Crystallization of progesterone polymorphs using polymer-induced heteronucleation (PIHn) method

Progesterone is a natural hormone steroid used in humans for several treatments and in livestock for artificial insemination, which exhibits two polymorphic forms at ambient conditions: form 1 and form 2. Form 2 is metastable and more soluble than form 1; however, it is not suitable to use as powder raw material because it transforms into form 1 by the effects of grinding. A polymorphic screening of progesterone based on polymer-induced heteronucleation method was performed as an alternative to prepare the metastable form. Polyvinyl alcohol, hydroxypropyl methylcellulose (HPMC), dextran, gelatin, polyisoprene (PI) and acrylonitrile-butadiene (NBR) copolymer were used. Crystals were prepared from 0.5, 10 and 40?mg/mL solutions in acetone at room temperature by solvent evaporation. The samples were characterized by X-ray powder diffraction, differential scanning calorimetry (DSC), scanning electron microcopy and attenuated total reflectance infrared Fourier transform spectroscopy. Form 1 was nucleated from 40?mg/mL solutions on the six polymers and from 10?mg/mL solutions on PI and NBR. The mixture of form 1 and form 2 was obtained from 10?mg/mL solution on HPMC, dextran and gelatin and from 0.5?mg/mL solution crystallizations. Therefore, the polymeric devices, which crystallized the metastable and more soluble polymorph (2) of progesterone, would be a promissory alternative for the pharmaceutical applications.     

A Simple and Effective Mass Spectrometric Approach to Identify the Adulteration of the Mediterranean Diet Component Extra-Virgin Olive Oil with Corn Oil

Extra virgin olive oil (EVOO) with its nutraceutical characteristics substantially contributes as a major nutrient to the health benefit of the Mediterranean diet. Unfortunately, the adulteration of EVOO with less expensive oils (e.g., peanut and corn oils), has become one of the biggest source of agricultural fraud in the European Union, with important health implications for consumers, mainly due to the introduction of seed oil-derived allergens causing, especially in children, severe food allergy phenomena. In this regard, revealing adulterations of EVOO is of fundamental importance for health care and prevention reasons, especially in children. To this aim, effective analytical methods to assess EVOO purity are necessary. Here, we propose a simple, rapid, robust and very sensitive method for non-specialized mass spectrometric laboratory, based on the matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS) coupled to unsupervised hierarchical clustering (UHC), principal component (PCA) and Pearson’s correlation analyses, to reveal corn oil (CO) adulterations in EVOO at very low levels (down to 0.5%).     

Single chamber Solid Oxide Fuel Cells selective electrodes: A real chance with brownmillerite-based nanocomposites

In this contribution brownmillerite-based nanocomposite cathode for Single-Chamber Solid Oxide Fuel Cells is developed. These cells can be very attractive especially for small and cheap devices because of the absence of seals. The efficiency of SC-SOFCs is strictly connected to the selectivity of anode and cathode, the bottleneck for this technology. The development of a cathode inert in fuel oxidation is particularly challenging. Our strategy is to start from a catalytically un-active support (CFA = Ca₂FeAl_0.95Mg_0.05O₅) and induce the formation of iron oxide based nanoparticles, expected to activate oxygen. Symmetric (CFA + FeO_x/CGO/CFA + FeO_x) and complete cells (CFA + FeO_x/CGO/Ni-CGO) are studied in air and methane/oxygen 2:1 mixture. The Area Specific Resistance of CFA + FeO_x is less than 1/3 that of CFA. The high selectivity allows to reach an efficiency of 25%; power still needs to be increased but we demonstrated the possibility to develop selective low cost electrodes. The effect of air, methane/oxygen exposure and the heat treatments were carefully investigated.     

Characterization of colloidal polymer particles through stability ratio measurements

We propose a general methodology for the estimation of the doublet formation rate constant (proportional to the stability ratio of primary particles) in colloidal dispersions from measurements obtained by common optical techniques, such as dynamic light scattering, static light scattering (nephelometry) or turbidimetry. In contrast to previous approaches relying on the initial slopes of the measured quantities, such as the mean hydrodynamic radius, scattered light intensity or turbidity, we introduce a transformation of the measurables to properly scaled quantities, which grow linearly in time with a slope proportional to the doublet formation rate. Analysis of systematic and random errors allows one to control the error in the estimated value of the aggregation rate. Using this approach, we measured the aggregation rate constant of colloidal polymer particles prepared by surfactant-free emulsion copolymerization of styrene and 2-hydroxyethyl methacrylate (HEMA). It was found that the stability ratio at constant ionic strength decreases with increasing dilution of the original polymer latex. This can be explained by the presence of non-reacted stabilizing species (most likely oxidized HEMA) that desorb from the particle surface upon latex dilution and thus diminish the repulsive interactions between particles. In order to check if the stability of latex particles is influenced by reversibly adsorbed species it is always necessary to perform aggregation experiments at various dilutions.     

