Lyotropic mesomorphism of alkyl esters of acyl-L-carnitines

The lyotropic polymorphism of a series of alkyl esters of acyl-L-carnitine has been studied by optical polarizing microscopy and X-ray diffraction. The different structures observed as a function of concentration and temperature have been characterized and their topology determined. As a result, two different phase sequence patterns have been detected: esters of normal alcohols bearing an alkyl chain of 6 or more carbon atoms in the acyl substituent display only a lamellar phase, while compounds which bear a relatively short alkyl chain (4 or less carbon atoms) show in addition non-lamellar type I hexagonal and cubic Q²³⁰ phases. From the analysis of the areas-per-molecule at the polar/apolar interface, the ability of the compounds investigated to form not only non-lamellar phases, but also direct micelles in isotropic solution has been related to the structural characteristics of the molecules. Curved, convex interfaces (in micelles and in non-lamellar phases) are possible only for the most polar acylcarnitines which have a relatively short alkyl chain, so that they behave like single chain surfactants; the most paraffinic derivatives, which have a relatively long alkyl chain, are effective double chain surfactants and then generate only quasi-planar interfaces.     

On the solution set of an equation of the type f(t, Φ(u(t)) = 0

We investigate the solution set Γ of an equation of the type f(t, Φ(u(t)) = 0, where Φ is a linear homeomorphism from a topological vector space X onto L ¹(T) and f: T×R → R is a Carathéodory function. More precisely, we characterize the property of Γ of intersecting each closed hyperplane of X.     

Ion–molecule reactions by chemical ionization: Determination of rate constants

Tungsten hexacarbonyl was studied by chemical ionization mass spectrometry using carbon monoxide as reagent gas. The variation of the relative abundances of ions as a function of reactant gas pressure was used for evaluating the relative rate constants for consecutive reactions. The results are in agreement with the rate constant ratios obtained from ion trap mass spectrometric data.     

Indole alkaloids from the roots of an african plant securidaca longipedunculata. I. Isolation by column chromatography and preliminary structural characterization by mass spectrometry

The extraction and the isolation of some alkaloids from the roots of an African plant (Securidaca Longipedunculata Fres) are reported. The structural characterization was performed by mass spectrometry. Alternative ionization methods (FAB and EI), collisionally-induced decomposition experiments and accurate mass measurements revealed the presence of elymoclavine and dehydroelymoclavine and the presence of a new ergoline alkaloid.     

Sodium Chloride Molar Conductance in Different Poly(ethylene glycol)–Water Mixed Solvents

The molar conductivities of NaCl in several poly(ethylene glycol)(PEG)–water “mixed solvents” are presented as a function of the PEG content in solution. Three different PEG samples, a monodispersed one and two polydispersed ones, have been used. The comparison between the molar conductivity values in the mixed solvents and the corresponding ones in pure water shows that the only effect of PEG on the ions’ motions is an obstruction effect despite the variation of the macroscopic dielectric constant induced by PEG itself. A comparison between the molar conductivities and the corresponding mutual main diffusion coefficients shows a tight correlation between the two quantities. This correlation is possible only in the absence of electrostatic effects due to the presence of PEG.     

The Oxidative Mechanism in Electrophilic C?H Activation: The Case of CH2F2 and CH2Cl2

The H^.‐atom transfer (HAT) reaction is investigated in the gas phase, starting from two different entrance channels, O₂^.+/CH₂X₂ and CH₂X₂^.+/O₂ (X=F, Cl), that correspond to a step of hydride transfer and to HAT, respectively. Analysis of the spin and charge along the reaction pathway shows that HAT occurs through the same reacting configuration, irrespective of whether the reactants are formed within the complex or are free isolated species.     

Calorimetric adaptation of the inhibited autoxidation method to determine the activity of individual antioxidants and natural extracts

Journal of Thermal Analysis and Calorimetry - This work aims to determine the antioxidants activity of individual antioxidants and natural extracts by isothermal calorimetry. The proposed...     

Optimizing daily agent scheduling in a multiskill call center

We examine and compare simulation-based algorithms for solving the agent scheduling problem in a multiskill call center. This problem consists in minimizing the total costs of agents under constraints on the expected service level per call type, per period, and aggregated. We propose a solution approach that combines simulation with integer or linear programming, with cut generation. In our numerical experiments with realistic problem instances, this approach performs better than all other methods proposed previously for this problem. We also show that the two-step approach, which is the standard method for solving this problem, sometimes yield solutions that are highly suboptimal and inferior to those obtained by our proposed method.     

Asymmetric radiation-induced inclusion polymerization of 3-methyl-1,4-pentadiene in deoxycholic acid

The radiation-induced polymerization of 3-methyl-1,3-pentadiene (3MPD) as an inclusion complex in deoxycholic acid (DOCA) has produced in good yield the optically active polymer poly(3-methyl-1,4-pentadiene) (P3MPD) whose structure and properties were studied by FT-IR spectroscopy and thermal analysis (TGA, DTG and DTA). The data show that the polymer is essentially trans-1,4-P3MPD as expected for the polymerization in constrained media. Trans-1,4-P3MPD is optically active with [α]_D values comprised between +4.3 and +5.6. The optical rotatory dispersion curve of the P3MPD is completely different from that of DOCA as expected.