Poli-líquidos iônicos e complexos solúveis de Eu3+ e Tb3+ : bioimageamento celular seletivo

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Avaliação da eficácia in vivo da L-arginina na elasticidade da pele

Dissertação (mestrado)—Universidade de Brasília, Faculdade de Ciências da Saúde, Programa de Pós-Graduação em Ciências da Saúde, 2012.

Influence of autogenous shrinkage on mass transport properties of concrete

La retracción autógena en el hormigón es el cambio volumétrico una vez iniciado su proceso de fraguado. Se desarrolla a edades muy tempranas debido a la retracción química y a la autodesecación. Éstos causan microfisuras en hormigones de alta resistencia y permiten el ingreso de agentes nocivos como dióxido de carbono, cloruros y sulfatos que deterioran al hormigón. A pesar de haber estudios de la retracción autógena, existe incertidumbre sobre su influencia en la durabilidad del hormigón. Por ello, el motivo del presente estudio es cuantificar y analizar el efecto de la retracción autógena en el hormigón usando tres pruebas de transporte: difusión de oxígeno, permeabilidad de oxígeno y absorción de agua. Dos métodos, para tres diferentes aglutinantes, fueron usados para determinar la mezcla control que produce menor retracción: utilizando SRA y realizando el curado en un cuarto de niebla. Posteriormente, los resultados de las pruebas de transporte entre la mezcla de control seleccionada y mezclas altamente afectadas por retracción autógena fueron comparados para diferentes aglutinantes. Resultados revelaron que muestras con SRA presentan menores retracciones autógenas y se sugiere que estas muestras sean consideradas de control. Se demostró que la retracción autógena afecta significativamente los coeficientes de transporte los cuales en un punto de vista de servicio pueden reducir la vida útil de cualquier estructura realizada con hormigón de alta resistencia. Esta investigación además confirmó que la mayor deformación autógena ocurre durante las dos primeras semanas; por lo tanto, se debe tomar cuidado suficiente en el curado.

Bioadhesive drug delivery system of diltiazem hydrochloride for improved bioavailability in cardiac therapy

Purpose: To prepare and evaluate bioadhesive buccal films of diltiazem hydrochloride (a L-type calcium channel blocker) for overcoming the limitations of frequent dosing, low bioavailability and gastrointestinal discomfort of oral delivery. Methods: Buccal films were prepared by solvent casting technique using sodium carboxymethylcellulose, polyvinyl pyrrolidone K-30 and polyvinyl alcohol. The films were evaluated for weight, thickness, surface pH, swelling index, in vitro residence time, folding endurance, in vitro release, ex-vivo permeation (across porcine buccal mucosa) and drug content uniformity. Results: The drug content of the formulations was uniform with a range of 18.94 ± 0.066 (F2) to 20.08 ± 0.07 mg per unit film (F1). The films exhibited controlled release ranging from 58.76 ± 1.62 to 91.45 ± 1.02 % over a period > 6 h. The films containing 20 mg diltiazem hydrochloride, polyvinyl alcohol (10 %) and polyvinyl pyrrolidone (1 % w/v) i.e. formulation F5, showed moderate swelling, convenient residence time and promising drug release, and thus can be selected for further development of a buccal film for potential therapeutic uses. Conclusion: The developed formulation is a potential bioadhesive buccal system for delivering diltiazem directly to systemic circulation, circumventing first-pass metabolism, avoiding gastric discomfort and improving bioavailability at a minimal dose.

