Micropartículas de poli (ácido lático-co-ácido glicólico) obtidas por spray drying para a liberação prolongada de metotrexato

Methotrexate (MTX) is a drug used in the chemotherapy of some kind of cancers, autoimmune diseases and non inflammatory resistant to corticosteroids uveits. However, the rapid plasmatic elimination limits its therapeutic success, which leads to administration of high doses to maintain the therapeutic levels in the target tissues, occurring potential side effects. The aim of this study was to obtain spray dried biodegradable poly-lactic acid co-glycolic acid (PLGA) microparticles containing MTX. Thus, suitable amounts of MTX and PLGA were dissolved in appropriate solvent system to obtain solutions at different ratios drug/polymer (10, 20, 30 and 50% m/m). The physicochemical characterizing included the quantitative analysis of the drug using a validate UV-VIS spectrophotometry method, scanning electron microscopy (SEM), infrared spectrophotometry (IR), thermal analyses and X-ray diffraction analysis. The in vitro release studies were carried out in a thermostatized phosphate buffer pH 7.4 (0.05 M KH2PO4) medium at 37°C ± 0.2 °C. The in vitro release date was subjected to different kinetics release models. The MTX-loaded PLGA microparticles showed a spherical shape with smooth surface and high level of entrapped drug. The encapsulation efficiency was greater then 80%. IR spectroscopy showed that there was no chemical bond between the compounds, suggesting just the possible occurrence of hydrogen bound interactions. The thermal analyses and X-ray diffraction analysis shown that MTX is homogeneously dispersed inside polymeric matrix, with a prevalent amorphous state or in a stable molecular dispersion. The in vitro release studies confirmed the sustained release for distinct MTX-loaded PLGA microparticles. The involved drug release mechanism was non Fickian diffusion, which was confirmed by Kornmeyer-Peppas kinetic model. The experimental results demonstrated that the MTX-loaded PLGA microparticles were successfully obtained by spray drying and its potential as prolonged drug release system.

Oxidação úmida de fenóis com catalisadores de ferro suportado em argilominerais em reator de leito de lama (slurry)

The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.

Excitações em cristais fotônicos unidimensionais

In this work, we present a theoretical study of the propagation of electromagnetic waves in multilayer structures called Photonic Crystals. For this purpose, we investigate the phonon-polariton band gaps in periodic and quasi-periodic (Fibonacci-type) multilayers made up of both positive and negative refractive index materials in the terahertz (THz) region. The behavior of the polaritonic band gaps as a function of the multilayer period is investigated systematically. We use a theoretical model based on the formalism of transfer matrix in order to simplify the algebra involved in obtaining the dispersion relation of phonon-polaritons (bulk and surface modes). We also present a quantitative analysis of the results, pointing out the distribution of the allowed polaritonic bandwidths for high Fibonacci generations, which gives good insight about their localization and power laws. We calculate the emittance spectrum of the electromagnetic radiation, in THZ frequency, normally and obliquely incident (s and p polarized modes) on a one-dimensional multilayer structure composed of positive and negative refractive index materials organized periodically and quasi-periodically. We model the negative refractive index material by a effective medium whose electric permittivity is characterized by a phonon-polariton frequency dependent dielectric function, while for the magnetic permeability we have a Drude like frequency-dependent function. Similarity to the one-dimensional photonic crystal, this layered effective medium, called polaritonic Crystals, allow us the control of the electromagnetic propagation, generating regions named polaritonic bandgap. The emittance spectra are determined by means of a well known theoretical model based on Kirchoff s second law, together with a transfer matrix formalism. Our results shows that the omnidirectional band gaps will appear in the THz regime, in a well defined interval, that are independent of polarization in periodic case as well as in quasiperiodic case

Polaritons de exciton em super-redes semicondutoras

In this work we study the spectrum (bulk and surface modes) of exciton-polaritons in infinite and semi-infinite binary superlattices (such as, ···ABABA···), where the semiconductor medium (A), whose dielectric function depends on the frequency and the wavevector, alternating with a standard dielectric medium B. Here the medium A will be modeled by a nitride III-V semiconductor whose main characteristic is a wide-direct energy gap Eg. In particular, we consider the numerical values of gallium nitride (GaN) with a crystal structure wurtzite type. The transfer-matrix formalism is used to find the exciton-polariton dispersion relation. The results are obtained for both s (TE mode: transverse electric) and p (TM mode: transverse magnetic) polarizations, using three diferent kind of additional boundary conditions (ABC1, 2 e 3) besides the standard Maxwell's boundary conditions. Moreover, we investigate the behavior of the exciton-polariton modes for diferent ratios of the thickness of the two alternating materials forming the superlattice. The spectrums shows a confinement of the exciton-polariton modes due to the geometry of the superlattice. The method of Attenuated Total Reflection (ATR) and Raman scattering are the most adequate for probing this excitations

