Determinação da energia de ativação e pureza de medicamentos de referência, genérico e similar utilizando técnicas termoanalíticas

In this work, the reference drugs, generic and similar to the active ingredients acetylsalicylic acid, paracetamol, captopril, hydrochlorothiazide and mebendazole were purchased from local pharmacies and studied by thermogravimetry (TG) and Differential Scanning Calorimetry (DSC). Thermal decomposition was assessed to obtain from the Ozawa method the activation energy in inert atmosphere (nitrogen), using three different heating ratios (5, 10 and 20 o C min-1). The pharmaceutical formulation of the AAS reference was the one who presented different from the others (generic and similar) Thermogravimetric profile indicating likely interaction between the active ingredient and excipients. Was observed at the heating rate of the inverse temperature that no linearity of the data, ie, there was no correlation between the percentage of mass loss and the activation energy involved in the thermal decomposition of the pharmaceutical formulation of the AAS reference log graph. The analysis by differential scanning calorimetry was performed in nitrogen atmosphere with a heating rate of 10 ° C min-1. In the analysis of these same drugs, the data curves found on the melting point were, except for hydrochlorothiazide, are consistent with the literature. Hydrochlorothiazide presented a melting point well below that found in the literature, which may be justified due to the interaction of the active ingredient with the excipient lactose. In the study of purity, using the Van't Hoff equation, the reference drugs hydrochlorothiazide and mebendazole reference generic and showed similar impurity content below the limit established that this equation must be greater than 2.5 mol%

Avaliação térmica e desempenho do processo de secagem de misturas de graviola e leite em secador de leito de jorro

The soursop (A. muricata) is a fruit rich in minerals especially the potassium content. The commercialization of soursop in natura and processed has increased greatly in recent years. Drying fruit pulp in order to obtain the powdered pulp has been studied, seeking alternatives to ensure the quality of dehydrated products at a low cost of production. The high concentration of sugars reducing present in fruits causes problems of agglomeration and retention during fruit pulp drying in spouted bed dryers. On the other hand in relation to drying of milk and fruit pulp with added milk in spouted bed, promising results are reported in the literature. Based on these results was studied in this work drying of the pulp soursop with added milk in spouted bed with inert particles. The tests were based on a 24 factorial design were evaluated for the effects of milk concentration (30 to 50% m/m), drying air temperature (70 to 90 °C), intermittency time (10 to 14 min), and ratio of air velocity in relation to the minimum spout (1.2 to 1.5) on the rate of production, of powder moisture, yield, rate of drying and thermal efficiency of the process. There were physical and chemical analysis of mixtures, of powders and of mixtures reconstituted by rehydration powders. Were adjusted statistical models of first order to data the rate of production, yield and thermal efficiency, that were statistically significant and predictive. An efficiency greater than 40% under the conditions of 50% milk mixture, at 70 ° C the drying air temperature and 1.5 for the ratio between the air velocity and the minimum spout has been reached. The intermittency time showed no significant effect on the analyzed variables. The final product had moisture in the range of 4.18% to 9.99% and water activity between 0.274 to 0.375. The mixtures reconstituted by rehydration powders maintained the same characteristics of natural blends.

Studio di stati fotoeccitati in nanoparticelle di V-TiO2 mediante scattering inelastico risonante di raggi X

La TiO2 è uno dei materiali più studiati degli ultimi decenni. I motivi sono da ricercarsi nelle sue numerose applicazioni, possibili in molti campi come dispositivi fotovoltaici, depurazione da agenti inquinanti o filtraggio di raggi UV. Per le celle elettrochimiche in particolare, il biossido di titanio offre molti vantaggi, ma non è privo di ostacoli. Il limite principale è lo scarso assorbimento dello spettro visibile, dovuto all’energy gap elevato (circa 3.2 eV). La ricerca da diversi anni si concentra sul tentativo di aumentare l’assorbimento di luce solare: promettenti sono i risultati raggiunti grazie alla forma nanoparticellare della TiO2, che presenta proprietà diverse dal materiale bulk. Una delle strategie più studiate riguarda il drogaggio tramite impurità, che dovrebbero aumentare le prestazioni di assorbimento del materiale. Gli elementi ritenuti migliori a questo scopo sono il vanadio e l’azoto, che possono essere usati sia singolarmente che in co-doping. In questo lavoro abbiamo realizzato la crescita di nanoparticelle di V-TiO2, tramite Inert Gas Condensation. La morfologia e la struttura atomica sono state analizzate attraverso microscopia a trasmissione, analizzandone la mappe tramite image processing. Successivamente abbiamo studiato le proprietà di assorbimento ottico dei campioni, nello spettro visibile e nel vicino ultravioletto, attraverso il metodo della riflettanza diffusa, determinando poi il bandgap tramite Tauc Plot. L’esperimento centrale di questo lavoro di tesi è stato condotto sulla beamline ID26 dell’European Synchrotron Radiation Facility, a Grenoble. Lì, abbiamo effettuato misure XANES, allo scopo di studiare gli stati fotoeccitati del materiale. L’eccitazione avveniva mediante laser con lunghezza d’onda di 532 nm. Tramite gli spettri, abbiamo analizzato la struttura locale e lo stato di ossidazione del vanadio. Le variazioni indotta dal laser hanno permesso di capire il trasferimento di carica e determinare la vita media.

