Effet sterique sur les vitesses de transfert protonique: cyclohexanols substitues dans le dimethylsulfoxyde

Steric effects on proton transfer from, and to, hydroxylic oxygen have been studied in a series of seventeen α-methyl and a-benzyl cyclohexanols in anhydrous DMSO, under both acid and base catalysed conditions, using dynamic MNR techniques. The protonation rate constants (k₁ ? 10⁶ M^-1 s^-1 at 25°C) obey a Taft-Ingold relationship, containing only a steric contribution E_s = E_s^OH + E_s^α, where: E_s^OH = 0 or 0.15 for an axial or equatorial hydroxyl respectively and E_s^α = ?0.070 (or ?0.115) for substituting an α-hydrogen by a methyl (or benzyl) group. An equatorial hydroxylic function is therefore 40% more reactive than its axial homologue. These kinetic data are fairly consistent with structural information resulting from IR spectroscopy (v_co and v_OH vibrations) and from NMR (hydroxylic chemical shifts and coupling constants).     

Beyond the diffusing-wave spectroscopy model for the temporal fluctuations of scattered light

We extend the theory of diffusing-wave spectroscopy using a random-walk approach and a numerical solution of the radiative transfer equation. The theory is not restricted to the diffusive regime and allows one to describe the crossover between the single-scattering and the diffusive regimes, which has been observed experimentally. It also predicts a lower bound of the scattered-field correlation time at long paths. This extended theory should have broad experimental applications in the field of imaging through biological tissues.     

Gas chromatography/mass spectrometric identification of dopaminergic metabolites in striata of rats treated with L-DOPA

The ex vivo identification of dopaminergic metabolites present in rat striata after (L-DOPA + benserazide) treatment is reported. The different metabolites have been identified as the trimethylsilyl derivatives in the striatal extracts by gas chromatography/mass spectrometry.     

Onset of Surface Damage in Modular Orthopedic Implants: Influence of Normal Contact Loading and Stress-assisted Dissolution

Surface damage at interfaces of modular implants results from repeated fretting contacts between metallic surfaces in a corrosive environment. As a first step in understanding this complex process, multi-asperity contact experiments were conducted to characterize roughness evolution due to action of contact loads and exposure to a reactive environment. Cobalt–chromium specimens with surface roughness similar to modular implant were first subjected to only contact loading and subsequently, to alternating contact loads and exposure to reactive environment. During repeated normal contact loading, amplitude of surface roughness reached a steady value after decreasing during the first few cycles. However during the second phase surface roughness amplitude continuously evolved—decreasing during contact loading and increasing on exposure to corrosive environment. The increase in roughness amplitude during surface reaction depended on the magnitude of applied contact loads. A damage mechanism that incorporates contact-induced residual stress development and stress-assisted dissolution is proposed to elucidate the measured surface roughness evolution.     

Characterization of Ce(3+) -tributyl phosphate coordination complexes produced by fused droplet electrospray ionization with a target capillary

Coordination complexes containing Ce(III) and tri-n-butyl phosphate (TBP) in the 1+, 2+ and 3+ charge states were generated using both direct infusion electrospray ionization (ESI) and fused droplet (FD) ESI using a target capillary, in which the analyte solutions are impinged by the ESI droplets. The same coordination complexes were produced in each experiment, and their relative abundances were also very close, suggesting that similar processes are occurring in both experiments. The ion species formed in both experiments have the general formula [Ce(NO(3) )(m=0-2) (TBP)(n=3-7) ]((3-m)+) . The appearance of abundant 1+ and 2+ ion pair complexes indicated that the ESI process was modifying the ion populations in the original solutions, which contain predominantly 3+ and 2+ species. The FD ESI experiments were less sensitive for coordination complexes compared to direct infusion ESI; however, mid-picomolar quantities of coordination complexes were measured using the target capillary, indicating that sensitivity would be sufficient for measuring species in many industrial separations processes.     

Le Spectre de L'Alcool Propargylique en Fonction du pH. Un Exemple de Transferts Protoniques Complexes sur un Diacide Organique

Dimethyl sulphoxide (DMSO) is used as a solvent to investigate the kinetic acidity of very weak organic diacids by ¹H d.n.m.r. An inspection of the spectrum of propargyl alcohol as a function of the pH allows the assignment of various proton transfer mechanisms:      

Antifilarial activity in vitro of polycarpol and 3-O-acetyl aleuritolic acid from cameroonian medicinal plants against Onchocerca gutturosa

Previous results have revealed the antifilarial activities of crude extracts and pure compounds from some Cameroonian medicinal plants against Onchocerca volvulus and Onchocerca gutturosa. In our efforts to find new filaricidal agents against adult male O. gutturosa worms, we have isolated and screened three compounds: polycarpol and polyveoline from Polyalthia suaveolens (Annonaceae) and 3-O-acetyl aleuritolic acid from Discoglypremna caloneura (Euphorbiaceae). Only polycarpol and 3-O-acetyl aleuritolic acid exhibited significant inhibitory activities on the vitality of adult male worms of O. gutturosa using Amocarzine as positive control compound. The motility reduction values were 28.6 and 57.1%, and the inhibition of MTT reduction values 80.0 and 64.8% respectively.     

Tool replacement policy for one-sided processes with low fraction defective

In most manufacturing industries, tool replacement policy is essential for minimizing the fraction defective and the manufacturing cost. Tool wear is caused by the action of sliding chips in the shear zone, and the friction generated between the tool flank and workpiece. This wear, apparently, is a dominant and irremovable component of variability in many machining processes, which is a systematic assignable cause. As the tool wear occurs in the machining processes, the fraction of defectives would gradually become significant. When the fraction defective reaches a certain level, the tool must be replaced. Therefore, detecting suitable time for tool replacement operation becomes essential. In this paper, we present an analytical approach for unilateral processes based on the one-sided process capability index C _PU (or C _PL ) to find the appropriate time for tool replacement. Accurate process capability must be calculated, particularly, when the data contains assignable cause variation. By calculating the index C _PU (or C _PL ) in a dynamical environment, we propose estimators of C _PU (or C _PL ) and obtain exact form of the sampling distribution in the presence of systematic assignable cause. The proposed procedure is then applied to a real manufacturing process involving tool wear problem, to demonstrate the applicability of the proposed approach.     

Determination of γ-γ' lattice misfit in a single-crystal nickel-based superalloy using convergent beam electron diffraction aided by finite element calculations

In single-crystal nickel-based superalloys, the lattice mismatch associated with interface coherency between γ matrix and γ' precipitates has a strong influence on mechanical properties. The unconstrained lattice misfit in a single-crystal of the MC2 nickel-based superalloy is determined using convergent beam electron diffraction measurements and finite element calculations. The apparent lattice parameters of both constrained phases are obtained in thin foils, using a new multi-pattern approach, which allows for unambiguous determination of all the lattice parameters considering the real symmetry of the strained crystals. Finite element calculations are used to establish relations between the constrained and unconstrained lattice parameters, with the stress relaxation resulting from the thin foil geometry taken into account.