Polaritons em materiais magnéticos nanoestruturados

In this work we present a theoretical study about the properties of magnetic polaritons in superlattices arranged in a periodic and quasiperiodic fashíons. In the periodic superlattice, in order to describe the behavior of the bulk and surface modes an effective medium approach, was used that simplify enormously the algebra involved. The quasi-periodic superlattice was described by a suitable theoretical model based on a transfer-matrix treatment, to derive the polariton's dispersion relation, using Maxwell's equations (including effect of retardation). Here, we find a fractal spectra characterized by a power law for the distribution of the energy bandwidths. The localization and scaling behavior of the quasiperiodic structure were studied for a geometry where the wave vector and the external applied magnetic field are in the same plane (Voigt geometry). Numerical results are presented for the ferromagnet Fe and for the metamagnets FeBr2 and FeCl2

Interações entre a carboximetilcelulose, carbonato de cálcio e bentonita: repercussões sobre as propriedades dos fluidos de perfuração aquosos

The role of carboxymethylcellulose (CMC) in association to calcium carbonate particles (CaCO3) in most water-based drilling fluids is to reduce the fluid loss to the surrounding formation. Another essential function is to provide rheological properties capable of maintaining in suspension the cuttings during drilling operation. Therefore, it is absolutely essential to correlate the polymer chemical structure (degree of substitution, molecular weight and distribution of substituent) with the physical-chemical properties of CaCO3, in order to obtain the better result at lower cost. Another important aspect refers to the clay hydration inhibitive properties of carboxymethylcellulose (CMC) in drilling fluids systems. The clay swelling promotes an undesirable damage that reduces the formation permeability and causes serious problems during the drilling operation. In this context, this thesis consists of two main parts. The first part refers to understanding of interactions CMC-CaCO3, as well as the corresponding effects on the fluid properties. The second part is related to understanding of mechanisms by which CMC adsorption occurs onto the clay surface, where, certainly, polymer chemical structure, ionic strength, molecular weight and its solvency in the medium are responsible to affect intrinsically the clay layers stabilization. Three samples of carboximetilcellulose with different molecular weight and degree of substitution (CMC A (9 x 104 gmol DS 0.7), CMC B (2.5 x 105 gmol DS 0.7) e CMC C (2.5 x 105 gmol DS 1.2)) and three samples of calcite with different average particle diameter and particle size distribution were used. The increase of CMC degree of substitution contributed to increase of polymer charge density and therefore, reduced its stability in brine, promoting the aggregation with the increase of filtrate volume. On the other hand, the increase of molecular weight promoted an increase of rheological properties with reduction of filtrate volume. Both effects are directly associated to hydrodynamic volume of polymer molecule in the medium. The granulometry of CaCO3 particles influenced not only the rheological properties, due to adsorption of polymers, but also the filtration properties. It was observed that the lower filtrate volume was obtained by using a CaCO3 sample of a low average size particle with wide dispersion in size. With regards to inhibition of clay swelling, the CMC performance was compared to other products often used (sodium chloride (NaCl), potassium chloride (KCl) and quaternary amine-based commercial inhibitor). The low molecular weight CMC (9 x 104 g/mol) showed slightly lower swelling degree compared to the high molecular weight (2.5 x 105 g/mol) along to 180 minutes. In parallel, it can be visualized by Scanning Electron Microscopy (SEM) that the high molecular weight CMC (2.5 x 105 g/mol e DS 0.7) promoted a reduction in pores formation and size of clay compared to low molecular weight CMC (9.0 x 104 g/mol e DS 0.7), after 1000 minutes in aqueous medium. This behavior was attributed to dynamic of interactions between clay and the hydrodynamic volume of CMC along the time, which is result of strong contribution of electrostatic interactions and hydrogen bounds between carboxylate groups and hydroxyls located along the polymer backbone and ionic and polar groups of clay surface. CMC adsorbs on clay surface promoting the skin formation , which is responsible to minimize the migration of water to porous medium. With the increase of degree of substitution, it was observed an increase of pores onto clay, suggesting that the higher charge density on polymer is responsible to decrease its flexibility and adsorption onto clay surface. The joint evaluation of these results indicate that high molecular weight is responsible to better results on control of rheological, filtration and clay swelling properties, however, the contrary effect is observed with the increase of degree of substitution. On its turn, the calcite presents better results of rheological and filtration properties with the decrease of average viii particle diameter and increase of particle size distribution. According to all properties evaluated, it has been obvious the interaction of CMC with the minerals (CaCO3 and clay) in the aqueous medium

