Synergic effect of catalyst/binder in passivation side-products of Li-oxygen cells

Journal of Solid State Electrochemistry - While used in minor proportion respect to other components in cathode formulations, binders play a crucial role in lithium batteries cathode. This is...     

Thermodynamic and structural study of complexation of phenylboronic acid with salicylhydroxamic acid and related ligands

Stability constants of boronate complexes with a highly efficient bioconjugation ligand salicylhydroxamic acid, its derivatives and some structurally related compounds were determined by potentiometric and spectroscopic titrations at variable pH allowing one to obtain detailed stability – pH profiles and to identify the optimum pH for complexation with each ligand. The N,O‐binding of salicylhydroxamic acid via condensation of boronic acid with phenolic OH and hydroxamic NH groups was established by crystal structure determination of isolated complexes with phenylboronic and 4‐nitrophenylboronic acids. Although this type of binding is impossible for N‐methylated salicylhydroxamic acid it still forms stable boronate complexes supposedly involving unusual 7‐membered –O‐B‐O‐ cycle supported by ¹H NMR studies. Hydroxamic acids lacking ortho‐OH group and salicyloyl hydrazide form less stable boronate complexes, which nevertheless possess stabilities similar to those of catechole complexes and may be useful for conjugation applications. In contrast to other ligands, which form tetrahedral anionic complexes, salicylamidoxime forms tetrahedral, but neutral boronate complex with high stability in weakly acid solutions. The highest affinity in neutral and acid solutions surpassing that of salicylhydroxamic acid is observed with 2,6‐dihydroxybenzhydroxamic acid (K_obs = 5.2 × 10⁴ at pH 7.4). Fairly stable mono‐ and bisboronate complexes are formed with 2,5‐dihydroxy‐1,4‐benzdihydroxamic acid, which also possesses intense fluorescence and may serve as a boronic acid sensor with detection limit 4 μM. Results presented in this study provide quantitative basis for rational applications of hydroxamic acid derivatives in bioconjugation and sensing.     

Report on the 47th IUVSTA Workshop ‘Angle‐Resolved XPS: the current status and future prospects for angle‐resolved XPS of nano and subnano films’

A summary of the workshop entitled ‘Angle‐Resolved XPS: The Current Status and Future Prospects for Angle‐resolved XPS of Nano and Subnano Films’ is given, which was held at the Riviera Maya, Mexico, 26–30 March 2007, under the main sponsorship of the International Union for Vacuum Science, Technique and Applications (IUVSTA). Angle‐resolved X‐ray photoelectron spectroscopy (ARXPS) can provide detailed chemical as well as depth profile information about the near‐surface composition of materials and thin films. This workshop was held to review the present status and level of understanding of Angle‐resolved XPS, and to stimulate discussions leading to a deeper understanding of current problems and new solutions. The main goal of the workshop was to find better ways to perform experiments and, very importantly, better ways to extract information from the experimental data. This report contains summaries of presentations and discussions that were held in sessions entitled ‘Basics and Present Limits of ARXPS’, the Analysis of ARXPS Data, Applications of ARXPS, Equipment for ARXPS, and Future Developments in ARXPS'. There were 33 participants at the workshop. Copyright © 2009 John Wiley & Sons, Ltd.     

Basin topology in dissipative chaotic scattering

Chaotic scattering in open Hamiltonian systems under weak dissipation is not only of fundamental interest but also important for problems of current concern such as the advection and transport of inertial particles in fluid flows. Previous work using discrete maps demonstrated that nonhyperbolic chaotic scattering is structurally unstable in the sense that the algebraic decay of scattering particles immediately becomes exponential in the presence of weak dissipation. Here we extend the result to continuous-time Hamiltonian systems by using the Henon-Heiles system as a prototype model. More importantly, we go beyond to investigate the basin structure of scattering dynamics. A surprising finding is that, in the common case where multiple destinations exist for scattering trajectories, Wada basin boundaries are common and they appear to be structurally stable under weak dissipation, even when other characteristics of the nonhyperbolic scattering dynamics are not. We provide numerical evidence and a geometric theory for the structural stability of the complex basin topology.     

Upper limit on the diffuse flux of ultrahigh energy tau neutrinos from the Pierre Auger Observatory

The surface detector array of the Pierre Auger Observatory is sensitive to Earth-skimming tau neutrinos that interact in Earth's crust. Tau leptons from nu(tau) charged-current interactions can emerge and decay in the atmosphere to produce a nearly horizontal shower with a significant electromagnetic component. The data collected between 1 January 2004 and 31 August 2007 are used to place an upper limit on the diffuse flux of nu(tau) at EeV energies. Assuming an E(nu)(-2) differential energy spectrum the limit set at 90% C.L. is E(nu)(2)dN(nu)(tau)/dE(nu)<1.3 x 10(-7) GeV cm(-2) s(-1) sr(-1) in the energy range 2 x 10(17) eV< E(nu)< 2 x 10(19) eV.     

