Epoxidation of soybean oil by the methyltrioxorhenium-CH2Cl2/H2O2 catalytic biphasic system

We studied the methyltrioxorhenium (MTO)-CH₂Cl₂/H₂O₂ biphasic system for epoxidizing soybean oil. The reactions were optimized (reactant ratio, time, and temperature), which resulted in a better performance (higher conversion and selectivity) than those described in the literature. Total doublebond conversion and 95% selectivity were obtained in 2 h at room temperature. Furthermore, it was possible to reach desired epoxidation degrees by changing the oxidant and MTO amounts. The rhenium-epoxidized soybean oil remained stable in the absence of stabilizers for up to 30 d when stored at mild conditions.     

Modelling the effects of past and future climate on the risk of bluetongue emergence in Europe

Vector-borne diseases are among those most sensitive to climate because the ecology of vectors and the development rate of pathogens within them are highly dependent on environmental conditions. Bluetongue (BT), a recently emerged arboviral disease of ruminants in Europe, is often cited as an illustration of climate''s impact on disease emergence, although no study has yet tested this association. Here, we develop a framework to quantitatively evaluate the effects of climate on BT''s emergence in Europe by integrating high-resolution climate observations and model simulations within a mechanistic model of BT transmission risk. We demonstrate that a climate-driven model explains, in both space and time, many aspects of BT''s recent emergence and spread, including the 2006 BT outbreak in northwest Europe which occurred in the year of highest projected risk since at least 1960. Furthermore, the model provides mechanistic insight into BT''s emergence, suggesting that the drivers of emergence across Europe differ between the South and the North. Driven by simulated future climate from an ensemble of 11 regional climate models, the model projects increase in the future risk of BT emergence across most of Europe with uncertainty in rate but not in trend. The framework described here is adaptable and applicable to other diseases, where the link between climate and disease transmission risk can be quantified, permitting the evaluation of scale and uncertainty in climate change''s impact on the future of such diseases.     

Determination of the Hydroxyl Value of Soybean Polyol by Attenuated Total Reflectance/Fourier Transform Infrared Spectroscopy

A rapid method for the quantitative determination of the hydroxyl value (OHV) of hydroxylated soybean oils by HATR/FTIR spectroscopy is described. Calibration standards were prepared by the formic acid/hydrogen peroxide method and OH values were determined by the official method of AOCS Tx 1a-66, covering an analytical range of 3.5–125 mg of KOH/g of sample. A partial least squares (PLS) calibration model for the prediction of the hydroxyl value (OHV) was developed based on eight different spectral subregions between 3,150 and 990 cm⁻¹ and combinations of them. On average, 36 samples were used for the modeling and 17 were used for external validation. The resulting calibration was linear over the analytical range and had a standard deviation of 2.334. Validation of the method was carried out by comparing the OHV of a series of hydroxylated soybean oils predicted by the PLS model to the values obtained by the AOCS standard method. A correlation coefficient of R ² = 0.9843 and RMSEC and RMSEP values of, respectively, 3.393 and 3.643 were obtained. After the calibration of the spectrometer, the OHV could be obtained in 2–3 min per sample, a major improvement over conventional wet chemical methods. The advantages of these methodologies are that they do not destroy the sample, have a lower cost, expedite the analysis and do not produce residues. Therefore, they may yield excellent results when used to quantify OHV of soybean polyols obtained by hydroxylation reaction.     

Multiwavelength imaging of defects in ultraviolet optical materials

Laser-induced damage in bare glass substrates and thin films has long been widely acknowledged as a localized phenomenon associated with the presence of micrometer and submicrometer scale defects. The scanning of both optical absorption and scattering allows us to discriminate between absorbing and nonabsorbing defects and can give specific information about the origin of the defects. We investigate the spectral properties of defects in thin films and fused-silica surfaces. Absorbing and scattering defects are studied at different wavelengths in the ultraviolet, visible, and infrared ranges. Absorbing defects are shown to be highly wavelength dependent, whereas we have observed significant correlation between scattering defects.     

Organic–Inorganic Hybrid Films Based on Hydroxylated Soybean Oils

Hybrid organic–inorganic films were prepared using four different hydroxylated soybean oils (HSO) or epoxidized soybean oil as organic precursor and tetraethyl orthosilicate (TEOS) as inorganic precursor in a mass ratio of HSO:TEOS of 90:10. The films were macroscopically homogeneous and were characterized by swelling and extraction in solvent, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) including energy dispersive spectroscopy (EDX), adhesion and hardness. Their properties varied as a function of the number of OH groups present in the HSO. The best hybrid system was HSOF198/TEOS, with an OH value of 198 mg of KOH/g, which presents lower swelling coefficient, very good adhesion on aluminium surface and good hardness.     

Data Driven Order Selection for Projection Estimator of the Spectral Density of Time Series with Long Range Dependence

Fractional exponential (FEXP) models have been introduced by Robinson (1991) and Beran (1993) to model the spectral density of a covariance stationary long-range dependent process. In this class of models, the spectral density f ( x ) of the process is decomposed as f ( x ) = |1 − exp( ix )|^{−2 d} f _*( x ), where f _*( x ) accounts for the short-memory component. In this contribution, FEXP models are used to construct semi-parametric estimates of the fractional differencing coefficient and of the spectral density, by considering an infinite Fourier series expansion of log f _*( x ). A data-driven order selection procedure, adapted from the Mallows' C _p procedure, is proposed to determine the order of truncation. The optimality of the data-driven procedure is established, under mild assumptions on the short-memory component f _*( x ). A limited Monte-Carlo experiment is presented to support our claims.     

Synthetic and Biological Studies of Sesquiterpene Polygodial: Activity of 9‐Epipolygodial against Drug‐Resistant Cancer Cells

Polygodial, a terpenoid dialdehyde isolated from Polygonum hydropiper L., is a known agonist of the transient receptor potential vanilloid 1 (TRPV1). In this investigation a series of polygodial analogues were prepared and investigated for TRPV1‐agonist and anticancer activities. These experiments led to the identification of 9‐epipolygodial, which has antiproliferative potency significantly exceeding that of polygodial. 9‐Epipolygodial was found to maintain potency against apoptosis‐resistant cancer cells as well as those displaying the multidrug‐resistant (MDR) phenotype. In addition, the chemical feasibility for the previously proposed mechanism of action of polygodial, involving the formation of a Paal–Knorr pyrrole with a lysine residue on the target protein, was demonstrated by the synthesis of a stable polygodial pyrrole derivative. These studies reveal rich chemical and biological properties associated with polygodial and its direct derivatives. These compounds should inspire further work in this area aimed at the development of new pharmacological agents, or the exploration of novel mechanisms of covalent modification of biological molecules with natural products.     

Toward the first nonpeptidic molecular tong inhibitor of wild-type and mutated HIV-1 protease dimerization

Herein we describe the synthesis and HIV-1 protease (PR) inhibitory activity of 16 new peptidomimetic molecular tongs with a naphthalene scaffold. Their peptidic character was progressively decreased. Two of these molecules exhibited the best dimerization inhibition activity toward HIV-1 wild-type and multimutated ANAM-11 proteases obtained to date for this class of molecules (～40?nM for wild-type PR and 100?nM for ANAM-11 PR). Although the peptidic character of one molecular tong was completely suppressed, the mechanism of inhibition and inhibitory potency toward both proteases were maintained.