Condutividade térmica de rochas: uma aplicação para granitos ornamentais

This dissertation focuses on rock thermal conductivity and its correlations with petrographic, textural, and geochemical aspects, especially in granite rocks. It aims at demonstrating the relations of these variables in an attempt to enlighten the behavior of thermal effect on rocks. Results can be useful for several applications, such as understanding and conferring regional thermal flow results, predicting the behavior of thermal effect on rocks based upon macroscopic evaluation (texture and mineralogy), in the building construction field in order to provide more precise information on data refinement on thermal properties emphasizing a rocky material thermal conductivity, and especially in the dimension stone industry in order to open a discussion on the use of these variables as a new technological parameter directly related to thermal comfort. Thermal conductivity data were obtained by using Anter Corporation s QuicklineTM -30 a thermal property measuring equipment. Measurements were conducted at temperatures ranging between 25 to 38 OC in samples with 2cm in length and an area of at least 6cm of diameter. As to petrography data, results demonstrated good correlations with quartz and mafics. Linear correlation between mineralogy and thermal conductivity revealed a positive relation of a quartz percentage increase in relation to a thermal conductivity increase and its decrease with mafic minerals increase. As to feldspates (K-feldspate and plagioclase) they show dispersion. Quartz relation gets more evident when compared to sample sets with >20% and <20%. Sets with more than 20% quartz (sienogranites, monzogranites, granodiorites, etc.), exhibit to a great extent conductivity values which vary from 2,5 W/mK and the set with less than 20% (sienites, monzonites, gabbros, diorites, etc.) have an average thermal conductivity below 2,5 W/mK. As to textures it has been verified that rocks considered thick/porphyry demonstrated in general better correlations when compared to rocks considered thin/medium. In the case of quartz, thick rocks/porphyry showed greater correlation factors when compared to the thin/medium ones. As to feldspates (K-feldspate and plagioclase) again there was dispersion. As to mafics, both thick/porphyry and thin/medium showed negative correlations with correlation factor smaller than those obtained in relation to the quartz. As to rocks related to the Streckeisen s QAP diagram (1976), they tend to fall from alcali-feldspates granites to tonalites, and from sienites to gabbros, diorites, etc. Thermal conductivity data correlation with geochemistry confirmed to a great extent mineralogy results. It has been seen that correlation is linear if there is any. Such behavior could be seen especially with the SiO2. In this case similar correlation can be observed with the quartz, that is, thermal conductivity increases as SiO2 is incremented. Another aspect observed is that basic to intermediate rocks presented values always below 2,5 W/mK, a similar behavior to that observed in rocks with quartz <20%. Acid rocks presented values above 2,5 W/mK, a similar behavior to that observed in rocks with quartz >20% (granites). For all the other cases, correlation factors are always low and present opposite behavior to Fe2O3, CaO, MgO, and TiO2. As to Al2O3, K2O, and Na2O results are not conclusive and are statistically disperse. Thermal property knowledge especially thermal conductivity and its application in the building construction field appeared to be very satisfactory for it involves both technological and thermal comfort aspects, which favored in all cases fast, cheap, and precise results. The relation between thermal conductivity and linear thermal dilatation have also shown satisfactory results especially when it comes to the quartz role as a common, determining phase between the two variables. Thermal conductivity studies together with rocky material density can function as an additional tool for choosing materials when considering structural calculation aspects and thermal comfort, for in the dimension stone case there is a small density variation in relation to a thermal conductivity considerable variation

Sistemas orbitais e aéreos aplicados à análise multi-escala da tectônica rúptil atuante na borda sudeste da Bacia do Parnaíba

The tectonics activity on the southern border of Parnaíba Basin resulted in a wide range of brittle structures that affect siliciclastic sedimentary rocks. This tectonic activity and related faults, joints, and folds are poorly known. The main aims of this study were (1) to identify lineaments using several remotesensing systems, (2) to check how the interpretation based on these systems at several scales influence the identification of lineaments, and (3) to contribute to the knowledge of brittle tectonics in the southern border of the Parnaíba Basin. The integration of orbital and aerial systems allowed a multi-scale identification, classification, and quantification of lineaments. Maps of lineaments were elaborated in the following scales: 1:200,000 (SRTM Shuttle Radar Topographic Mission), 1:50,000 (Landsat 7 ETM+ satellite), 1:10,000 (aerial photographs) and 1:5,000 (Quickbird satellite). The classification of the features with structural significance allowed the determination of four structural sets: NW, NS, NE, and EW. They were usually identified in all remote-sensing systems. The NE-trending set was not easily identified in aerial photographs but was better visualized on images of medium-resolution systems (SRTM and Landsat 7 ETM+). The same behavior characterizes the NW-trending. The NS-and EW-trending sets were better identified on images from high-resolution systems (aerial photographs and Quickbird). The structural meaning of the lineaments was established after field work. The NEtrending set is associated with normal and strike-slip faults, including deformation bands. These are the oldest structures identified in the region and are related to the reactivation of Precambrian basement structures from the Transbrazilian Lineament. The NW-trending set represents strike-slip and subordinated normal faults. The high dispersion of this set suggests a more recent origin than the previous structures. The NW-trending set may be related to the Picos-Santa Inês Lineament. The NS-and EW-trending sets correspond to large joints (100 m 5 km long). The truncation relationships between these joint sets indicate that the EW-is older than the NS-trending set. The methodology developed by the present work is an excellent tool for the understanding of the regional and local tectonic structures in the Parnaíba basin. It helps the choice of the best remote-sensing system to identify brittle features in a poorly known sedimentary basin