehyde and a ketone possessing a methylene group α to the carbonyl function, in the presence of a polystyrene (1) or fluorinated (2) ion-exchange catalyst, leads to the corresponding 1,3-dioxane and is characterized by excellent yield and selectivity.     

Promotion of nickel catalysts for the steam reforming of methane

The influence of additives (Cu, Fe and Al₂O₃) on the textural and catalytic properties of nickel in steam reforming of methane is described. The effects of structural promoting by Al₂O₃ and of electronic promoting by copper are reported. The rate of steam reforming of methane was measured in a gradientless reactor at atmospheric pressure.

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(Cu, Fe Al₂O₃) . Al₂O₃ . .

     

Unmanned platform for long-range remote analysis of volatile compounds in air samples

This paper describes a long-range remotely controlled CE system built on an all-terrain vehicle. A four-stroke engine and a set of 12-V batteries were used to provide power to a series of subsystems that include drivers, communication, computers, and a capillary electrophoresis module. This dedicated instrument allows air sampling using a polypropylene porous tube, coupled to a flow system that transports the sample to the inlet of a fused-silica capillary. A hybrid approach was used for the construction of the analytical subsystem combining a conventional fused-silica capillary (used for separation) and a laser machined microfluidic block, made of PMMA. A solid-state cooling approach was also integrated in the CE module to enable controlling the temperature and therefore increasing the useful range of the robot. Although ultimately intended for detection of chemical warfare agents, the proposed system was used to analyze a series of volatile organic acids. As such, the system allowed the separation and detection of formic, acetic, and propionic acids with signal-to-noise ratios of 414, 150, and 115, respectively, after sampling by only 30 s and performing an electrokinetic injection during 2.0 s at 1.0 kV.     

Growth and Atomic-Scale Characterization of Ultrathin Silica and Germania Films: The Crucial Role of the Metal Support

The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO₄ (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth.     

Probing the Local Reaction Environment During High Turnover Carbon Dioxide Reduction with Ag-Based Gas Diffusion Electrodes

Discerning the influence of electrochemical reactions on the electrode microenvironment is an unavoidable topic for electrochemical reactions that involve the production of OH⁻ and the consumption of water. That is particularly true for the carbon dioxide reduction reaction (CO₂RR), which together with the competing hydrogen evolution reaction (HER) exert changes in the local OH⁻ and H₂O activity that in turn can possibly affect activity, stability, and selectivity of the CO₂RR. We determine the local OH⁻ and H₂O activity in close proximity to a CO₂-converting Ag-based gas diffusion electrode (GDE) with product analysis using gas chromatography. A Pt nanosensor is positioned in the vicinity of the working GDE using shear-force-based scanning electrochemical microscopy (SECM) approach curves, which allows monitoring changes invoked by reactions proceeding within an otherwise inaccessible porous GDE by potentiodynamic measurements at the Pt-tip nanosensor. We show that high turnover HER/CO₂RR at a GDE lead to modulations of the alkalinity of the local electrolyte, that resemble a 16 m KOH solution, variations that are in turn linked to the reaction selectivity.