Synthesis of Lipid Derivatives of Colchicine

The synthesis of glycero-lipids linked to colchicine derivatives is reported. The lipid structures are designed to perform two-dimensional crystallization experiments with tubulin, the structural subunit protein of microtubules.     

Hilbert subsets ands-integral points

A classical tool for studying Hilbert's irreducibility theorem is Siegel's finiteness theorem forS-integral points on algebraic curves. We present a different approach based ons-integral points rather thanS-integral points. Given an integers>0, an elementt of a fieldK is said to bes-integral if the set of placesv ∈M _K for which |t|_v > l is of cardinality ≤s (instead of contained inS for “S-integral”). We prove a general diophantine result fors-integral points (Th.1.4). This result, unlike Siegel's theorem, is effective and is valid more generally for fields with the product formula. The main application to Hilbert's irreducibility theorem is a general criterion for a given Hilbert subset to contain values of given rational functions (Th.2.1). This criterion gives rise to very concrete applications: several examples are given (§2.5). Taking advantage of the effectiveness of our method, we can also produce elements of a given Hilbert subset of a number field with explicitely bounded height (Cor.3.7). Other applications, including the case thatK is of characteristicp>0, will be given in forthcoming papers ([8], [9]).     

Effect of flow history on the structure of a non-polar polymer/clay nanocomposite model system

The effect of flow history on the linear and non-linear viscoelastic properties of non-polar polymer nanocomposites (PNCs) has been investigated by means of a suitable model system based on a Newtonian matrix. The structural recovery of this model suspension after cessation of different pre-shear rates was monitored by measuring its linear viscoelastic properties while its structural evolution under shear flow was followed by using stepwise changes in shear rate including flow reversal measurements. To assess the kinetics of the structural evolution at rest and under flow, empirical relations of stretched exponential form were used. It is shown that for different pre-shear rates, different equilibrium structures were reached at rest but with a similar kinetics of recovery. As a result, the low frequency behaviour was typical of solid-like or weak gel material, strongly dependent on the flow history. After any given shear rate under steady state, only one reversible equilibrium structure was reached after a kinetics that was dependent on the pre-shear history. Finally, typical flow reversal responses as observed for PNCs are reported and interpreted in light of the microstructure evolution under flow. This paper was presented at the Annual Meeting of the European Society of Rheology, Hersonisos, Greece April 2006.     

Simulations of rare events in fiber optics by interacting particle systems

In this paper we study the robustness of linear pulses, solitons, and dispersion-managed solitons, under the influence of random perturbations. First, we address the problem of the estimation of the outage probability due to polarization-mode dispersion. Second, we compare the pulse broadening due to random fluctuations of the group-velocity dispersion. We use an original interacting particle system to estimate the tails of the probability density functions of the pulse widths. A new adaptative Monte Carlo method is applied that enforces the simulations to probe the regions of practical importance by selection and mutation steps.     

Application of spin trapping to the kinetic study in the photolysis of sulfonium salts

The UV irradiated triarylsulfonium salts decompose under formation of phenyl radicals. Using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) spin trap the formation and the decay of DMPO-Ph adduct was followed during the irradiation and after irradiation stop at various DMPO and Ph₃S⁺BF^? ₄ concentrations. The experimental data observed were well fitted by the simulation and are in good agreemnt with the kinetic model suggested. The technique developed can be effectively used in various kinetic investigations.     

Enhanced activity and selectivity in cyclohexane autoxidation by inert H-bond acceptor catalysts.

Herein, we demonstrate that the chain-initiating dissociation of cyclohexyl hydroperoxide, CyOOH, is substantially accelerated by H-bond acceptors (e.g. Teflon), which assist O-O bond breaking by stabilising the leaving *OH radical. This is a completely new approach to boost the chain-propagating radical concentration. Indeed, up to now, literature has remained focussed on transition metal catalysis. In addition to this initiation effect, we demonstrate how inert perfluorinated compounds are also able to steer the selectivity at the molecular level, by promoting the conversion of the intermediate cyclohexyl hydroperoxide to the most desired end-product, cyclohexanone. This effect is explained by an enhanced, H-bond-assisted, hydroperoxide propagation. This hitherto overlooked hydroperoxide propagation was recently presented by us as the dominant cyclohexanone and cyclohexanol source. We herein thus confirm our previously reported autoxidation scheme, and illustrate its usefulness as a solid basis for designing new catalytic systems.