For the characterization of the new materials and for a better understanding of the connection between structure and properties it is necessary to use more and more sensible methods to study molecular movement at nanometric scale. This paper presents the experimental basis for a new electrical method to study the fine molecular movements at nanometric scale in dielectric materials. The method will be applied for polar and non-polar materials characterization. Traditionally, the electrical methods used to study the molecular movements are based on the movements of the dipoles that are parts of the molecules. We have proposed recently a combined protocol to analyze charge injection/extraction, transport, trapping and detrapping in low mobility materials. The experimental results demonstrate that the method can be used to obtain a complex thermogram which contains information about all molecular movements, even at nanoscopic level. Actually during the charging process we are decorating the structure with space charge and during the subsequent heating we are observing an apparent peak and the genuine peaks that are related to charge de-trapping determined by the molecular movement. The method is very sensitive, very selective and allows to determinate the parameters for local and collective molecular movements, including the temperature dependence of the activation energy and the relaxation time.

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The isothermal charging current and the isothermal discharging current in low mobility materials are analyzed either in terms of polarization mechanisms or in terms of charge injection/extraction at the metal-dielectric interface and the conduction current through the dielectric material. We propose to measure the open-circuit isothermal charging and discharging currents just to overpass the difficulties related to the analysis of the conduction mechanisms in dielectric materials. We demonstrate that besides a polarization current there is a current related to charge injection or extraction at the metal-dielectric interface and a reverse current related to the charge trapped into the shallow superficial or near superficial states of the dielectric and which can move at the interface in the opposite way that occurring during injection. Two important parameters can be determined (i) the highest value of the relaxation time for the polarization mechanisms which are involved into the transient current and (ii) the height of the potential barrier W-0 at the metal-dielectric interface. The experimental data demonstrate that there is no threshold field for electron injection/extraction at a metal-dielectric interface.

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The inductive fault current limiter is less compact and harder to scale to high voltage networks than the resistive one. Nevertheless, its simple construction and mechanical robustness make it attractive in low voltage grids. Thus, it might be an enabling technology for the advent of microgrids, low voltage networks with dispersed generation, controllable loads and energy storage. A new methodology for reverse engineering of inductive fault current limiters based on the independent analysis of iron cores and HTS cylinders is presented in this paper. Their electromagnetic characteristics are used to predict the devices' hysteresis loops and consequently their dynamic behavior. Previous models based on the separate analysis of the limiters' components were already derived, e.g. in transformer like equivalent models. Nevertheless, the assumptions usually made may limit these models' application, as shown in the paper. The proposed methodology obviates these limitations. Results are validated through simulations.

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The effect of kefir grains on the proteolysis of major milk proteins in milk kefir and in a culture of kefir grains in pasteurized cheese whey was followed by reverse phase-HPLC analysis. The reduction of kappa-, alpha-, and beta-caseins (CN), alpha-lactalbumin (alpha-LA), and beta-lactoglobulin (beta-LG) contents during 48 and 90 h of incubation of pasteurized milk (100 mL) and respective cheese whey with kefir grains (6 and 12 g) at 20 degrees C was monitored. Significant proteolysis of alpha-LA and kappa-, alpha-, and beta-caseins was observed. The effect of kefir amount (6 and 12 g/100 mL) was significant for alpha-LA and alpha- and beta-CN. alpha-Lactalbumin and beta-CN were more easily hydrolyzed than alpha-CN. No significant reduction was observed with respect to beta-LG concentration for 6 and 12 g of kefir in 100 mL of milk over 48 h, indicating that no significant proteolysis was carried out. Similar results were observed when the experiment was conducted over 90 h. Regarding the cheese whey kefir samples, similar behavior was observed for the proteolysis of alpha-LA and beta-LG: alpha-LA was hydrolyzed between 60 and 90% after 12 h (for 6 and 12 g of kefir) and no significant beta-LG proteolysis occurred. The proteolytic activity of lactic acid bacteria and yeasts in kefir community was evaluated. Kefir milk prepared under normal conditions contained peptides from proteolysis of alpha-LA and kappa-, alpha-, and beta-caseins. Hydrolysis is dependent on the kefir: milk ratio and incubation time. beta-Lactoglobulin is not hydrolyzed even when higher hydrolysis time is used. Kefir grains are not appropriate as adjunct cultures to increase beta-LG digestibility in whey-based or whey-containing foods.

Benzyl azide and the three methylbenzyl azides were synthesized and characterized by mass spectrometry (MS) and ultraviolet photoelectron spectroscopy (UVPES). The electron ionization fragmentation mechanisms for benzyl azide and their methyl derivatives were studied by accurate mass measurements and linked scans at constant B/E. For benzyl azide, in order to clarify the fragmentation mechanism, labelling experiments were performed. From the mass analysis of methylbenzyl azides isomers it was possible to differentiate the isomers ortho, meta and para. The abundance and nature of the ions resulting from the molecular ion fragmentation, for the three distinct isomers of substituted benzyl azides, were rationalized in terms of the electronic properties of the substituent. Concerning the para-isomer, IRC calculations were performed at UHF/6-31G(d) level. The photoionization study of benzyl azide, with He(I) radiation, revealed five bands in the 8-21 eV ionization energies region. From every photoelectron spectrum of methylbenzyl azides isomers it has been identified seven bands, on the same range as the benzyl azide. Interpretation of the photoelectron spectra was accomplished applying Koopmans' theorem to the SCF orbital energies obtained at HF/6-311++G(d, p) level.

