Kinetic parameter estimation of solvent‐free reactions monitored by 13C NMR spectroscopy,a case study: Mono‐ and di‐(hydroxy)ethylation of aniline with ethylene carbonate

The kinetics of solvent‐free reactions can be followed in situ by ¹³C nuclear magnetic resonance (NMR) spectroscopy, provided that the reaction mixture can be maintained liquid at the monitoring temperature. The pros and cons of the technique and the correct translation of the signal intensities into concentrations are discussed. A good model for this investigation is the reaction of ethylene carbonate ( 1 ) with aniline ( 2 ) at 140°C, two alkylation products of N‐mono‐ and N, N‐bis‐(2‐hydroxy)ethylation of aniline form (compounds 3 and 4 , respectively). The overall reaction occurs with heavy volume shrinking, so that the physical as well as the chemical features evolve during the course of the process. The chemical evolution is described by the kinetic constants k₁ and k₂ of the two N‐alkylation steps, the physical evolution by the time‐dependent activity coefficients α(t). Two complementary procedures are utilized for the determination of these parameters. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 154–160, 2011     

Spatial and vertical distributions of natural and anthropogenic radionuclides and cesium fractionation in sediments of the Var river and its tributaries (southeast France)

This paper reports results on the natural and anthropogenic radionuclides activity concentrations in sediments of the Var river and its tributaries. Natural (²³⁸U, ²³²Th and ⁴⁰K) and artificial (¹³⁷Cs) radionuclides activities were measured using high purity germanium detector. Measured activity concentrations differ widely; they depend on the pertinent environmental situation such as the presence of dams, and sediments type. Other factors controlling the distribution of the studied radioisotopes have been discussed. A sequential extraction method consisting of six operationally-defined fractions has been used for determining the geochemical partitioning of anthropogenic radionuclide ¹³⁷Cs in a 405–410 cm deep sediments collected in the lower valley of the Var river. This method corresponds to a modification of the three-stage sequential extraction procedure proposed by the Commission of the European Communities Bureau of Reference (BCR, now Standards, Measurements and Testing Program). Two steps with weak reagents, (fraction A: water; fraction B: nitric acid 0.001 M), were added before the first step of BCR (carbonate fraction) in order to better detect anthropogenic components. A total acid digestion of solid residues by microwave assisted was also added. The 6-steps extraction method was tested and validated by certified reference materials. ¹³⁷Cs was found mostly in the hydrosoluble fraction (20–24 %), oxide and hydroxide fraction (22–25 %) and in the residue (51–58 %), while ¹³³Cs was mostly found in the residual fraction (>97 %).     

A Hydrodynamic Model for Covalent Semiconductors with Applications to GaN and SiC

In this paper we present a hydrodynamical model which, in principle, is able to describe charge transport in a generic compound semiconductor. The model makes use of an analytic approximation for the conduction bands. Energy dispersion relationships in the neighbors (valleys) of the lowest minima are, in fact, taken to be spherical, nonparabolic. The model considers the main scattering mechanisms in polar semiconductors, that is the acoustic, polar optical, intervalley non-polar optical phonon interactions and the ionized impurity scattering. Simulations are shown for the cases of bulk GaN and SiC.     

Comparing stage-scenario with nodal formulation for multistage stochastic problems

To solve real life problems under uncertainty in Economics, Finance, Energy, Transportation and Logistics, the use of stochastic optimization is widely accepted and appreciated. However, the nature of stochastic programming leads to a conflict between adaptability to reality and tractability. To formulate a multistage stochastic model, two types of formulations are typically adopted: the so-called stage-scenario formulation named also formulation with explicit non-anticipativity constraints and the so-called nodal formulation named also formulation with implicit non-anticipativity constraints. Both of them have advantages and disadvantages. This work aims at helping the scholars and practitioners to understand the two types of notation and, in particular, to reformulate with the nodal formulation a model that was originally defined with the stage-scenario formulation presenting this implementation in the algebraic language GAMS. In addition, this work presents an empirical analysis applying the two formulations both without any further decomposition to perform a fair comparison. In this way, we show that the difficulties to implement the model with the nodal formulation are somehow reworded making the problem tractable without any decomposition algorithm. Still, we remark that in some other applications the stage-scenario formulation could be more helpful to understand the structure of the problem since it allows to relax the non-anticipativity constraints.

