Magister Pharmaceuticae - MPharm / Fast dispersible tablets (FDTs) are solid single-unit dosage forms that are placed in the mouth and allowed to disperse or dissolve in the saliva without the need of water. The basic approach to formulating FDTs consists of adding a superdisintegrant to a tablet formulation. These tablets offer both the advantages of conventional tablets and liquid dosage forms along with distinctive properties which include accurate dosing, ease of administration, quick onset of action, enhanced bioavailability, and increased patient adherence. FDTs have been found to be effective in remedying therapeutic in-adherence caused by dysphagia (swallowing difficulties) particularly in paediatric and geriatric subjects. There is a strong correlation between therapeutic success and patient adherence especially with HIV/AIDS treatment regimens, consequently the dosage form should be patient friendly and devoid of unappealing characteristics. This study aimed at developing a cost effective fast dispersible tablet of lamivudine using alternative excipients and conventional techniques. Only conventional tablets and oral liquid dosage forms of lamivudine are available on the South African market. Two natural polymers reported to have superdisintegrating properties were selected to serve as multipurpose excipients in this study. The polymers were identified, characterised and compared using thermal, spectroscopic and micromeritic analytical tools. The polymer that displayed the best characteristics in terms of micromeritic, tableting and disintegrating properties was retained and used for the optimum formulation. The optimum formulation was composed of 150 mg of lamivudine, 23% w/w unripe banana powder and 2% w/w magnesium stearate. FDTs of lamivudine were obtained using the compression technique with and without wet granulation. The tablets were assessed as per the United States Pharmacopoeia (USP) guidelines and other evaluation procedures pertaining to FDTs. The wet granulated tablets were found to be less friable and thus more resilient than the directly compressed tablets. In-vitro disintegration of the wet granulated tablets occurred within 50±3 sec in deionised water (pH 7) and 35±2 sec in a phosphate buffer solution (pH 6.8). Consequently, the innovative tablets fulfilled the core requirement of FDTs i.e. rapid disintegration. Drug release studies were carried out by analysing dissolution aliquots of the innovative tablets using a validated High Performance Liquid Chromatography (HPLC) method, and comparing them to Aspen Lamivudine®, a conventional tablet of lamivudine presently on the South African market. Complete dissolution in deionised water (pH 7) was attained within 10 minutes and 30 minutes for the innovative tablets and Aspen Lamivudine® respectively.

Reduced bioavailability in some formulations of phytosterols accounts for the variable results observed in LDL- C- lowering efficacy among trials. This study examined the effects of a water-dispersible formulation of free phytosterols (WD-PS) versus phytosterol esters (PS-esters) on plasma lipid and fat soluble vitamins concentrations in hypercholesterolemic individuals. Using a double-blind, randomized, crossover study, 47 hypercholesterolemics were provided for 4 wk: WD-PS-enriched yogurt (2g/d), PS-esters-enriched yogurt (2g/d), or yogurt alone (placebo), in a random order. Each study phase was separated by 4 wk washout intervals. Supplementation of WD-PS or PS-esters similarly decreased serum TC (7.7% and 6.3%, respectively) and LDL-C levels (11.7% and 11.6%, respectively, p<0.001). The ratio of TC/ HDL-C decreased for WD-PS (10.6%, p<0.05) but not for PS-esters. Moreover, WD-PS reduced serum TG (13.9%, p<0.05) as compared to PS-esters (0.6%). The results of the current study confirm the importance of the formulation of phytosterols in their bioavailability and efficacy.

Reduced bioavailability in some formulations of phytosterols accounts for the variable results observed in LDL- C- lowering efficacy among trials. This study examined the effects of a water-dispersible formulation of free phytosterols (WD-PS) versus phytosterol esters (PS-esters) on plasma lipid and fat soluble vitamins concentrations in hypercholesterolemic individuals. Using a double-blind, randomized, crossover study, 47 hypercholesterolemics were provided for 4 wk: WD-PS-enriched yogurt (2g/d), PS-esters-enriched yogurt (2g/d), or yogurt alone (placebo), in a random order. Each study phase was separated by 4 wk washout intervals. Supplementation of WD-PS or PS-esters similarly decreased serum TC (7.7% and 6.3%, respectively) and LDL-C levels (11.7% and 11.6%, respectively, p<0.001). The ratio of TC/ HDL-C decreased for WD-PS (10.6%, p<0.05) but not for PS-esters. Moreover, WD-PS reduced serum TG (13.9%, p<0.05) as compared to PS-esters (0.6%). The results of the current study confirm the importance of the formulation of phytosterols in their bioavailability and efficacy.

