Circularly Polarized Luminescence from Cyclic (Alkyl)(Amino) Carbene Derived Propellers

Organic circularly polarized luminescence (CPL)-active molecular emitters featuring dynamic propeller-like luminophores were prepared in one step from cyclic(alkyl)(amino) carbenes (CAACs). These molecules exhibit through-space arene-arene π-delocalization and rapid intramolecular inter-system crossing (ISC) in line with their helical character.     

Synthesis and luminescence properties of new red-shifted absorption lanthanide(III) chelates suitable for peptide and protein labelling

The synthesis and photo-physical properties of an original bis-pyridinylpyrazine chromophore efficiently sensitising europium(III) and samarium(III) are described. The corresponding lanthanide(III) complexes display in aqueous solutions a maximum excitation wavelength which is significantly red-shifted compared to the usual terpyridine-based chelates, and a valuable luminescence brightness above 2,000 dm(3) mol(-1) cm(-1) at 345 nm was obtained with a europium(III) derivative. Further functionalisation with three different bioconjugatable handles was also investigated and their ability to efficiently label a model hexapeptide was evaluated and compared. Finally, the best bioconjugatable europium(III) chelate was used in representative labelling experiments involving monoclonal antibodies and the luminescence features of the corresponding bioconjugates remained satisfactory.     

A Morse-Sard theorem for the distance function on Riemannian manifolds

We prove that the set of critical values of the distance function from a submanifold of a complete Riemannian manifold is of Lebesgue measure zero. In this way, we extend a result of Itoh and Tanaka. Mathematics Subject Classification (2000):53C22, 28A78, 49J52     

Spatio-temporal correlation analysis of turbulent flows using global and single-point measurements

A method to extract whole-field spatio-temporal correlations by combining global and single-point measurement techniques of different time resolutions is proposed. For fluid mechanics applications, the emphasis is on the combination of low repetition rate particle image velocimetry (PIV) results with experimental data obtained at largely higher sampling frequencies. The experimental feasibility of the procedure is established from results obtained in the wake of a cylinder, using PIV and constant temperature hot wire anemometry (CTA). The method is then applied to examine the shear layer in the core of a round subsonic jet using PIV and laser Doppler velocimetry (LDV). The accuracy of the cross-correlation functions is compared to the auto- and cross-correlation functions obtained from series of LDV and CTA measurements.     

Experimental characterization of the 3D dynamics of a laminar shallow vortex dipole

Experimental results on the dynamics of a vortex dipole evolving in a shallow fluid layer are presented. In particular, the generation of a spanwise vortex at the front of the dipole is observed in agreement with previous experiments at larger Reynolds numbers. The results show that this secondary vortex is of comparable strength to the dipole. The present physical analysis suggests that the origin of this structure involves the stretching induced by the dipole of the boundary-layer vorticity generated by the dipole’s advection over the no-slip bottom.     

Large Eddy Simulation of a Motored Single-Cylinder Piston Engine: Numerical Strategies and Validation

This paper describes a compressible Large Eddy Simulation (LES) used to investigate cyclic variations for nonreacting flow in an optical single cylinder engine setup. The simulated operating point is part of a large experimental database designed to validate LES for cycle-to-cycle prediction, and constitutes a first step towards the realization of fired operating points. The computational domain covers almost the whole experimental setup (intake and exhaust plenums, intake and exhaust ducts, cylinder) to account for acoustic phenomena. The assessment of the computation is performed in two regions of the domain: the intake and exhaust duct predictions are compared to the results of a Helmholtz solver and the experiment (pressure transducers and Particle Image Velocimetry (PIV)) while the in-cylinder dynamics are compared to PIV measurements. The ability of the developed methodology to capture the correct level of cycle-to-cycle variations is demonstrated considering in-cylinder pressure and velocity fields predictions. Cycle-to-cycle variations in velocity are highlighted and localized using a proper orthogonal decomposition analysis.     

Some laws of the iterated logarithm in Hilbertian autoregressive models

We consider the law of the iterated logarithm for the empirical covariance of Hilbertian autoregressive processes. As an application, we obtain laws of the iterated logarithm for the eigenvalues and associated projectors of the empirical covariance.     

Self-templating polythiophene derivatives: electronic decoupling of conjugated strands through staggered packing

Whereas molecular electronics needs well-controlled 3D geometries for decoupling or interconnecting individual molecules, conjugated polymers form disordered structures when deposited on a substrate. We show that this trend can be overcome in polythiophene derivatives designed so as to exploit weak sulfur-bromine interactions. A self-template effect follows, leading to staggered organizations of well-aligned electronically decoupled conjugated strands, as observed in situ by scanning tunneling microscopy and spectroscopy on graphite.     

Solvent/base effects in the selective domino synthesis of phenanthridinones that involves high-valent palladium species: experimental and theoretical studies

The domino reaction of o-bromobenzamides 1a-m in the presence of K(2)CO(3) and the [PdCl(2)(PPh(3))(2)] catalyst granted a selective access to phenanthridinones 2 or to the new 1-carboxamide phenanthridinones 3 depending on the solvent, DMF or 1,4-dioxane, respectively. Investigations of the reaction parameters provided the first example of a direct correlation between the base dissociation and the solvent polarity on the selectivity observed. Moreover, mechanistic studies (NMR spectroscopy and ESI-MS monitoring) allowed us to characterize Pd(II) palladacycle 4 and biaryl species as common intermediates for these two domino processes. On that basis, C(sp(2))-C(sp(2)) bond formation is envisaged by generation of a Pd(IV) complex after oxidative addition of 1 into Pd(II) palladacycle 4, a rationale that is supported by DFT calculations. A general catalytic cycle is proposed to account for these observations.     

A theoretical study of abiotic methylation reactions of gaseous elemental mercury by halogen-containing molecules

Methylation reactions of gaseous elementary mercury by halogen containing molecules such as halogenomethane species CH(3)X (with X = Cl, Br, and I) and the dimethylchlorinium ion CH(3)ClCH(3)(+) were investigated at the density functional level. With CH(3)X, the reaction is predicted to be almost athermic and kinetically demanding for a thermal reaction. The reaction can proceed photochemically in the visible range; therefore sunlight may increase the reaction rate. These results compare well with the experimental data. Consecutive methylation of the CH(3)HgX products (with X = Cl, Br, and I) and subsequent formation of CH(3)HgCH(3) were also studied. These reactions are predicted to be kinetically inaccessible and thermodynamically unfavorable. With CH(3)ClCH(3)(+), the reaction is predicted to be athermic but kinetically easy. This is due to the suitability of the methyl transfer reagent. Geometrical and electronic data were systematically analyzed in order to rationalize the results.