Benzyl azide and the three methylbenzyl azides were synthesized and characterized by mass spectrometry (MS) and ultraviolet photoelectron spectroscopy (UVPES). The electron ionization fragmentation mechanisms for benzyl azide and their methyl derivatives were studied by accurate mass measurements and linked scans at constant B/E. For benzyl azide, in order to clarify the fragmentation mechanism, labelling experiments were performed. From the mass analysis of methylbenzyl azides isomers it was possible to differentiate the isomers ortho, meta and para. The abundance and nature of the ions resulting from the molecular ion fragmentation, for the three distinct isomers of substituted benzyl azides, were rationalized in terms of the electronic properties of the substituent. Concerning the para-isomer, IRC calculations were performed at UHF/6-31G(d) level. The photoionization study of benzyl azide, with He(I) radiation, revealed five bands in the 8-21 eV ionization energies region. From every photoelectron spectrum of methylbenzyl azides isomers it has been identified seven bands, on the same range as the benzyl azide. Interpretation of the photoelectron spectra was accomplished applying Koopmans' theorem to the SCF orbital energies obtained at HF/6-311++G(d, p) level.

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Starch-based polymers have been proposed for different tissue engineering applications due to their inherent properties. In this work, a polymeric blend of starch-poly-(?-caprolactone) (SPCL) was processed using supercritical fluid technology, namely, by supercritical assisted phase inversion. As SPCL is a biodegradable polymer, the matrices produced are susceptible of undergoing enzymatic degradation upon implantation in the human body. In vitro assessment of the enzymatic degradation of SPCL was carried out in different buffer solutions containing a-amylase and/or lipase. The effect of the presence ofthese enzymes was studied by monitoring different parameters in order to characterise both bulk and the surface of the scaffolds. As regards to bulk analysis, weight loss of the samples incubated for 1, 3, 7, 14 and 21 days was determined, further differential scanning calorimetry was carried out. The morphology of the scaffolds after these periods was analysed by micro-computed tomography (?-CT) and surface chemistry was characterised by infra-red spectroscopy and contact angle measurements. Results suggest that SPLC scaffolds undergo bulk degradation, which is typically characterised by hydrolysis of chemical bonds in the polymer chain at the centre of the matrix, resulting in a highly porous material. ? 2010 Elsevier Ltd. All rights reserved.

In the tissue engineering (TE) field, the concept of producing multifunctional scaffolds, capable not only of acting as templates for cell transplantation but also of delivering bioactive agents in a controlled manner, is an emerging strategy aimed to enhance tissue regeneration. In this work, a complex hybrid release system consisting in a three-dimensional (3D) structure based on poly(d,l-lactic acid) (PDLLA) impregnated with chitosan/chondroitin sulfate nanoparticles (NPs) was developed. The scaffolds were prepared by supercritical fluid foaming at 200 bar and 35 °C, and were then characterized by scanning electron microscopy (SEM) and micro-CT. SEM also allowed to assess the distribution of the NPs within the structure, showing that the particles could be found in different areas of the scaffold, indicating a homogeneous distribution within the 3D structure. Water uptake and weight loss measurements were also carried out and the results obtained demonstrated that weight loss was not significantly enhanced although the entrapment of the NPs in the 3D structure clearly enhances the swelling of the structure. Moreover, the hybrid porous biomaterial displayed adequate mechanical properties for cell adhesion and support. The possibility of using this scaffold as a multifunctional material was further evaluated by the incorporation of a model protein, bovine serum albumin (BSA), either directly into the PDLLA foam or in the NPs that were eventually included in the scaffold. The obtained results show that it is possible to achieve different release kinetics, suggesting that this system is a promising candidate for dual protein delivery system for TE applications. © 2010 Elsevier B.V.

This work addresses the preparation of 3D porous scaffolds of blends of chitosan and poly(l-lactic acid), CHT and PLLA, using supercritical fluid technology. Supercritical assisted phase-inversion was used to prepare scaffolds for tissue engineering purposes. The physicochemical and biological properties of chitosan make it an excellent material for the preparation of drug delivery systems and for the development of new biomedical applications in many fields from skin to bone or cartilage regeneration. On the other hand, PLLA is a synthetic biodegradable polymer widely used for biomedical applications. Supercritical assisted phase-inversion experiments were carried out in samples with different polymer ratios and different polymer solution concentrations. The effect of CHT:PLLA ratio and polymer concentration and on the morphology and topography of the scaffolds was assessed by SEM and Micro-CT. Infra-red spectroscopic imaging analysis of the scaffolds allowed a better understanding on the distribution of the two polymers within the matrix. This work demonstrates that supercritical fluid technology constitutes a new processing technology, clean and environmentally friendly for the preparation of scaffolds for tissue engineering using these materials. © 2010 Elsevier B.V.