Implementation of PLS discriminant analysis to rank indirubin derivatives against decoys

Partial Least Squares Discriminant Analysis (PLS-DA) is employed to obtain novel combinations of energetic terms present in classical scoring functions, which exceed and compensates the “traditional” consensus scheme. These novel scoring functions were involved to rank the database of indirubin inhibitors of glycogen synthase kinase-3β and cyclin dependent kinase-2 decoys from Directory of Useful Decoys. The ability of docking-scoring algorithm to prioritize the actives is assessed by means of several metrics. The best classification function includes donor component of Chemgauss2, steric contribution from Chemgauss3 and rotatable bond term of ScreenScore and provide significant improvement of enrichment factor at 5% of database.      

The Melting Temperature of 99.97 wt.% Al Estimated from Activation Energy for Viscous Flow

The viscous flow phenomenon in molten aluminium and the viscosity, in the vicinity of its melting temperature, was analyzed. When the temperature decreases, both the viscosity and the activation energy for viscous flow increase. This is explained on the basis of the atomic rearrangement due to interatomic interactions prior to the separation of the solid phase. The latter was found to be nonlinear as the temperature is decreased wherein the solid phase is separated from the liquid. The second derivative of the activation energy for viscous flow with respect to temperature was found to show discontinuity in the vicinity of the melting temperature. Thus, the second derivative offers a way of estimating the melting temperature of metals. Our estimations indicate that the break of the second derivative vs. temperature could be observed at 938 K.     

Application of new methodologies based on design of experiments, independent component analysis and design space for robust optimization in liquid chromatography

HPLC separations of an unknown sample mixture and a pharmaceutical formulation have been optimized using a recently developed chemometric methodology proposed by W. Dewé et al. in 2004 and improved by P. Lebrun et al. in 2008. This methodology is based on experimental designs which are used to model retention times of compounds of interest. Then, the prediction accuracy and the optimal separation robustness, including the uncertainty study, were evaluated. Finally, the design space (ICH Q8(R1) guideline) was computed as the probability for a criterion to lie in a selected range of acceptance. Furthermore, the chromatograms were automatically read. Peak detection and peak matching were carried out with a previously developed methodology using independent component analysis published by B. Debrus et al. in 2009. The present successful applications strengthen the high potential of these methodologies for the automated development of chromatographic methods.     

Designing thermotropic liquid crystalline polyazomethines based on fluorene and/or oxadiazole chromophores

The main objective of this paper was to synthesize luminescent thermotropic liquid crystalline polyazomethines containing chromophoric mesogen, which design has been addressed to optoelectronic materials. The investigation of the thermotropic behavior by three complementary methods of analyses, i.e. polarized optical microscopy, differential scanning calorimetry and wide angle X-ray diffraction, indicated a nematic mesophase for the polymers containing oxadiazole units, either alternating or random ones. A mesomorphic state maintaining the degree of order of the semicrystalline state while being viscous fluid was evidenced too. The photoluminescence spectra recorded for both polymer solutions and films exhibited a blue light emission. These results point to the possibility of obtaining monodomain or multidomain ordered thin films without grain boundaries showing good mechanical and luminescent properties.     

A method to convexify functions via curve evolution

This paper is devoted to a new method which allows to compute the convex envelope of a given function, by an evolution equation and techniques of curve evolution. We study the problem in the context of viscosity solutions and we propose numerical algorithms, to convexify a function, in one and two dimensions. In the end, we validate the model by presenting various numerical results. Key words: convex envelope, curve evolution, viscosity solutions, nonlinear second order elliptic and parabolic PDE's, finite differences scheme.     

Thermal behaviour of the TiO<Subscript>2</Subscript>-based gels obtained by microwave-assisted sol–gel method

This work aims to elucidate whether the hypothesis of zero oxygen at the mixture layer when flame takes place is assumable for every kind of material. For that purpose, we investigated the oxygen concentration there by cone calorimeter tests. A modified holder was developed in order to collect oxygen in this mixture layer. In addition, thermogravimetric tests were carried out so as to relate the possible effects of the presence of oxygen in the atmosphere where the pyrolysis process takes place, since the cone calorimeter does not allow to control the oxygen level of the atmosphere during the experiment. The reaction rates and per cent of residue in the cone calorimetric tests were measured and compared with the results from thermogravimetric tests. Six products were analysed which can be classified in three main groups: lignocellulosic, thermoplastic polymers and thermoset polymers. Cone calorimetric results showed that for some of the materials analysed (PET, Nylon and PUR foam) the oxygen level at mixture layer decreased until values close to zero. The comparison of reaction rates between cone calorimetric and thermogravimetric tests revealed the char layer created in cone calorimetric tests over the exposed face for brushed fir, Nylon and PET established an important heat barrier that modifies the thermal behaviour of these materials.     

N,N′ and N,O chelated phosphenium cations containing aminotroponiminate or aminotroponate units

New phosphenium cations stabilized by bidentate monoanionic N-isopropyl-2-(isopropylamino)troponiminate or 2-(isopropylamino)troponate units have been synthesized. These complexes were characterized by ³¹P, ¹H and ¹³C NMR spectroscopies, and the molecular structures were determined by X-ray crystallography. These data indicate the formation of N,N′- and N,O-chelate derivatives having three-coordinate phosphorous atoms included in planar heterobicycles. Moreover, computational studies support the presence of high delocalization of the positive charge into the π-conjugated carbon backbone and of the high-lying phosphorus lone-pair orbital.     

The acidity of tert-butyl alcohol in near- and supercritical water: a polarizable continuum approach

We use a polarizable continuum approach to study the acidity of tert-butyl alcohol in water at ambient, near-critical, and supercritical conditions. In the most straightforward calculation, the bare ionic species (the tert-butoxy anion and the hydronium cation) are placed in cavities surrounded by a dielectric continuum, using a dielectric constant corresponding to the state point. A second method is first to solvate these ions with a small number of explicit water molecules and then surround this cluster with the dielectric. This is the cluster-continuum approach. We discuss the advantages and disadvantages of these two schemes and we also discuss various ways in which the second method can be implemented. No method showed quantitative agreement with all available experimental results but the first, straightforward method was the most successful in predicting the correct trends. From both a numerical and a theoretical point of view, we believe this is the method of choice.