This dissertation research addresses the interrelationships between chemistry and network structure in epoxy networks as well as how mechanical properties of the resulting networks are affected by these relationships. The effects of chemistry and network structure on interphase morphology and performance in vinyl ester/carbon fiber composites have also been investigated on both a macro and nanoscale. Thermosets were prepared with blends of bisphenol-A and novel phosphine oxide based diepoxide oligomers using a siloxane or a novolac crosslinking agent. In the siloxane cured networks the incorporation of the phosphine oxide group yielded networks with increased glass transition temperatures, from 71°C to 92°C, and water absorption, from 1 wt % to 5.5 wt %, due to the polar nature of the phosphine oxide bond. Higher char yields were also observed with the addition of the phosphorus, 27 wt % compared to 11 wt % for bisphenol-A epoxy networks. The bisphenol-A based epoxy/siloxane network was exceptionally ductile with a fracture toughness (K1c) of 2 MPa-m1/2. In networks prepared with the novolac crosslinking agent hydrogen bonding, observed using FTIR, was evident even at temperatures above the network Tg and resulted in increased rubbery moduli with phosphine oxide incorporation. Adhesive strengths to steel increased from ~9.7 MPa with bisphenol-A epoxy to ~13.8 MPa when the phosphine oxide containing epoxy was incorporated into the network. Within carbon fiber/vinyl ester composites, a series of tough ductile thermoplastics and a series of one-phase polyurethanes were investigated as carbon fiber sizings. The three poly(hydroxyether)s resulted in different interphase morphologies due to their respective interdiffusion into the vinyl ester resin. The unmodified poly(hydroxyether) was miscible with the vinyl ester resin at the elevated cure temperatures and adhesion between the fiber and bulk matrix was increased from 28 MPa with unsized fibers to 45 MPa with sized fibers. The carboxylate modified poly(hydroxyether) was also miscible at elevated temperatures, however the interdiffused region was narrower, ~5 mm. This system showed an increase in the fiber/matrix adhesion similar to that found for the unmodified poly(hydroxyether)/vinyl ester system and composite cyclic fatigue durability was improved by ~50 %. Using a poly(hydroxyether ethanolamine) interphase material, which was not miscible with the resin, resulted in a sharp interface. While the adhesion was not improved through the use of this sizing, the composite fatigue durability was still increased by a moderate amount, ~ 25%. The one-phase polyurethanes were dispersible in water with incorporation of a minimum of 0.08 equivalents of N-methyldiethanolamine per mole of diisocyanate. Fatigue durability in composite panels was not improved by the addition of the polyurethane sizings due to the miscibility of the sizing and the matrix. / Ph. D.

Iron oxide magnetic nanoparticle synthesis and their surface functionalization hold a crucial position in the design and fabrication of functional materials for a variety of biomedical applications. Non-uniform nanoparticles with poor crystallinity, prepared by conventional methods, have only limited value in biological areas. Large scale synthesis methods that are able to produce high quality, mono-dispersed iron oxide nanoparticles using low cost and environment friendly chemicals are highly desirable. Following synthesis, appropriate surface functionalization is necessary to direct the dispersibility of nanoparticles in aqueous solution in order to provide them with acceptable colloidal stability against the ion strength and many biomolecules that nanoparticles may encounter under physiological conditions. Poorly stabilized nanoparticles that easily aggregate and form large size agglomerates would be quickly cleared by the liver and other organs and are not suitable for clinical purposes. Additionally, many interesting functionalities such as fluorescence, targeting and anti-cancer properties can be immobilized onto the surface of iron oxide magnetic nanoparticles during the surface functionalization process so as to build multifunctional platforms for disease diagnosis and treatment. Polyol method can be an effective way to prepare magnetite nanoparticles that are suitable for biological applications. In a polyol system, selected surface functionalities were introduced to the nanoparticle surface via a hot injection technique. The morphology, uniformity, crystallinity and magnetic properties were examined to understand the effect of different ligand molecules on the final product. Their surface chemistry, colloidal properties and surface reactivity were also studied to evaluate their practicability in different applications. A high efficiency in-situ method for the preparation of magnetite nanoparticles attached to silica nanospheres was also developed in a polyol system. This approach eliminates several time-consuming processing steps that are in the conventional fabrication route and directly produces water-stable magnetite-silica hybrid materials with surface availability for subsequent modifications. In addition to polyalcohol, the potential of polyamine in the preparation of water-soluble magnetite nanoparticles with amine surface functionalities was also evaluated. And it is suggested that polyamine acts as solvent, stabilizing agent and reducing agent simultaneously during the synthesis. The characterization of polyamine coated nanoparticles, their surface functionalization, and subsequent application for bioseparation and drug delivery were reported.