(Table 2) Zinc complexation data from POLARSTERN cruise ANT-XXIV/3

The speciation of dissolved zinc (Zn) was investigated by voltammetry in the Atlantic sector of the Southern Ocean along two transects across the major frontal systems: along the Zero Meridian and across the Drake Passage. In the Southern Ocean south of the APF we found detectable labile inorganic Zn throughout the surface waters in contrast to studies from lower latitudes. Using a combination of ASV titrations and pseudopolarography revealed the presence of significant concentration of electrochemically inert Zn ligands throughout the Southern Ocean. These ligands however were nearly always saturated due to the presence of excess concentrations of dissolved Zn that were associated with the high nutrient waters south of the Antarctic Polar Front (APF). Only in surface waters did the concentration of Zn complexing ligands exceed the dissolved Zn concentrations suggesting a biological source for these ligands. Our findings have clear implications for the biogeochemical cycling of Zn and for the interpretation of paleo records utilizing Zn in opal as a tracer of Zn speciation in the water column.

High-Resolution In Situ Oxygen-Argon Studies of Surface Biological and Physical Processes in the Polar Oceans

The Arctic Ocean and Western Antarctic Peninsula (WAP) are the fastest warming regions on the planet and are undergoing rapid climate and ecosystem changes. Until we can fully resolve the coupling between biological and physical processes we cannot predict how warming will influence carbon cycling and ecosystem function and structure in these sensitive and climactically important regions. My dissertation centers on the use of high-resolution measurements of surface dissolved gases, primarily O2 and Ar, as tracers or physical and biological functioning that we measure underway using an optode and Equilibrator Inlet Mass Spectrometry (EIMS). Total O2 measurements are common throughout the historical and autonomous record but are influenced by biological (net metabolic balance) and physical (temperature, salinity, pressure changes, ice melt/freeze, mixing, bubbles and diffusive gas exchange) processes. We use Ar, an inert gas with similar solubility properties to O2, to devolve distinct records of biological (O2/Ar) and physical (Ar) oxygen. These high-resolution measurements that expose intersystem coupling and submesoscale variability were central to studies in the Arctic Ocean, WAP and open Southern Ocean that make up this dissertation.

Key findings of this work include the documentation of under ice and ice-edge blooms and basin scale net sea ice freeze/melt processes in the Arctic Ocean. In the WAP O2 and pCO2 are both biologically driven and net community production (NCP) variability is controlled by Fe and light availability tied to glacial and sea ice meltwater input. Further, we present a feasibility study that shows the ability to use modeled Ar to derive NCP from total O2 records. This approach has the potential to unlock critical carbon flux estimates from historical and autonomous O2 measurements in the global oceans.

