Acidobasic properties of molten potassium tetrahalogenogallates (X=Cl,I)

Molten potassium tetrachlorogallate and potassium tetraiodogallate were studied in terms of halogenoacidity, based on X^? ion-exchange. Titration of KX solution with GaX₃ were achieved and characterized by the shift of cathodic voltammetric curves. Autodissociation constants K_i,X/mol² kg^?1 were determined: ?log K_i,Cl=4.25±0.05 and ?log K_i,I=2.6±0.05, as well as the solubility values of KX: 0.41±0.02 and 0.80±0.02 mol kg^?1 for KCl and KI respectively.     

Open-tubular capillary electrochromatography/electrospray ionization-mass spectrometry using polymeric surfactant as a stationary phase coating

We describe the use of the polymeric surfactant poly(sodium undecylenic sulfate) (poly-SUS) as a stationary phase coating in open-tubular capillary electrochromatography (OT-CEC) coupled with electrospray ionization-mass spectrometry (ESI-MS) for the analysis of beta-blocker and benzodiazepine analytes. The production of a polymeric surfactant coating on the capillary inner wall involves (i) adsorption of the cationic polymer poly(diallyldimethylammonium chloride) (PDADMAC) to the inner surface of capillary, and (ii) adsorption of the negatively charged poly-SUS onto the cationic polymer layer via strong physical interaction of the two polymer layers. As compared with micellar electrokinetic chromatography (MEKC) coupled with ESI-MS, the main advantage of this proposed method is minimization of introduction of the monomeric or polymeric surfactant into the mass spectrometer, thus avoiding the interference of the nonvolatile micelle in ESI-MS. The effects of buffer pH and applied voltage on the separation of the analytes are also discussed. Under optimum conditions, four of the five beta-blockers and four benzodiazepines are separated.     

Robust and accurate inference for generalized linear models

In the framework of generalized linear models, the nonrobustness of classical estimators and tests for the parameters is a well known problem, and alternative methods have been proposed in the literature. These methods are robust and can cope with deviations from the assumed distribution. However, they are based on first order asymptotic theory, and their accuracy in moderate to small samples is still an open question. In this paper, we propose a test statistic which combines robustness and good accuracy for moderate to small sample sizes. We combine results from Cantoni and Ronchetti [E. Cantoni, E. Ronchetti, Robust inference for generalized linear models, Journal of the American Statistical Association 96 (2001) 1022–1030] and Robinson, Ronchetti and Young [J. Robinson, E. Ronchetti, G.A. Young, Saddlepoint approximations and tests based on multivariate M-estimators, The Annals of Statistics 31 (2003) 1154–1169] to obtain a robust test statistic for hypothesis testing and variable selection, which is asymptotically χ²-distributed as the three classical tests but with a relative error of order O(n⁻¹). This leads to reliable inference in the presence of small deviations from the assumed model distribution, and to accurate testing and variable selection, even in moderate to small samples.     

“Miniaturized” Linearizations for Quadratic 0/1 Problems

In order to solve a quadratic 0/1 problem, some techniques, consisting in deriving a linear integer formulation, are used. Those techniques, called “linearization”, usually involve a huge number of additional variables. As a consequence, the exact resolution of the linear model is, in general, very difficult. Our aim, in this paper, is to propose “economical” linear models. Starting from an existing linearization (typically the so-called “classical linearization”), we find a new linearization with fewer variables. The resulting model is called “Miniaturized” linearization. Based on this approach, we propose a new linearization scheme for which numerical tests have been performed.     

Erasure Decoding for Gabidulin Codes

We present a new approach of the decoding algorithm for Gabidulin Codes. In the same way as efficient erasure decoding for Generalized Reed Solomon codes by using the structure of the inverse of the VanderMonde matrices, we show that, the erasure(t erasures mean that t components of a code vector are erased) decoding Gabidulin code can be seen as a computation of three matrice and an affine permutation, instead of computing an inverse from the generator or parity check matrix. This significantly reduces the decoding complexity compared to others algorithms. For t erasures with t ≤ r, where r = n − k, the erasure algorithm decoding for Gab _{n, k} (g) Gabidulin code compute the t symbols by simple multiplication of three matrices. That requires rt + r(k − 1) Galois field multiplications, t(r − 1) + (t + r)k field additions, r ² + r(k + 1) field negations and t(k + 1) field inversions.     

On the electronic structure and hydrogen evolution reaction activity of platinum group metal-based high-entropy-alloy nanoparticles

We report the synthesis of high-entropy-alloy (HEA) nanoparticles (NPs) consisting of five platinum group metals (Ru, Rh, Pd, Ir and Pt) through a facile one-pot polyol process. We investigated the electronic structure of HEA NPs using hard X-ray photoelectron spectroscopy, which is the first direct observation of the electronic structure of HEA NPs. Significantly, the HEA NPs possessed a broad valence band spectrum without any obvious peaks. This implies that the HEA NPs have random atomic configurations leading to a variety of local electronic structures. We examined the hydrogen evolution reaction (HER) and observed a remarkably high HER activity on HEA NPs. At an overpotential of 25 mV, the turnover frequencies of HEA NPs were 9.5 and 7.8 times higher than those of a commercial Pt catalyst in 0.05 M H₂SO₄ and 1.0 M KOH electrolytes, respectively. Moreover, the HEA NPs showed almost no loss during a cycling test and were much more stable than the commercial Pt catalyst. Our findings on HEA NPs may provide a new paradigm for the design of catalysts.

RuRhPdIrPt high-entropy-alloy nanoparticles with a broad and featureless valence band spectrum show high hydrogen evolution reaction activity.     

Detection of Cadmium and Copper Cations Using Amorphous Nitrogenated Carbon Thin Film Electrodes

Nitrogenous amorphous carbon (a‐CN_x) thin films were deposited by radio‐frequency cathodic magnetron sputtering (13.56 MHz) on polished and etched titanium disks. While these films are cheaper to prepare than commonly reported carbon‐based electrodes, the usable electrochemical window in aqueous solution is within the same range and spans from ?1.5 to +1.8 V vs. SCE. The electrochemical reactivity was tested using the ferri‐ferrocyanide redox couple as a function of the thin films preparation parameters. The obtained electrochemical properties allow the use of these a‐CN_x thin films for stripping electroanalysis of cations in water, minimizing potential solvent reactivity. Cadmium and copper were used to test these detection abilities. Better analytical properties (notably sensitivity and linearity) were obtained as compared to a commercial boron doped diamond electrode. Preliminary competition/interaction experiments for these two cations were performed.     

A linearization framework for unconstrained quadratic (0-1) problems

In this paper, we are interested in linearization techniques for the exact solution of the Unconstrained Quadratic (0-1) Problem. Our purpose is to propose “economical” linear formulations. We first extend current techniques in a general linearization framework containing many other schemes and propose a new linear formulation. Numerical results comparing classical, Glover’s and the new linearization are reported.     

Measurement of the high energy two-body deuteron photodisintegration differential cross section

The first measurements of the d(gamma,p)n differential cross section at forward angles and photon energies above 4 GeV were performed at the Thomas Jefferson National Accelerator Facility (JLab). The results indicate evidence of an angular dependent scaling threshold. Results at straight theta(cm) = 37 degrees are consistent with the constituent counting rules for E(gamma) greater, similar 4 GeV, while those at 70 degrees are consistent with the constituent counting rules for E(gamma) greater, similar 1.5 GeV.