     

Polymorphism of the co-crystalline forms of syndiotactic polystyrene with chloroform: Crystal structure of the δ clathrate

The crystal structure of the δ clathrate form of syndiotactic polystyrene (s-PS) containing CHCl₃, a molecule having a pivotal role in respect to the co-crystalline phases formation of this polymer, has been determined through X-ray diffraction data and molecular mechanics calculations. Analogously to all the other δ clathrate forms of s-PS, this structure presents a monoclinic unit cell (cell constants a = 1.77 nm, b = 1.32 nm, c = 0.78 nm and γ = 121.5°) in which the s(2/1)2 polymer helices and guest molecules are packed according the space group P2₁/a. At variance with all the other δ clathrate forms of s-PS whose crystal structure has been reported in the literature, probably due to the not planar shape of the chloroform guest molecule, in this structure guest molecules occupy each centrosymmetric cavity in a very low efficient way, giving rise to a disorder in the positioning of the guest molecules along the b + a/2 direction of the unit cell. A comparison with the ε type clathrate with the same guest, for which some preliminary results have been reported too, is also presented.     

A compactness result for differentiable functions with an application to boundary value problems

We characterize the relative compactness of subsets of the space ${\mathcal{BC}^m([0,+\infty [;E)}$ of bounded and m-differentiable functions defined on [0, +∞[ with values in a Banach space E. Moreover, we apply this characterization to prove the existence of solutions of a boundary value problem in Banach spaces.     

Drop deformation in microconfined shear flow

The deformation and breakup of a drop in an immiscible equiviscous liquid undergoing unbounded shear flow has been extensively investigated in the literature, starting from the pioneering work of Taylor. In this Letter, we address the case of microconfined shear flow, a problem which is relevant for microfluidics and emulsion processing applications. The main effects of confinement include complex oscillating transients and drop stabilization against breakup. In particular, very elongated drop shapes are observed, which would be unstable in the unbounded case and can be explained in terms of wall-induced distortion of the shear flow field. We show that wall effects can be exploited to obtain nearly monodisperse emulsions in microconfined shear flow.     

Observation of magnetophonon resonance of Dirac fermions in graphite

Coherent coupling of Dirac fermion magnetoexcitons with an optical phonon is observed in graphite as marked magnetic-field dependent splittings and anticrossing behavior of the two coupled modes. The sharp magnetophonon resonance occurs in regions of the graphite sample with properties of superior single-layer graphene having enhanced lifetimes of Dirac fermions. The greatly reduced carrier broadening to values below the graphene electron-phonon coupling constant explains the appearance of sharp resonances that reveal a fundamental interaction of Dirac fermions.     

Accidental exposure to UV radiation produced by germicidal lamp: case report and risk assessment

Ultraviolet radiation is known to cause both benefits and harmful effects on humans. The adverse effects mainly involve two target organs, skin and eye, and can be further divided into short- and long-term effects. The present case report describes an accidental exposure of two health-care workers to ultraviolet radiation produced by a germicidal lamp in a hospital pharmacy. The germicidal lamp presented a spectrum with an intense UV-C component as well as a modest UV-B contribution. Overexposure to UV-C radiation was over 100 times as large as the ICNIRP exposure limits. A few hours after the exposure, the two subjects reported symptoms of acute UV injury and both of them continued having significant clinical signs for over 2 years. In this study, we describe acute and potentially irreversible effects caused by high UV exposure. In addition, we present the results of risk assessment by occupational exposure to germicidal lamps.