Enhanced selectivity of the isolation of basic drugs from body fluids by means of extraction minicolumns and sophisticated elution schemes.

The paper presents results and experience obtained in the isolation of a number of basic polar/non-polar solutes (drugs, their metabolites and structural derivatives) from biological samples by using the separation minicolumns Separcol SI and Separcol SI C18 L/T. The aim was to provide insight into some simple procedures yielding optimal selectivity/specificity of the isolation of the studied solutes either by proper selection of the sorbent or by applying sophisticated elution schemes which use to advantage different properties of the eluents/solvents.     

Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.     

Calculation of cyclodextrin-mediated enantiomer ratio shifting of racem norgestrel in aqueous solutions

Enantioselective solubility of rac-norgestrel was found in the presence of γ-cyclodextrin or hydroxypropyl-γ-cyclodextrin. In both cases the efficacious enantiomer was dissolved in greater extent. Calculating the molar absorptivity and molar ellipticity spectra of the γ- and hydroxypropyl-γ-cyclodextrin aqueous complexes, a simple and rapid direct circular dichroism (CD) spectrometric method was obtained for the determination of the enantiomer ratio in aqueous solutions.     

Thickness dependence of free‐standing thin films

Below a critical thickness, of about 60 nm, the glass transition temperature of polystyrene (PS) films decreases with film thickness, as demonstrated using free‐standing films. A geometrical model is developed here describing this phenomenon in the case of ideal (Gaussian) chains. This model, which can be considered as an application of the free volume model, assumes that the decrease of the glass transition temperature from thick to ultrathin films is due to the modification of the interpenetration between neighboring chains. The theoretical curve deduced from the model is in excellent agreement with the PS experimental results, without using any adjustable parameters. From these results, it can be concluded that new chain motions, usually buried in bulk samples, are expressed by the presence of the surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 10–17, 2007     

Producing and transferring low-spatial-frequency grids for measuring displacement fields with moiré and grid methods

Experimental Techniques -     

Rate of Convergence of a Stochastic Particle System for the Smoluchowski Coagulation Equation

By continuing the probabilistic approach of Deaconu et al. (2001), we derive a stochastic particle approximation for the Smoluchowski coagulation equations. A convergence result for this model is obtained. Under quite stringent hypothesis we obtain a central limit theorem associated with our convergence. In spite of these restrictive technical assumptions, the rate of convergence result is interesting because it is the first obtained in this direction and seems to hold numerically under weaker hypothesis. This result answers a question closely connected to the Open Problem 16 formulated by Aldous (1999).     

Diffraction of transverse horizontal waves in Fibonacci piezoelectric superlattices

The transfer matrix and global matrix techniques are used in the analysis of diffraction of transverse horizontal waves in piezoelectric superlattices. The system is composed of a set of different piezoelectric layers with quasiperiodic structure according to the Fibonacci sequence. The diffraction spectrum of different configurations of piezoelectric Fibonacci structures is studied. Numerical results for the diffraction spectrum for the piezoelectric Fibonacci superlattice are obtained and a comparison between the results of the transfer and global matrix methods is given, exhibiting the advantage of the latter.     

Analysis of some combination-overtone infrared bands of SO3

Several new infrared absorption bands for ³²S¹⁶O₃ have been measured and analyzed. The principal bands observed were ν₁+ν₂ (at 1561 cm⁻¹), ν₁+ν₄ (at 1594 cm⁻¹), ν₃+ν₄ (at 1918 cm⁻¹), and 3ν₃ (at 4136 cm⁻¹). Except for 3ν₃, these bands are very complicated because of (a) the Coriolis coupling between ν₂ and ν₄, (b) the Fermi resonance between ν₁ and 2ν₄, (c) the Fermi resonance between ν₁ and 2ν₂, (d) ordinary l-type resonance that couples levels that differ by 2 in both the k and l quantum numbers, and (e) the vibrational l-type resonance between the A₁^′ and A₂^′ levels of ν₃+ν₄. The unraveling of the complex pattern of these bands was facilitated by a systematic approach to the understanding of the various interactions. Fortunately, previous work on the fundamentals permitted good estimates of many constants necessary to begin the assignments and the fit of the measurements. In addition, the use of hot band transitions accompanying the ν₃ band was an essential aid in fitting the ν₃+ν₄ transitions since these could be directly observed for only one of four interacting states. From the hot band analysis we find that the A₁^′ vibrational level is 3.50 cm⁻¹ above the A₂^′ level, i.e., r₃₄=1.75236(7) cm⁻¹. In the case of the 3ν₃ band, the spectral analysis is straightforward and a weak Δk=±2, Δl₃=±2 interaction between the l₃=1 and l₃=3 substates locates the latter A₁^′ and A₂^′ “ghost” states 22.55(4) cm⁻¹ higher than the infrared accessible l₃=1 E^′ state.     

An iterative procedure for differential analysis of gene expression

Microarrays are a popular technology to study genes that are differentially expressed between two conditions. In this Note, we propose an iterative procedure to determine the biggest subset of non-differentially expressed genes. We prove a pseudo Markov relationship that allows practical computations. We obtain explicit expressions for FDR and the level of the proposed test at each step. To cite this article: A. Bar-Hen, S. Robin, C. R. Acad. Sci. Paris, Ser. I 337 (2003).