Evaporation maps for ternary non-ideal liquid mixtures

This thesis deals with the evaporation of non-ideal liquid mixtures using a multicomponent mass transfer approach. It develops the concept of evaporation maps as a convenient way of representing the dynamic composition changes of ternary mixtures during an evaporation process. Evaporation maps represent the residual composition of evaporating ternary non-ideal mixtures over the full range of composition, and are analogous to the commonly-used residue curve maps of simple distillation processes. The evaporation process initially considered in this work involves gas-phase limited evaporation from a liquid or wetted-solid surface, over which a gas flows at known conditions. Evaporation may occur into a pure inert gas, or into one pre-loaded with a known fraction of one of the ternary components. To explore multicomponent masstransfer effects, a model is developed that uses an exact solution to the Maxwell-Stefan equations for mass transfer in the gas film, with a lumped approach applied to the liquid phase. Solutions to the evaporation model take the form of trajectories in temperaturecomposition space, which are then projected onto a ternary diagram to form the map. Novel algorithms are developed for computation of pseudo-azeotropes in the evaporating mixture, and for calculation of the multicomponent wet-bulb temperature at a given liquid composition. A numerical continuation method is used to track the bifurcations which occur in the evaporation maps, where the composition of one component of the pre-loaded gas is the bifurcation parameter. The bifurcation diagrams can in principle be used to determine the required gas composition to produce a specific terminal composition in the liquid. A simple homotopy method is developed to track the locations of the various possible pseudo-azeotropes in the mixture. The stability of pseudo-azeotropes in the gas-phase limited case is examined using a linearized analysis of the governing equations. Algorithms for the calculation of separation boundaries in the evaporation maps are developed using an optimization-based method, as well as a method employing eigenvectors derived from the linearized analysis. The flexure of the wet-bulb temperature surface is explored, and it is shown how evaporation trajectories cross ridges and valleys, so that ridges and valleys of the surface do not coincide with separation boundaries. Finally, the assumption of gas-phase limited mass transfer is relaxed, by employing a model that includes diffusion in the liquid phase. A finite-volume method is used to solve the system of partial differential equations that results. The evaporation trajectories for the distributed model reduce to those of the lumped (gas-phase limited) model as the diffusivity in the liquid increases; under the same gas-phase conditions the permissible terminal compositions of the distributed and lumped models are the same.

Modernist Ecology: Modernism and the Reimagination of Nature

Countering the trend in contemporary ecocriticism to advance realism as an environmentally responsible mode of representation, this essay argues that the anti-realist aesthetics of literary modernism were implicitly “ecological.” In order to make this argument I distinguish between contemporary and modernist ecological culture (both of which I differentiate in turn from ecological science); while the former is concerned primarily with the practical reform characteristic of what we now call “environmentalism,” the latter demanded an all-encompassing reimagination of the relationship between humanity and nature. “Modernist ecology,” as I call it, attempted to envision this change, which would be ontological or metaphysical rather than simply social, through thematically and formally experimental works of art. Its radical vision, suggestive in some ways of today’s “deep” ecology, repudiated modern accounts of nature as a congeries of inert objects to be manipulated by a sovereign subject, and instead foregrounded the chiasmic intertexture of the subject/object relationship. In aesthetic modernism we encounter not “objective” nature, but “nature-being” – a blank substratum beneath the solid contours of what philosopher Kate Soper calls “lay nature” – the revelation of which shatters historical constructions of nature and alone allows for radical alternatives. This essay looks specifically at modernist ecology as it appears in the works of W. B. Yeats, D. H. Lawrence, and Samuel Beckett, detailing their attempts to envision revolutionary new ecologies, but also their struggles with the limited capacity of esoteric modernist art to effect significant ecological change on a collective level.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

The significance of nitrogen regeneration for new production within a filament of the Mauritanian upwelling system

The Lagrangian progression of a biological community was followed in a filament of the Mauritanian upwelling system, north-west Africa, during offshore advection. The inert dual tracers sulfur hexafluoride and helium-3 labelled a freshly upwelled patch of water that was mapped for 8 days. Changes in biological, physical, and chemical characteristics were measured, including phytoplankton productivity, nitrogen assimilation, and regeneration. Freshly upwelled water contained high nutrient concentrations but was depleted in N compared to Redfield stoichiometry. The highest rate of primary productivity was measured on the continental shelf, associated with high rates of nitrogen assimilation and a phytoplankton community dominated by diatoms and flagellates. Indicators of phytoplankton abundance and activity decreased as the labelled water mass transited the continental shelf slope into deeper water, possibly linked to the mixed layer depth exceeding the light penetration depth. By the end of the study, the primary productivity rate decreased and was associated with lower rates of nitrogen assimilation and lower nutrient concentrations. Nitrogen regeneration and assimilation took place simultaneously. Results highlighted the importance of regenerated NHC 4 in sustaining phytoplankton productivity and indicate that the upwelled NO3 pool contained an increasing fraction of regenerated NO3 as it advected offshore. By calculating this fraction and incorporating it into an f ratio formulation, we estimated that of the 12:38Tg C of annual regional production, 4:73Tg C was exportable.

