Evidence for complexes of different stoichiometries between organic solvents and cyclodextrins

The influence of the organic solvent on the acid and basic hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in the presence of alpha- and beta-cyclodextrins has been studied. The observed rate constant was found to decrease through the formation of an unreactive complex between MNTS and the cyclodextrins. In the presence of dioxane, acetonitrile or DMSO, the inhibitory effect of beta-CD decreased on increasing the proportion of organic cosolvent as a result of a competitive reaction involving the formation of an inclusion complex between beta-CD and the cosolvent. The disparate size of the organic solvent molecules resulted in stoichiometric differences between the complexes; the beta-CD-dioxane and beta-CD-DMSO complexes were 1 : 1 whereas the beta-CD-acetonitrile complex was 1 : 2. The basic and acid hydrolysis of MNTS in the presence of alpha-CD showed a different behavior; thus, the reaction gave both 1 : 1 and 2 : 1 alpha-CD-MNTS complexes, of which only the former was reactive. This result was due to the smaller cavity size of alpha-CD and the consequent decreased penetration of MNTS into the cavity in comparison to beta-CD. The acid hydrolysis of MNTS in the presence of alpha-CD also revealed decreased penetration of MNTS into the cyclodextrin cavity, as evidenced by the bound substrate undergoing acid hydrolysis. In addition, the acid hydrolysis of MNTS in the presence of acetonitrile containing alpha-CD gave 1 : 1 alpha-CD-acetonitrile inclusion complexes, which is consistent with a both a reduced cavity size and previously reported data.     

Effects of zwitterionic vesicles on the reactivity of benzoyl chlorides

A systematic study on the solvolysis reaction of substituted benzoyl chlorides in the presence of zwitterionic vesicles of dipalmitoyl phosphatidylcholine (DPPC) has been performed. Size, shape, surface charge, and polarity of the interface of the vesicular aggregates were determined using various techniques. The application of the pseudophase formalism allowed us to obtain the thermodynamic and kinetic coefficients characteristic of the reaction. The effects of vesicular aggregates on the solvolysis of benzoyl chlorides, which are known to be sensitive to the physical properties of the medium, depend on the nature of the substrate. For benzoyl chlorides with electron-donating groups, which react predominantly through a dissociative mechanism which is strongly affected by medium properties, the rate constant decreases as the vesicle concentration increases. On the other hand, for benzoyl chlorides with electron-withdrawing groups, which react mainly via an associative pathway, DPPC vesicles catalyze the solvolysis reaction.     

Robust multiobjective optimization with application to Internet routing

Robust optimization addressing decision making under uncertainty has been very well developed for problems with a single objective function and applied to areas of human activity such as portfolio selection, investment decisions, signal processing, and telecommunication-network planning. As these decision problems typically have several decisions or goals, we extend robust single objective optimization to the multiobjective case. The column-wise uncertainty model can be carried over to the multiobjective case without any additional assumptions. For the row-wise uncertainty model, we show under additional assumptions that robust efficient solutions are efficient to specific instance problems and can be found as the efficient solutions of another deterministic problem. Being motivated by the fact that Internet traffic must be maintained in a reliable yet affordable manner in situations of complex and dynamic usage, we apply the row-wise model to an intradomain multiobjective routing problem with polyhedral traffic uncertainty. We consider traditional objective functions corresponding to link utilizations and implement the biobjective case using the parametric simplex algorithm to compute robust efficient routings. We also present computational results for the Abilene network and analyze their meaning in the context of the application.     

High-order dimensionally split Lagrange-remap schemes for compressible hydrodynamics

We first propose a new class of finite volume schemes for solving the 1D Euler equations. Applicable to arbitrary equations of state, these schemes are based on a Lagrange-remap approach and are high-order accurate in both space and time in the nonlinear regime. A multidimensional extension on nD Cartesian grids is then proposed, using a high-order dimensional splitting technique. Numerical results up to 6th-order are provided.     

Few-cycle solitons in supercontinuum generation dynamics

We review several propagation models that do not rely on the slowly-varying-envelope approximation (SVEA), and can thus be considered as fundamental models addressing the formation and propagation of few-cycle pulsed field structures and solitary waves arising in the course of intense ultrashort optical pulse evolution in nonlinear media and beyond octave-bandwidth optical spectrum broadening. These generic models are: the modified-Korteweg-de Vries (mKdV), the sine-Gordon (sG), and the mixed mKdV-sG equations. To include wave polarization dynamics, the vector extensions of both mKdV and sG equations are introduced. Multi-octave-spanning supercontinuum generation and few-cycle soliton structures are highlighted from numerical simulations.     

EPR of free radicals formed from 3-hydroxyesculetin and related derivatives

EPR spectroscopy of 3-hydroxyesculetin (1, solid and in solution) and of the radicals formed during the aerobic oxidation of alkaline solutions of 1 and related compounds was investigated. 1 in the solid state was studied by pulsed EPR experiments and showed a radical character. The aerobic oxidation of alkaline solutions of 1 was also followed by EPR spectroscopy. A ring contraction occurred leading to a 5,6-dihydroxybenzofuran-2-carboxylate radical. The autoxidation of an alkaline solution of (Z)-3-(3,4-dihydroxyphenyl)-2-hydroxypropenoic acid allowed the observation of a spectrum attributable to 5,6-dihydroxybenzofuran-3-one-2-carboxylate radical. The formation mechanisms of these radicals are discussed.     

Easy access to phosphonothioates

A new and particularly mild method for the formation of phosphorus-sulfur bonds has been achieved through base-catalyzed addition of thiocyanate to the corresponding H-phosphine oxide, phosphinate, or phosphonate. This reaction procedure offers many advantages: the use as starting material of a stable and not oxygen-sensitive phosphorus(v) species, particularly mild and nonaqueous reaction conditions and workup (a pivotal point for these sensitive phosphonothioates), and, through optimized access to thiocyanates, a wider scope of substrates. This method has been applied to achieve the synthesis of substrate analogues for the study of antibody-catalyzed hydrolysis of acetylcholinesterase inhibitor PhX (11).     

Dependence on sampling rates of Radiello((R)) diffusion sampler for BTEX measurements with the concentration level and exposure time

Radiello^® diffusive samplers filled with a thermally desorbable adsorbent (graphitised charcoal Carbograph 4) have been tested for the monitoring of BTEX. The sampling rates have been estimated under various controlled atmospheres in order to evaluate the effects of two factors (exposure time, concentration levels and their interaction) on the performances of the Radiello^® sampler. Experiments have been carried out under various atmospheres in exposure chamber. A total of 174 Radiello^® samplers were exposed while varying two conditions: exposure time (1, 3, 7 and 14 days) and BTEX concentrations (low, medium and high levels). The results show that the sampling rates of benzene and toluene decrease for exposure of 14 days and especially for high concentration levels: decrease of 30% at 10 μg m⁻³ for benzene and 14% at 30 μg m⁻³ for toluene.

To try to explain the variations of these sampling rates, the breakthrough volumes (V_B) of BTEX on Carbograph 4 have been determined at different temperature and concentration conditions in order to evaluate the Langmuir parameters and their adsorption enthalpy (−ΔH_ads) using the Van’t Hoff equation. With regard to these adsorption characteristics, the dependence of sampling rates with concentration level and exposure time were analysed and discussed.