An invariance property of quadratic forms in random vectors with a selection distribution,with application to sample variogram and covariogram estimators

We study conditions under which an invariance property holds for the class of selection distributions. First, we consider selection distributions arising from two uncorrelated random vectors. In that setting, the invariance holds for the so-called C{\cal{C}} -class and for elliptical distributions. Second, we describe the invariance property for selection distributions arising from two correlated random vectors. The particular case of the distribution of quadratic forms and its invariance, under various selection distributions, is investigated in more details. We describe the application of our invariance results to sample variogram and covariogram estimators used in spatial statistics and provide a small simulation study for illustration. We end with a discussion about other applications, for example such as linear models and indices of temporal/spatial dependence.     

Amino Acid derived enamides: synthesis and aminopeptidase activity

Recently developed copper-catalyzed coupling methodology has been applied to the synthesis of amino acid derived enamides. Bond formation proved to be strongly influenced by protection strategy and vinyl iodide substitution while tolerant of limited side chain functionality. Assessment of aminopeptidase activity revealed a preference for (E)-1,2-disubstituted constructs.     

Comparison of Derivatization Methods for the Determination of Butyl- and Phenyl-tin Compounds in Mussels by Gas Chromatography

Two different derivatization methods, alkylation with Grignard reagents, and ethylation with sodium tetraethylborate, were compared for the determination of organotin compounds, viz. tributyltin, dibutyltin, monobutyltin, triphenyltin, diphenyltin and monophenyltin, in mussel samples. Temperature, reaction time and concentration of Grignard reagents were optimized in the former method; in the latter the effect of pH, concentration of sodium tetraethylborate and reaction time were studied. In the derivatization with Grignard reagents hexyl, pentyl, propyl, ethyl and methyl were used as alkyl Grignard groups. A critical evaluation of the different derivatization methods is presented. © 1997 John Wiley & Sons, Ltd.     

Shotgun lipidomics on a LTQ Orbitrap mass spectrometer by successive switching between acquisition polarity modes

Top-down shotgun lipidomics relies on direct infusion of total lipid extracts into a high-resolution tandem mass spectrometer and implies that individual lipids are recognized by their accurately determined m/z. Lipid ionization efficiency and detection specificity strongly depend on the acquisition polarity, and therefore it is beneficial to analyze lipid mixtures in both positive and negative modes. Hybrid LTQ Orbitrap mass spectrometers are widely applied in top-down lipidomics; however, rapid polarity switching was previously unfeasible because of the severe and immediate degradation of mass accuracy. Here, we report on a method to rapidly acquire high-resolution spectra in both polarity modes with sub-ppm mass accuracy and demonstrate that it not only simplifies and accelerates shotgun lipidomics analyses but also improves the lipidome coverage because more lipid classes and more individual species within each class are recognized. In this way, shotgun analysis of total lipid extracts of human blood plasma enabled to quantify 222 species from 15 major lipid classes within 7?min acquisition cycle.     

Best one-sided L1 approximation to the Heaviside and sign functions

We find the polynomials of the best one-sided approximation to the Heaviside and sign functions. The polynomials are obtained by Hermite interpolation at the zeros of some Jacobi polynomials. Also we give an estimate of the error of approximation and characterize the extremal points of the convex set of the best approximants.     

Influence of Organophilic Ammonium-Free Nanoclay Incorporation on Mechanical Properties and Biodegradability of Biodegradable Polyester

Summary: Disposal of petroleum-derived polymers is a growing global environmental problem of alarming proportions, which has increased interest in the use and production of biodegradable materials. In addition to biodegradation, investment in research and development in the nanotechnology area is also significant. This study evaluated the effect of incorporation of an organophilic nanoclay ammonium-free salt (Novaclay™) on the mechanical properties and biodegradation of a biodegradable polyester (Ecoflex®), according to ASTM G 160. Ecoflex with and without incorporated Novaclay was characterized before and after biodegradation in organically enriched soil for up to 180 days, by visual analysis, optical microscopy, weight loss, differential scanning calorimetry, dynamic mechanical analysis, mechanical testing, and scanning electron microscopy. The pure Ecoflex and the Ecoflex/Novaclay nanocomposite were partially biodegraded by the method used, and showed changes in their morphological and mechanical properties.     

Initiation Efficiency Reduction in Semicontinuous Styrene and Butyl Acrylate Emulsion Copolymerization Reactions

The decrease of initiation efficiency (radical entry efficiency) during seeded emulsion copolymerizations of styrene and butyl acrylate with different residual monomer reduction strategies was evaluated. Experiments were carried out using 50 and 99wt.% of styrene in monomer feed stream. Simulations were performed with a detailed mathematical model of the process that takes into account the diffusion control of initiation, propagation and termination. Results showed that the radical entry into polymer particles is strongly influenced by the aqueous phase kinetics and by the monomer solubility in aqueous phase. Simulation results were compared to experimental results of residual monomer and showed that the residual monomer content can be reduced by a temperature increase at the end of the polymerization. However, an additional feeding of more initiator, even when combined with such an increase of temperature, did not lead to a smaller residual monomer content due, mainly, the kinetic of termination in aqueous phase and radical anchoring. A model that accounts for the reduction of initiator efficiency (free radical entry efficiency) was successfully used to explain the behavior of the experimental observations and was able to correctly predict the qualitative trends of the effectiveness of different residual monomer reduction strategies.