Lead: Inorganic Chemistry

The article covers basic inorganic chemistry of lead. As an introduction, the properties and historical uses of metallic lead are discussed, followed by aspects of lead toxicity, including the toxicity origins and effects of lead poisoning. Properties of lead as a heavy p-block element are discussed, with emphasis on the modern view of the so-called “inert pair effect”, including its origin, the influence on stability of lead oxidation states, and on the coordination chemistry of lead(II), viz., “sterically active lone pair”. This is followed by an overview of lead inorganic compounds, including halides, pseudohalides, oxides and chalcogenides, hydroxides and their chalcogenide analogs, alkoxides, oxoacids, O-donors, S- and Se-donors, Group 15 donors, compounds with lead-transition metal bonds, and finally metallic clusters (Zintl phases). This is by no means a comprehensive review, rather compounds representative for each class were presented. In most sections, structural aspects of each class of compounds are discussed, followed by applications, with the focus on modern uses in material science.

Process Gas Infiltration in Inconel 718 Samples during SLM Processing

Argon infiltration is a well-known problem of hot isostatic pressed components. Thus, the argon content is one quality attribute which is measured after a hot isostatic pressing (HIP) process. Since the Selective Laser Melting (SLM) process takes place under an inert argon atmosphere; it is imaginable that argon is entrapped in the component after SLM processing. Despite using optimized process parameters, defects like pores and shrink holes cannot be completely avoided. Especially, pores could be filled with process gas during the building process. Argon filled pores would clearly affect the mechanical properties. The present paper takes a closer look at the porosity in Inconel 718 samples, which were generated by means of SLM. Furthermore, the argon content of the powder feedstock, of samples made by means of SLM, of samples which were hot isostatic pressed after the SLM process, and of conventionally manufactured samples were measured and compared. The results showed an increased argon content in the Inconel 718 samples after SLM processing compared to conventional manufactured samples.

Production of Gaseous Radiotracers Ch3i and I2 Through Na123i Salt

The objective of the present work was to develop, separately, methodology for production of two gaseous tracers through the sodium iodide NaI marked with 123I. Found in the nature in form different, the iodine has been used in diverse works in the area of the industry and health. These two forms of the gaseous iodine, the methyl iodide, CH3I, and molecular iodine, I2, are very unstable and volatile in the ambient temperature and presents different problems in clean-up and monitoring systems. The syntheses were processed with sodium iodide (NaI) 1M aqueous solution marked with 123I. The production of gas I2 was realized with in chlorine acid (HCl) and sodium iodate salt (NaIO3) and the CH3I was used, the salt of NaI and the reagent (CH3)2SO4. The production of gases was initially realized through in unit in glass with an inert material and the purpose was to study the kinetic of reaction and to determine the efficiency of production. The two synthesis occurs in the reaction bottle and after of produced, the gas is stored in the collect bottle that contains a starch solution for fixed the I2, and in syntheses of CH3I contains a silver nitrate solution for your fixation. To determine the efficiency of production of gases, analytic tests were realized, where the consumption of iodide ions of the bottle of reaction are measured. The optimization of production of the each gaseous tracer was studied varying parameter as: concentration of iodide, concentration of acid and temperature. After, the syntheses of the radiotracers were realized in the compact unit, having been used as main reagent the salt radiated of sodium iodide, Na123I. The transportation of elementary iodine and methyl iodine was studied by a scintillation detector NaI (2 x 2)” positioned in the reaction bottle.

Production of Gaseous Tracer I2 from the Sodiumiodide Salt

Found in the nature in form different, the iodine has been used in diverse works in the area of the industry and health. The iodine is very unstable and volatile in the ambient temperature and the I2 is one of the diverse gaseous forms found. In this work was developed methodology for production of gaseous tracer from the sodium iodide (NaI) 0,1 M marked with 123I. The synthesis was processed with in chlorine acid (HCl) 1M and sodium iodate salt (NaIO3). The production of gas I2 initially was carried through in unit of glass with the inert material and the purpose was to study the kinetic of reaction. The synthesis occurs in the reaction bottle and the produced gas is stored in the collect bottle that contains a starch solution (5 g/100 mL water). To determine the efficiency of production of gas I2, analytic tests had been carried through, where the consumption of iodide ions of the bottle of reaction is measured. The optimization of production of the gaseous tracer was studied varying parameters as: concentration of iodide and iodate, concentration of acid and temperature. Then, the synthesis of the radiotracer was realized in the compact unit, being utilized as main reagent the salt radiated of sodium iodide, Na123I. The transportation of elementary iodine was studied by a scintillation detector NaI (2 x 2)” placed in the reaction bottle. To acquire the data, the detector use a set of electronic modules for the acquisition of signals generated.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

Insight into Biological Small-Molecule Activation from Enzymes, Model Complexes, and X-ray Spectroscopy

Thesis (Ph.D.)--University of Washington, 2016-08