DILIGENT: integrating digital library and Grid technologies for a new Earth observation research infrastructure

This paper introduces DILIGENT, a digital library infrastructure built by integrating digital library and Grid technologies and resources. This infrastructure allows different communities to dynamically build specialised digital libraries capable to support the entire e-Science knowledge production and consumption life-cycle by using shared computing, storage, content, and application resources. The paper presents some of the main software services that implement the DILIGENT system. Moreover, it exemplifies the provided features by presenting how the DILIGENT infrastructure is being exploited in supporting the activity of user communities working in the Earth Science Environmental sector. This work is partially funded by the European Commission in the context of the DILIGENT project, under the 2nd call of FP6 IST priority.     

Importance of out-of-plane dispersion of the excitation spectrum of superconducting bilayers with Josephson coupling

We study the effect of Josephson coupling between adjacent superconducting layers on the BCS energy spectrum. We find that the interference between the gap functions of two layers can lead to vanishing condensation energy for perpendicular momenta corresponding to the formation of standing waves. We therefore predict a conventional energy spectrum for large interlayer spacings, if the gap of the single layers has no nodes, and in all cases a gapless spectrum for small spacings. Within the experimental error, our numerical results account for the low-temperature dependence of the penetration depth reported in Nd_1.85Ce_0.15CuO₄ and YBa₂Cu₃O_6.9.     

Gyrotron coaxial cylindrical resonators with corrugated innerconductor: Theory and experiment

Gyrotron coaxial resonators with a longitudinally slotted inner cylinder are examined analytically using a surface impedance model, from which expressions for the electromagnetic field, ohmic quality (Q) factor, and characteristic equation of the transverse eigenvalues χ _m,p are obtained. The major attributes of such resonators are expressed by the dependence of χ_m,p on the parameter C-defined as the ratio of the outer to inner radii of the coaxial structure. In that connection, the effect of the corrugation parameters on χ_m,p is particularly investigated on the basis of an expression derived for the slope function dχ_m,p,p/dC. It is shown that the χ_m,p(C) curve may either exhibit oscillatory behavior or present a flat portion over a wide range of C depending on the corrugation parameters chosen. The theory is checked against experiment in which resonant frequencies and total Q factors were measured for TE modes operating in the range of 8-16 GHz in a coaxial cavity with 40 slots. Good agreement is found in that the magnitude of the relative error in frequency is less than 0.5%. Corrugated coaxial resonators prove to be relevant to megawatt gyrotrons where highly selective cavities are required to ensure high conversion efficiency     

The Generic Bilinear Calibration-Estimation Problem

We identify a very general, recurring pattern in a number of well known problems in biological and machine vision. Many problems are of a peculiar double-sided nature: One attempts to estimate certain properties of the environment using a certain type of equipment and simultaneously one attempts to calibrate the same equipment on the structure of the environment. At first sight this appears the kind of the chicken and the egg problem that might well prove to be insoluble. However, due to basic constraints that universally apply (e.g., the world is only three-dimensional), a solution—up to a certain class of ambiguity transformations—often exists. The more complicated the problem is, the less important the remaining ambiguity will be, at least in a relative sense. Many well known problems are special in that they can be cast in bilinear form, sometimes after transformation or the introduction of dummy variables. Instances include photometric stereo, photometric estimations (e.g., of lightness), local (differential) image operators, a variety of photogrammetric problems, etc. It turns out that many of these problems—and together these make up a large fraction of the generic problems in machine vision today—can be cast in a simple universal framework. This framework enables one to handle arbitrarily large (that is, not minimal, consistent configurations), noisy (thus inconsistent) date sets automatically. The level at which prior information (either of a deterministic or a statistical nature) is used (assumptions such as constant albedo, rigidity, uniform distributions, etc.) is clearly separated as an additional, typically nonlinear, stage.