Accurate measurements of peak variances: importance of this accuracy in the determination of the true corrected plate heights of chromatographic columns

The true efficiency of a column is derived from the differences between the variances of the peak profiles of the same compound recorded in the presence and the absence of the chromatographic column. These variances are usually derived using one of three methods: (1) the retention time of the peak apex and its half-height width; (2) the moments of the best fit between the experimental data and a hybrid response function, e.g., an exponentially convoluted Gaussian; or (3) the exact moments of the experimental band profiles. Comparisons of the results of these methods show that the first method is always inaccurate because all the band profiles recorded are strongly tailing. The peak fit method is accurate only for 4.6mm I.D. columns operated with instruments having low extra-column volume but fails for short narrow-bore columns due to the severe tailing of peaks passing through the complex channels of the extra-column volumes and to the inaccuracies in the fit of experimental data to the selected function. Although far better, the moment method may be inaccurate when the zero dead volume union used to measure the extra-column peak variances has a higher permeability than the column, causing the upstream part of the instrument to operate under comparatively low pressures.     

Protonation of the oxygen axial ligand in galactose oxidase model compounds as seen with high resolution X-ray emission experiments and FEFF simulations

X-ray Emission Spectroscopy (XES) crossover peaks were shown to be sensitive to the protonation state of solvent molecules in the Zn protein carbonic anhydrase and its model compounds. Here we extend such studies to galactose oxidase models i.e. Cu(ii) open d-shell systems, illustrating that XES combined with FEFF8 simulations reflect changes in the protonation state of the phenolate ligand for the copper center.     

Quaternionic Brownian Windings

Journal of Theoretical Probability - We define and study the three-dimensional windings along Brownian paths in the quaternionic Euclidean, projective and hyperbolic spaces. In particular, the...     

Bayesian Inference of a Parametric Random Spheroid from its Orthogonal Projections

Methodology and Computing in Applied Probability - The paper focuses on a new method for the inference of a parametric random spheroid from the observations of its 2D orthogonal projections. Such a...     

Quantum Spatial Search with Electric Potential: Long-Time Dynamics and Robustness to Noise

We present various results on the scheme introduced in a previous work, which is a quantum spatial-search algorithm on a two-dimensional (2D) square spatial grid, realized with a 2D Dirac discrete-time quantum walk (DQW) coupled to a Coulomb electric field centered on the the node to be found. In such a walk, the electric term acts as the oracle of the algorithm, and the free walk (i.e., without electric term) acts as the “diffusion” part, as it is called in Grover’s algorithm. The results are the following. First, we run long time simulations of this electric Dirac DQW, and observe that there is a second localization peak around the node marked by the oracle, reached in a time O(N), where N is the number of nodes of the 2D grid, with a localization probability scaling as O(1/lnN). This matches the state-of-the-art 2D-DQW search algorithms before amplitude amplification We then study the effect of adding noise on the Coulomb potential, and observe that the walk, especially the second localization peak, is highly robust to spatial noise, more modestly robust to spatiotemporal noise, and that the first localization peak is even highly robust to spatiotemporal noise.     

Partition coefficients of organic compounds in new imidazolium based ionic liquids using inverse gas chromatography

Partition coefficients of organic compounds in four ionic liquids: 1-ethanol-3-methylimidazolium tetrafluoroborate, 1-ethanol-3-methylimidazolium hexafluorophosphate, 1,3-dimethylimidazolium dimethylphosphate and 1-ethyl-3-methylimidazolium diethylphosphate were measured using inverse gas chromatography from 303.3 to 332.55 K. The influence of gas–liquid and gas–solid interfacial adsorption of different solutes on ionic liquids was also studied. Most of the polar solutes were retained largely by partition while light hydrocarbons were retained predominantly by interfacial adsorption on the ionic liquids studied in this work. The solvation characteristics of the ionic liquids were evaluated using the Abraham solvation parameter model.     

Anisotropic catalytic activity of the orientation controlled Nd2NiO4 + δ/YSZ hetero-epitaxial system for SOFC cathode

Electrode–electrolyte hetero-epitaxial systems for solid oxide fuel cells (SOFCs) with two different configuration of Nd₂NiO_4 + δ(110)//YSZ(100) and Nd₂NiO_4 + δ(100)//YSZ(110) were successfully fabricated by pulsed laser deposition. Thin films of Nd₂NiO_4 + δ approximately 20 nm thick were grown on a commercial single crystal of YSZ. The preferred two-dimensional diffusion paths of the oxide ions were perpendicular to the substrate for both configurations and showed oxygen reduction capability different from each other. This opens up new research direction focusing on the details of anisotropic catalytic activity of SOFC cathode depending on the crystalline surface.     

Convergence of the parabolic Ginzburg–Landau equation to motion by mean curvature

We present some new results for the asymptotic behavior of the complex parabolic Ginzburg–Landau equation. In particular, we establish that, as the parameter ε tends to 0, vorticity evolves according to motion by mean curvature in Brakke's weak formulation. The only assumption we make is a natural energy bound on the initial data. In some cases, we also prove convergence to enhanced motion in the sense of Ilmanen. To cite this article: F. Bethuel et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003).     

Stationary Analysis of a Fluid Queue Driven by Some Countable State Space Markov Chain

Motivated by queueing systems playing a key role in the performance evaluation of telecommunication networks, we analyze in this paper the stationary behavior of a fluid queue, when the instantaneous input rate is driven by a continuous-time Markov chain with finite or infinite state space. In the case of an infinite state space and for particular classes of Markov chains with a countable state space, such as quasi birth and death processes or Markov chains of the G/M/1 type, we develop an algorithm to compute the stationary probability distribution function of the buffer level in the fluid queue. This algorithm relies on simple recurrence relations satisfied by key characteristics of an auxiliary queueing system with normalized input rates.      

Smoothing and dispersive estimates for 1D Schrödinger equations with BV coefficients and applications

We prove smoothing estimates for Schrödinger equations it_∂?+x_∂(a(x)x_∂?)=0 with a(x)∈BV, real and bounded from below. We then bootstrap these estimates to obtain optimal Strichartz and maximal function estimates, all of which turn out to be identical to the constant coefficient case. We also provide counterexamples showing a∈BV to be in a sense a minimal requirement. Finally, we provide an application to sharp well-posedness for a generalized Benjamin-Ono equation.