A THEORETICAL STUDY OF INTERACTION OF NANOPARTICLES WITH BIOMOLECULE

Many types of materials at nanoscale are currently being used in everyday life. The production and use of such products based on engineered nanomaterials have raised concerns of the possible risks and hazards associated with these nanomaterials. In order to evaluate and gain a better understanding of their effects on living organisms, we have performed first-principles quantum mechanical calculations and molecular dynamics simulations. Specifically, we will investigate the interaction of nanomaterials including semiconducting quantum dots and metallic nanoparticles with various biological molecules, such as dopamine, DNA nucleobases and lipid membranes. Firstly, interactions of semiconducting CdSe/CdS quantum dots (QDs) with the dopamine and the DNA nucleobase molecules are investigated using similar quantum mechanical approach to the one used for the metallic nanoparticles. A variety of interaction sites are explored. Our results show that small-sized Cd4Se4 and Cd4S4 QDs interact strongly with the DNA nucleobase if a DNA nucleobase has the amide or hydroxyl chemical group. These results indicate that these QDs are suitable for detecting subcellular structures, as also reported by experiments. The next two chapters describe a preparation required for the simulation of nanoparticles interacting with membranes leading to accurate structure models for the membranes. We develop a method for the molecular crystalline structure prediction of 1,2-Dimyristoyl-sn-glycero-3-phosphorylcholine (DMPC), 1,2-Dimyristoyl-sn-glycero-3-phosphorylethanolamine (DMPE) and cyclic di-amino acid peptide using first-principles methods. Since an accurate determination of the structure of an organic crystal is usually an extremely difficult task due to availability of the large number of its conformers, we propose a new computational scheme by applying knowledge of symmetry, structural chemistry and chemical bonding to reduce the sampling size of the conformation space. The interaction of metal nanoparticles with cell membranes is finally carried out by molecular dynamics simulations, and the results are reported in the last chapter. A new force field is developed which accurately describes the interaction forces between the clusters representing small-sized metal nanoparticles and the lipid bilayer molecules. The permeation of nanoparticles into the cell membrane is analyzed together with the RMSD values of the membrane modeled by a lipid bilayer. The simulation results suggest that the AgNPs could cause the same amount of deformation as the AuNPs for the dysfunction of the membrane.

Hydro-Physical Characterization of Media Used in Agricultural Systems to Develop the Best Management Practices for operation of an Environmentally Sustainable Agricultural Enterprise

Florida is the second leading horticulture state in the United States with a total annual industry sale of over $12 Billion. Due to its competitive nature, agricultural plant production represents an extremely intensive practice with large amounts of water and fertilizer usage. Agrochemical and water management are vital for efficient functioning of any agricultural enterprise, and the subsequent nutrient loading from such agricultural practices has been a concern for environmentalists. A thorough understanding of the agrochemical and the soil amendments used in these agricultural systems is of special interest as contamination of soils can cause surface and groundwater pollution leading to ecosystem toxicity. The presence of fragile ecosystems such as the Everglades, Biscayne Bay and Big Cypress near enterprises that use such agricultural systems makes the whole issue even more imminent. Although significant research has been conducted with soils and soil mix, there is no acceptable method for determining the hydraulic properties of mixtures that have been subjected to organic and inorganic soil amendments. Hydro-physical characterization of such mixtures can facilitate the understanding of water retention and permeation characteristics of the commonly used mix which can further allow modeling of soil water interactions. The objective of this study was to characterize some of the locally and commercially available plant growth mixtures for their hydro-physical properties and develop mathematical models to correlate these acquired basic properties to the hydraulic conductivity of the mixture. The objective was also to model the response patterns of soil amendments present in those mixtures to different water and fertilizer use scenarios using the characterized hydro-physical properties with the help of Everglades-Agro-Hydrology Model. The presence of organic amendments helps the mixtures retain more water while the inorganic amendments tend to adsorb more nutrients due to their high surface area. The results of these types of characterization can provide a scientific basis for understanding the non-point source water pollution from horticulture production systems and assist in the development of the best management practices for the operation of environmentally sustainable agricultural enterprise

Le pore oméga, un défaut biophysique commun aux mutations des canaux Nav1.5 causant le développement des arythmies associées à la cardiomyopathie dilatée

Les canaux sodiques dépendants du voltage (Nav) sont des protéines transmembranaires largement exprimées au sein de l’organisme. Ils sont responsables de l’initiation des potentiels d’action au niveau des cellules excitables et régissent ainsi de nombreuses fonctions physiologiques telles que les fonctions cognitives et sensorielles, les fonctions motrices et la fonction cardiaque. Au niveau du coeur, le sous-type Nav1.5 est majoritairement exprimé à la surface des cardiomyocytes. Leurs dysfonctions sont traditionnellement associées à de nombreux troubles électriques cardiaques. Des mutations de ces canaux ont récemment été reliées au développement d’un phénotype clinique complexe associant diverses arythmies et la cardiomyopathie dilatée (DCM), une atteinte morphologique. L’objectif de mon doctorat a donc été l’identification mais aussi la caractérisation d’un potentiel défaut biophysique commun à l’ensemble des mutations Nav1.5 associées au développement de ce phénotype clinique atypique. Premièrement, nous nous sommes intéressés à deux mutations des canaux Nav1.5 retrouvées chez des patients atteints de DCM, et dont les altérations biophysiques ont été décrites comme divergentes. L’étude parallèle de ces deux mutants nous a amenés à identifier une caractéristique commune : la création d’une nouvelle voie de perméation alternative au sein des canaux Nav1.5, le pore oméga. Dans un second temps, nous avons souhaité consolider l’association entre la création du pore oméga et le développement pathologique. Cette seconde étude portant sur deux autres mutants Nav1.5 a permis de confirmer l’apparition d’un pore oméga et ainsi d’accroître la suspicion du caractère délétère de ce pore oméga. Finalement, à l’aide d’une cinquième mutation des canaux Nav1.5, nous avons investigué les conséquences physiopathologiques de la création d’un pore oméga. Cette étude, a clairement démontré les conséquences néfastes d’un tel pore au niveau de l’homéostasie ionique cellulaire. Ces perturbations se répercutent par la suite sur les signaux électriques, les propriétés morphologiques mais aussi fonctionnelles des cardiomyocytes. Les études menées lors de mon doctorat ont ainsi abouti à l’identification du pore oméga comme étant une caractéristique biophysique commune aux mutations des canaux Nav1.5 associées au développement des arythmies et de la dilatation cardiaque.

