Biased Diffusion in a One-Dimensional Adsorbed Monolayer

We study the dynamics of a probe particle, which performs biased diffusive motion in a one-dimensional adsorbed monolayer composed of mobile hard-core particles undergoing continuous exchanges with a vapor phase. In terms of a mean-field-type approach, based on the decoupling of the third-order correlation functions into the product of pairwise correlations, we determine analytically the density profiles of the monolayer particles, as seen from the stationary moving probe, and calculate the terminal velocity V _pr, mobility _pr and the self-diffusion coefficient D _pr of the probe. Our analytical results are confirmed by Monte Carlo simulations.     

Shape-controlled bridged silsesquioxanes: hollow tubes and spheres

A new approach for the morphological control of bridged silsesquioxanes has been achieved by the hydrolysis of silylated organic molecules bearing urea groups. The urea groups are responsible for the auto-association of the molecules through intermolecular hydrogen-bonding interactions. The self-assembly leads to supramolecular architectures that have the ability to direct the organization of hybrid silicas under controlled hydrolysis. The hydrolysis of the chiral diureido derivatives of trans-(1,2)-diaminocyclohexane 1 under basic conditions has been examined. The solid-state NMR spectra ((29)Si and (13)C) showed the hybrid nature of these materials with wholly preserved S-C bond covalent bonds throughout the silicate network. Hybrid silicas with hollow tubular morphologies were obtained by the hydrolysis of the enantiomerically pure compounds, (R,R)-1 or (S,S)-1, whereas the corresponding racemic mixture, rac-1, led to a hybrid with ball-like structures. The tubular shape is likely to result from a combination of two phenomena: the auto-association abilities and a self-templating structuration of the hybrid materials by the organic crystalline precursor. Electronic microscopy techniques (SEM and TEM) gave evidence for the self-templating pathway. The formation of the ball-like structures occurs through a usual nucleation growth phenomenon owing to a higher solubility of the corresponding crystals in the same medium.     

Determination of the active metabolite of molsidomine in human plasma by reversed-phase high-performance liquid chromatography

A reversed-phase high-performance liquid chromatographic method, with ultraviolet detection, is proposed for the plasma determination of SIN-1, the active metabolite of molsidomine, which involves propoxycarbonyl derivatization. The internal standard is the ethoxycarbonyl derivative of SIN-1 (i.e. molsidomine). Derivatization and extraction are each performed in one step (2 min) with 70% yield. The nature of a by-product is discussed. The method provides rapid elution (less than 15 min), linearity over the range 0.4-200 ng/ml, day-to-day precision between 2.5 and 11.3% and a limit of determination of 0.5 ng/ml. This method is also suitable for the simultaneous determination of molsidomine and SIN-1. In this case the internal standard is an ethoxycarbonyl derivative of a piperazino-3-sydnonimine, a SIN-1 analogue.     

Maleimide polymers. III. Color reactions and kinetics

We have shown previously that the free-radical polymerization kinetics of maleimide can be explained by a scheme for retarded polymerization. The steps involve tautomerization of a growing maleimidyl chain to succinimidyl, the retarded addition of maleimide to the latter, and termination solely by resonance-stabilized succinimidyl radicals. Combination termination is preferred, since this yields a very stable N,N′-bisuccinimidyl structure. Other authors also invoke tautomerization to succinimidyl radicals which they believe terminate by disproportionation with growing maleimidyl chains to generate polymer with unsaturated endgroups. Free-radical-initiated polymaleimides are colored in the presence of base. Our measurements of the absorbance of polymaleimides at 387 and 500 nm in the presence of excess strong organic base show there is essentially no dependence on molecular weight. This suggests that the chromophoric groups are intramolecular and that color does not arise from the ionization of allylic protons associated with terminal double bonds. The near-ultraviolet spectra of polymaleimides in slightly acidic media contain absorption bands at about 288, 320, and 360 nm. The structural impurities that account for these bands cannot be terminal unsaturation. We propose that the origin of these bands is pyrrolinone type structures which are formed by a retarded polymerization step through succinimidyl oxygen.     

Clean conditions for the determination of ultra-low levels of mercury in ice and snow samples

Laboratory facilities and methods are presented for the determination of ultra-low levels of mercury (Hg) in ice and snow samples originating from polar ice caps or temperate regions. Special emphasis will be given to the presentation of the clean laboratory and the cleaning procedures. The laboratory is pressurized with air filtered through high efficiency particle filters. This first filtration is not enough to get rid of contamination by Hg in air. Experiments are conducted in a clean bench, especially built for Hg analysis, equipped with both particle filter and activated charcoal filter. It allows to obtain very low levels of atmospheric Hg contamination. Ultrapure water is produced for cleaning all the plastic containers that will be used for ice and snow samples and also for the dilution of the standards. Hg content in laboratory water is about ¶0.08 ± 0.02 pg/g. A Teflon system has been developed for the determination of Hg in ice and snow samples based on Hg(II) reduction to Hg(0) with a SnCl₂/HNO₃ solution followed by the measurement of gaseous Hg(0) with a Hg analyzer GARDIS 1A+ based on the Cold Vapor Atomic Absorption Spectroscopy method. Blank determination is discussed.     

