Associative and preassociative functions

We investigate the associativity property for functions of multiple arities and introduce and discuss the more general property of preassociativity, a generalization of associativity which does not involve any composition of functions.     

A Characterization of Barycentrically Preassociative Functions

We provide a characterization of the variadic functions which are barycentrically preassociative as compositions of length-preserving associative string functions with one-to-one unary maps. We also discuss some consequences of this characterization.     

Multiple injection technique for the determination and quantitation of insulin formulations by capillary electrophoresis and time-of-flight mass spectrometry

This paper describes an efficient CE-UV-ESI-TOF/MS method for the determination and quantitation of intact insulin (INS) in a pharmaceutical formulation. The CE conditions were optimized to avoid the adsorption of proteins onto the capillary wall. Particular attention was paid regarding the choice of the internal standard (IS). A strategy based on multiple injections was selected and the methodology was validated according to international guidelines. The optimized method was applied with success to the analysis of INS formulations obtained from regular and parallel markets.     

High pressure phase equilibria in methane + waxy systems. 2. Methane + waxy ternary mixture

Liquid–vapour and fluid–solid phase transitions were experimentally determined under pressure on the system methane + a ternary waxy mixture using a full visibility cell. The wax was an approximately equimolar mixture of n-C₁₆, n-C₁₇ and n-C₁₈, the composition being chosen to obtain a mixture with an average molecular weight similar to heptadecane. Measurements were performed according to the synthetic method on different mixtures ranging from 0 to 99.5 mol% of methane. The liquid–solid phase transitions were investigated up to 100 MPa and fluid phase boundary was studied in the temperature domain from 293 to 373 K. Measurements performed on this pseudo-binary system were compared to the phase diagram of the binary system methane + heptadecane.     

Diels-Alder cycloaddition of o-quinonedimethides and alkylidene-5H-furan-2-ones: new and rapid access to lambertellol cores and arthrinone derivatives

An efficient synthesis of deoxy-lambertellols was reported through a highly chemo- and diastereoselective intermolecular Diels-Alder cycloaddition between trans-1,2-disiloxybenzocyclobutenes and 2-methylprotoanemonine. Such transformation with δ-substituted γ-alkylidenebutenolides, to prepare new analogues of these tricyclic spirolactones, which would be very difficult to prepare by other ways, was also studied.     

Diastereoselective access to trans-2-substituted cyclopentylamines

A highly diastereoselective synthesis of trans-2-substituted cyclopentylamines via a tandem hydrozirconation/Lewis acid-mediated cyclization sequence applied to butenyl oxazolidines is described. The method allows an easy preparation of diversely substituted cyclopentylamines which appear to be useful synthetic intermediates. This was further illustrated by the syntheses of (±)-Rodocaine, (±)-trans-pentacin, and enantiomerically enriched trans-cyclopentane-1,2-diamine.     

Stirring by swimming bodies

We consider the stirring of an inviscid fluid caused by the locomotion of bodies through it. The swimmers are approximated by non-interacting cylinders or spheres moving steadily along straight lines. We find the displacement of fluid particles caused by the nearby passage of a swimmer as a function of an impact parameter. We use this to compute the effective diffusion coefficient from the random walk of a fluid particle under the influence of a distribution of swimming bodies. We compare with the results of simulations. For typical sizes, densities and swimming velocities of schools of krill, the effective diffusivity in this model is five times the thermal diffusivity. However, we estimate that viscosity increases this value by two orders of magnitude.     

Effect of electronic polarization on charge-transport parameters in molecular organic semiconductors

Theoretical investigations of charge transport in organic materials are generally based on the "energy splitting in dimer" method and routinely assume that the transport parameters (site energies and transfer integrals) determined from monomer and dimer calculations can be reliably used to describe extended systems. Here, we demonstrate that this transferability can fail even in molecular crystals with weak van der Waals intermolecular interactions, due to the substantial (but often ignored) impact of polarization effects, particularly on the site energies. We show that the neglect of electronic polarization leads to qualitatively incorrect values and trends for the transfer integrals computed with the energy splitting method, even in simple prototypes such as ethylene or pentacene dimers. The polarization effect in these systems is largely electrostatic in nature and can change dramatically upon transition from a dimer to an extended system. For example, the difference in site energy for a prototypical "face-to-edge" one-dimensional stack of pentacene molecules is calculated to be 30% greater than that in the "face-to-edge" dimer, whereas the site energy difference in the pentacene crystal is vanishingly small. Importantly, when computed directly in the framework of localized monomer orbitals, the transfer integral values for dimer and extended systems are very similar.