New functional polythiophene based materials: fine-tuning of photovoltaic or chiroptical properties

There is a remarkable level of interest in the development of π-conjugated polymers (ICPs) which have been employed, thanks to their promising optical and electronic properties, in numerous applications including photovoltaic cells, light emitting diodes and thin-film transistors. Although high power conversion efficiency can be reached using poly(3-alkylthiophenes) (P3ATs) as electron-donating materials in polymeric solar cells of the Bulk-Heterojunction type (BHJ), their relatively large band gap limits the solar spectrum fraction that can be utilized. The research work described in this dissertation thus concerns the synthesis, characterization and study of the optical and photoactivity properties of new organic semiconducting materials based on polythiophenes. In detail, various narrow band gap polymers and copolymers were developed through different approaches and were characterized by several complementary techniques, such as gel permeation chromatography (GPC), NMR spectroscopy, thermal analyses (DSC, TGA), UV-Vis/PL spectroscopy and cyclic voltammetry (CV), in order to investigate their structural and chemical/photophysical properties. Moreover, the polymeric derivatives were tested as active material in air-processed organic solar cells. The activity has also been devoted to investigate the behavior of polythiophenes with chiral side chain, that are fascinating materials capable to assume helix supramolecular structures, exhibiting optical activity in the aggregated state.

Synthesis, Modification and Characterization of Polymeric Membranes for CO2 Separation

This doctorate focused on the development of dense polymeric membranes for carbon capture, mostly in post combustion applications, and for natural gas sweetening. The work was supported by the European Project NANOMEMC2 funded under H2020 program. Different materials have been investigated, that rely on two main transport mechanisms: the solution-diffusion and the facilitated transport. In both cases, proper nano-fillers have been added to the matrix, in order to boost the mechanical and permselective properties of the membranes. Facilitated transport membranes were based on the use of was polyvinylamine (PVAm), as main matrix with fixed-site carriers, and L-Arginine as mobile carrier; the filler, used mostly as reinforcer, was carboxymethylated nanocellulose (cNFC). Humid test showed interesting results, and especially the blend made of PVAm/cNFC/Arg in weight ratio 27,5/27,5/45 crossed the Robeson CO2/N2 upper bound, representing current state of the art membranes, with a CO2 permeability of 271 Barrer and CO2/N2 selectivity of 70. Solution diffusion membranes were based on Pebax®2533 matrix which was added with three different graphene oxide (GO)-based materials, namely pristine GO, Porous Graphene Oxide (PGO) and a GO functionalized with polyetheramine (PEAGO). All of them provided a modest but clear increment of permeability of the Pebax matrix, from plus 2% (GO) to plus 8% (PGO), with no change in selectivity. The gas tested with this type of composites were CO2 and N2, for Post combustion capture applications. Pebax®2533 was also chemically modified, obtaining the product called “Benzoyl-P2533”, that was fully characterized, and tested in term of permeation using five gas: CO2, N2, CH4, O2, and He. Modified material showed an increment of the overall permeability of the material of a fair 10% for all gases tested, apart from helium, that increased of almost 50%.