Nucleation theory for a model bistable chemical reaction

The theory of homogeneous nucleation is developed for a model nonlinear bistable chemical reaction driven far from equilibrium (trimolecular Schlögl model). The theory is restricted to the vicinity of the stable/unstable transition, where the nucleation barrier is small but nonvanishing. The nucleation rates are derived for two types of fluctuations: first, fluctuations due to a homogeneous external white noise source, and second, internal chemical fluctuations, described by a reastion-diffusion multivariate master equation. In the white noise case, a Landau-Ginzburg potential can be defined, and the standard nucleation formalism can be applied; this is not true for the internal case and a new result is used. The inhomogeneous chemical fluctuations, due to the coupling between the nonlinear reaction and diffusion, are shown to have an influence on the nucleation rate. Quantitative conditions are also given to evaluate the possibility of homogeneous nucleation in nonlinear chemical systems.     

Numerical prediction of turbulent boundary layer noise from a sharp-edged flat plate

An efficient hybrid uncorrelated wall plane waves–boundary element method (UWPW-BEM) technique is proposed to predict the flow-induced noise from a structure in low Mach number turbulent flow. Reynolds-averaged Navier-Stokes equations are used to estimate the turbulent boundary layer parameters such as convective velocity, boundary layer thickness, and wall shear stress over the surface of the structure. The spectrum of the wall pressure fluctuations is evaluated from the turbulent boundary layer parameters and by using semi-empirical models from literature. The wall pressure field underneath the turbulent boundary layer is synthesized by realizations of uncorrelated wall plane waves (UWPW). An acoustic BEM solver is then employed to compute the acoustic pressure scattered by the structure from the synthesized wall pressure field. Finally, the acoustic response of the structure in turbulent flow is obtained as an ensemble average of the acoustic pressures due to all realizations of uncorrelated plane waves. To demonstrate the hybrid UWPW-BEM approach, the self-noise generated by a flat plate in turbulent flow with Reynolds number based on chord Re_c = 4.9 × 10⁵ is predicted. The results are compared with those obtained from a large eddy simulation (LES)-BEM technique as well as with experimental data from literature.     

Alternated π‐conjugated polymers based on a 1,2‐diiminocyclohexane chiral unit for nitroaromatics sensing

The detection of 2,4‐dinitrotoluene (DNT) by fluorescence quenching of a new class of polyimines consisting in π‐conjugated segments regularly alternated with chiral C₂ symmetry units has been studied for solutions and thin films. Their photophysical properties and their sensitivity towards DNT detection has been compared to those of a small model molecule incorporating the same π‐conjugated segment. In solution, all the compounds exhibit the same photo‐physical properties and sensitivity towards DNT detection. In contrast, for thin films, better performances are observed in static conditions for this new class of polyimines compared to the small model molecule. It seems that C₂ symmetry units prevent from the stacking of the π‐conjugated segments and provide in addition to high fluorescence signal an improved diffusion of the analyte inside the films. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4141–4149, 2009     

Lamellar bridged silsesquioxanes: self-assembly through a combination of hydrogen bonding and hydrophobic interactions

The synthesis of four bis(trialkoxysilylated) organic molecules capable of self-assembly--(EtO)3Si(CH2)3NHCONH-(CH2)n-NHCONH(CH2)3Si(OEt)3 (n = 9-12)--associating urea functional groups and alkylidene chains of variable length is described. These compounds behave as organogelators, forming supramolecular assemblies thanks to the intermolecular hydrogen bonding of urea groups. Whereas fluoride ion-catalysed hydrolysis in ethanol in the presence of a stoichiometric amount of water produced amorphous hybrids, acid-catalysed hydrolysis in an excess of water gave rise to the formation of crystalline lamellar hybrid materials through a self-organisation process. The structural features of these nanostructured organic/inorganic hybrids were analysed by several techniques: attenuated Fourier transformed infrared (ATR-FTIR), solid-state NMR spectroscopy (13C and 29Si), scanning and transmission electron microscopy (SEM and TEM) and powder X-ray diffraction (PXRD). The reaction conditions, the hydrophobic properties of the long alkylidene chains and the hydrogen-bonding properties of the urea groups are determining factors in the formation of these self-assembled nanostructured hybrid silicas.