Observation of the suppression of the flux of cosmic rays above 4 x 10 (19) eV

The energy spectrum of cosmic rays above 2.5 x 10;{18} eV, derived from 20,000 events recorded at the Pierre Auger Observatory, is described. The spectral index gamma of the particle flux, J proportional, variantE;{-gamma}, at energies between 4 x 10;{18} eV and 4 x 10;{19} eV is 2.69+/-0.02(stat)+/-0.06(syst), steepening to 4.2+/-0.4(stat)+/-0.06(syst) at higher energies. The hypothesis of a single power law is rejected with a significance greater than 6 standard deviations. The data are consistent with the prediction by Greisen and by Zatsepin and Kuz'min.     

Chemistry of dicationic electrophiles: superacid-catalyzed reactions of amino acetals

Amino acetals are shown to form highly electrophilic systems in Bronsted superacids. It is proposed that amino acetals give dicationic electrophiles, and this proposal is supported by the direct observation of a dication by low-temperature (13)C NMR. When reacted with C(6)H(6) and superacidic CF(3)SO(3)H, amino acetals are shown to provide 1-(3,3-diphenylpropyl)amines and 1-(2,2-diphenylethyl)amines as condensation products in good yields (50-99%).     

Investigation of determinism in heart rate variability

The article searches for the possible presence of determinism in heart rate variability (HRV) signals by using a new approach based on NARMA (nonlinear autoregressive moving average) modeling and free-run prediction. Thirty-three 256-point HRV time series obtained from Wistar rats submitted to different autonomic blockade protocols are considered, and a collection of surrogate data sets are generated from each one of them. These surrogate sequences are assumed to be nondeterministic and therefore they may not be predictable. The original HRV time series and related surrogates are submitted to NARMA modeling and prediction. Special attention has been paid to the problem of stationarity. The results consistently show that the surrogate data sets cannot be predicted better than the trivial predictor-the mean-while most of the HRV control sequences are predictable to a certain degree. This suggests that the normal HRV signals have a deterministic signature. The HRV time series derived from the autonomic blockade segments of the experimental protocols do not show the same predictability performance, albeit the physiological interpretation is not obvious. These results have important implications to the methodology of HRV analysis, indicating that techniques from nonlinear dynamics and deterministic chaos may be applied to elicit more information about the autonomic modulation of the cardiovascular activity. (c) 2000 American Institute of Physics.     

Couplage d'un modèle stochastique lagrangien sous-maille avec une simulation grandes échelles

A large eddy simulation (LES) is used to compute passive scalar dispersion in a turbulent flow. Instead of resolving the passive scalar transport equation, fluid particles are tracked in a Lagrangian way and a Langevin stochastic modelling is used for the small scale component of the velocity of fluid particles at a subgrid-scale level. The stochastic model is written in terms of subgrid-scale statistics. The specificity of this study resides in the coupling of a LES with a stochastic model using the filtered subgrid-scale statistics in inhomogeneous turbulence. The results are compared with the wind tunnel experiments of Fackrell and Robins [J. Fluid Mech. 117 (1982) 1–26]. To cite this article: I. Vinkovic et al., C. R. Mecanique 333 (2005).     

Large eddy simulation of droplet dispersion for inhomogeneous turbulent wall flow

A large eddy simulation (LES) coupled with a Lagrangian stochastic model has been applied to the study of droplet dispersion in a turbulent boundary layer. Droplets are tracked in a Lagrangian way. The velocity of the fluid particle along the droplet trajectory is considered to have a large-scale part and a small-scale part given by a modified three-dimensional Langevin model using the filtered subgrid scale (SGS) statistics. An appropriate Lagrangian correlation timescale is considered in order to include the influences of gravity and inertia. Two-way coupling is also taken into account. The inter-droplet collision has been introduced as the main mechanism of secondary breakup. A stochastic model for breakup has been generalized for coalescence simulation, thereby two phenomena, coalescence and breakup are simulated in the framework of a single stochastic model. The parameters of this model, selectively for coalescence and for breakup, are computed dynamically by relating them to the local resolved properties of the dispersed phase compared to the main fluid. The model is validated by comparison with an agglomeration model and with experimental results on secondary breakup. The LES coupled with Lagrangian particle tracking and the model for droplet coalescence and breakup is applied to the study of the atmospheric dispersion of wet cooling tower plumes. The simulations are done for different droplet size distributions and volume fractions. We focused on the influence of these parameters on mean concentration, concentration variance and mass flux profiles.