Novel membranes for hemodialysis application

The present work is focused on the synthesis and characterization of novel materials for hemodialysis applications. Cellulose acetate was chosen as base polymer for the preparation of porous Mixed Matrix Membrane adsorbers (MMMAs) and for the synthesis of hybrid ultrafiltration membranes. Hemodialysis is a renal replacement therapy used to eliminate,the waste products and excess fluids accumulating in the blood of people affected by an end stage renal disease. The main environmental drawback associated to it is the large water consumption. The MMMAs were prepared with the porpoise of eliminating waste metabolites (uremic toxins) from the spent dialysate solution, with the prospective limiting the consumption of water related to the process. Batch tests of MMMAs showed that the removal of uric acid is almost complete while the one of urea and creatinine is limited to a 20/30 %. The thinking behind the concept of MMMAs was aimed to develop a small a lab scale chromatographic cartridge to continuously remove uremic toxins from an aqueous feed solution. The cartridge was packed with MMMAs and tested with a mixture of toxins. Experiments results shown a promising removal capability of the system even if the necessity of a higher surface area to achieve better efficiency is denoted. The other important issue related to hemodialysis is the assessment of an overall mass transfer rates in hemodialyzers. The mass transfer correlations proposed in literature do not take into account the effect of permeation and are developed for turbulent flow regime. Therefore, hybrid cellulose acetate/Silica ultrafiltration membranes were prepared to characterize a surrogate system of an artificial kidney (AK) in terms of fluid mechanics and mass transfer. The effect of surface roughness and suction on the velocity profiles was determined and a new dimensionless mass transfer correlation accounting for permeation was developed.

Study of the second hyperpolarizability of poly(3-alkylthiophenes) using the third-harmonic scattering technique

During the past years, the considerable need in the domain of communications for more potent photonic devices has focused the research activities into the nonlinear optical (NLO) materials which can be used for modern optical switches. In this regard, a lot of research activities are focused on the organic materials and conjugated polymers which offer more advantages compared to the inorganic ones. On this matter, poly(3-alkylthiophene) (P3AT), an organic conjugated polymer, can be investigated as potential optical material with in particular the focus on the NLO properties such as the first- and second-hyperpolarizability, β and γ respectively. The activities carried out at the Laboratory of Polymer Synthesis of the KU Leuven, during the master's thesis work, focused on the study of conjugated polymers in order to evaluate their NLO properties for the future purpose of applications in optical systems. In particular, three series of polythiophenes functionalized with an alkyl side chain in the 3-position were synthesized: poly(3-hexylthiophene) (P3HT), poly[3-(2-ethylhexyl)thiophene] (P3EHT) and random copolymer of the two regio-isomers of P3HT. They were made in order to study the influence of molar mass, branching and regio-irregularity on the γ-value. The Kumada catalyst transfer condensative polymerization (KCTCP) and the Pd(RuPhos)-protocol were used for the polymerizations in order to have control over the molar mass of the growing chain and consequently to obtain well-defined and reproducible materials. The P3AT derivatives obtained were characterized by gel permeation chromatography (GPC), spectroscopic techniques (1H-NMR, UV-Vis) and the γ-value was investigated using the third-harmonic scattering (THS) technique. In particular, the THS technique is useful to investigate the optical behavior of the series of polymers in solution.

Natural Wax-Based Water Vapour Barrier Coatings on PLA for MAP Food Packaging

PLA is a bio-based polymer that is obtained from renewable resources and it is very promising for a sustainable packaging manufacturing. However, its gas and vapour barrier properties are not enough to comply with the requirements of MAP packaging of fresh foods, which need specific concentration of water and oxygen to avoid spoilage and to keep the organoleptic properties unaltered throughout their shelf-life. The use of waxes from natural renewable sources such as plants (e.g., candelilla wax, carnauba wax, rice bran wax, sunflower wax) or animals (e.g., beeswax) could tackle down the permeation of water vapour through the packaging without affecting its bio-based content. The core of this work is developing wax-based coatings with enhanced thermo-mechanical properties so that they can undergo thermoforming and a proper adhesion to the PLA substrate can be ensured. Chemical modifications and crosslinking of waxes are performed to produce wax-based alkyd resins. The synthesised materials are characterised both by DSC and FTIR. Films of the wax-based alkyds are produced in order to assess their water vapour permeability.

Design, synthesis and photovoltaic properties of some thiophene-based conjugated polymers for organic solar cells

The current issue of the resource of energy combined with the tendency to give a green footprint to our lifestyle have prompted the research to focus the attention on alternative sources with great strides in the optimization of polymeric photovoltaic devices. The research work described in this dissertation consists in the study of different semiconducting π-conjugated materials based on polythiophenes (Chapter I). In detail, the GRIM polymerization was deepened defining the synthetic conditions to obtain regioregular poly(3-alkylthiophene) (Chapter II). Since the use of symmetrical monomers functionalized with oxygen atom(s) allows to adopt easy synthesis leading to performing materials, disubstituted poly(3,4-dialkoxythiophene)s were successfully prepared, characterized and tested as photoactive materials in solar cells (Chapter III). A “green” resource of energy should be employed through sustainable devices and, for this purpose, the research work was continued on the synthesis of thiophene derivatives soluble in eco-friendly solvents. To make this possible, the photoactive layer was completely tailored starting from the electron-acceptor material. A fullerene derivative soluble in alcohols was successfully synthetized and adopted for the realization of the new devices (Chapter IV). New water/alcohol soluble electron-donor materials with different functional groups were prepared and their properties were compared (Chapter V). Once found the best ionic functional group, a new double-cable material was synthetized optimizing the surface area between the different materials (Chapter VI). Finally, other water/alcohol soluble materials were synthetized, characterized and used as cathode interlayers in eco-friendly devices (Chapter VII). In this work, all prepared materials were characterized by spectroscopy analyses, gel permeation chromatography and thermal analyses. Cyclic voltammetry, X-ray diffraction, atomic force microscopy and external quantum efficiency were used to investigate some peculiar aspects.

Study and development of BaCe0.65Zr0.20Y0.1503-Δ (BCZY) – Gd0.2Ce0.8O2-Δ (GDC) dense ceramic membranes sysyem for high temperature H2 purification

The first main conclusion drawn from this dissertation concerns the amount of Pt deposited on the asymmetric layer of membrane produced by tape casting porosity shaping method. Three different amounts were investigated (0.15, 1.5 and 4.5 mg cm-2 ). The most optimal performance, based on H2 permeation performances, was attained when 1.5 mg cm-2 of Pt was deposited on the porous layer, resulting in a 0.642 mL min-1 cm-2 permeated H2 when 80% H2 in He was employed as the feed. Pt deposition method is influenced by the concentration of the Pt precursor, which results in different morphology of the catalyst. The second development focused on further optimization on tape casting membranes concerning the solvent employed for the Pt catalyst deposition. The same concentration of Pt was employed, depositing 1.5 mg cm-2 on the porous side of the membrane, but a mixture of acetone and water was employed as solvent. This mixture allowed the suppression of effects leading to poorly dispersed particles. As a result, it was possible to achieve 0.74 mL min-1 cm-2 at 750°C with 50% H2 in He. Lastly, first-ever permeation performance measurements into an innovative ceramic membrane type for hydrogen separation was investigated. In-depth research was done on a group of hierarchically-structured BaCe0.65Zr0.20Y0.15O3-δ(BCZY) - Gd0.2Ce0.8O2-δ(GDC) membranes produced by freeze casting porosity shaping method. Membranes were investigated observing the effect of deposition solvent and the effect of porous layer thickness. Employing a mixture of Acetone and water resulted in better hydrogen permeation at temperatures (T > 650°C), reaching 0.26 mL min-1 cm-2 at 750°C with 50% H2 in He. The reduction of porous layer thickness led to a hydrogen flow of 0.33 mL min-1 cm-2 , at 750°C with 50% H2 in He.

Analisys of gas permeability in perfluorosufonated polymeric membranes for CO2 separation

The present thesis focuses on the permebility analisys of Aquivion® 980 Perfluoro sulfonic acid (PFSA) polymer with particular reference to the influence of the equivalent weight (gram of polymer per molSO3H) on the permeation properties. Aquivion grade tested, indeed, were characterized by a lower equivalent weight ( 870 g/molSO3H against 980 of the present material) with respect to data present in the open literature. Permeability of different gases (CO2, N2, and CH4) was tested at different temperatures and different humidity, a parameter which greatly influences the gas transport in such hydrophilic material- Aquivion® swells consistently in humid conditions increasing its gas permeability of more than one order of magnitude with respect to values prevailing in dry conditions. Present data confirm such behavior being the permeability of all gases and vapors tested substantially increased in presence of water. Interestingly the increase in permeability results be similar for all the gases inspected, hence such enhanced permeation capability is not associated to a selectivity loss that happens in polymeric membranes. Although, the results, of CO2, are lower compared to those obtained with the different grades, with lower equivalent weight, of Aquivion, thus suggesting that an increase of this parameter is detrimental for both permeability and selectivity of the membranes with respect to CO2. This is likely related to the fact that a lower content of SO3H groups makes it difficult to have an interconnected water domain inside the membranes. A modeling approach was considered to describe the experimental data and to give a better insight into the observed behavior, unfortunately, it resulted not sensitive enough to catch the differences between the gas permeability in PSFAs with high and low equivalent weight. The latter were indeed usually contained within 10-20% which results to be the in the same range of model precision when used in a predictive way.