Polyaniline (PANI), when doped with small-molecule acids, is an attractive candidate for organic and polymer electronics because of its high electrical conductivity. Its utility as functional components in electrical devices, however, has been severely restricted because such PANI has limited processibility stemming from its limited solubility in common solvents. To overcome this barrier, we have developed water dispersible PANI that is template polymerized in the presence of a polymer acid, poly(2-acrylamido-2-methyl-1-propanesulfonic acid), or PAAMPSA. The polymer acid serves two roles: it acts as a dopant to render PANI conductive and excess water soluble pendant groups provide dispersibility of PANI in aqueous media. While the introduction of polymer acids renders the conducting polymer processible, such gain in processibility is often accompanied by a significant reduction in conductivity. As such, PANI that is doped with polymer acids has only seen limited utility in organic electronics. Given the promise of conducting polymers in organic electronics in general, this thesis focuses on the elucidation of processing-structure-property relationships of PANI-PAAMPSA with the aim of ultimately improving the electrical conductivity of polymer acid-doped PANI. By controlling the molecular weight and molecular weight distribution of the polymer acid template, we have improved the conductivity of PANI-PAAMPSA from 0.4 to 2.5 S/cm. The conductivity increases with decreasing molecular weight of PAAMPSA, and it further increases with narrowing the molecular weight distribution of PAAMPSA. Strong correlations between the structure and the conductivity of PANI-PAAMPSA are observed. In particular, the crystallinity of PANI increases with increasing the conductivity of PANI-PAAMPSA. Given that the crystallinity qualifies the molecular order in PANI-PAAMPSA, we observe a linear correlation between molecular order and macroscopic charge transport in PANI-PAAMPSA. PANI-PAAMPSA forms electrostatically stabilized sub-micron particles during polymerization due to strong ionic interactions between the sulfonic acid groups of PAAMPSA and aniline. When cast as films, the connectivity of these particles must play an important role in macroscopic conduction. The size and size distribution of PANI-PAAMPSA particles is strongly influenced by the molecular characteristics of polymer acid template. Templating the synthesis of PANI-PAAMPSA with a higher molecular weight PAAMPSA results in larger particles, and templating with a PAAMPSA having a larger molecular weight distribution results in a large size distribution in the particles. Because conduction in PANI-PAAMPSA films is governed by how these particles pack, the macroscopic conductivity of PANI-PAAMPSA films increases with increasing particle density, that is reducible from the molecular characteristics of PAAMPSA. Moreover, PANI-PAAMPSA particles are structurally and chemically inhomogeneous. The conductive portions of the polymer preferentially segregate to the particle surface. Conduction in these materials is therefore mediated by the particle surface and conductivity thus scales superlinearly with particle surface area per unit film volume. We further have improved the electrical conductivity of PANI-PAAMPSA by more than two orders of magnitude via post-processing solvent annealing with dichloroacetic acid (DCA). Since DCA is a good plasticizer for PAAMPSA and its pKa is lower than that of PAAMPSA (pKas of DCA and PAAMPSA are 1.21 and 2.41, respectively, at room temperature), DCA can effectively moderate the ionic interactions between PANI and PAAMPSA, thereby relaxing the sub-micron particulate structure arrested during polymerization. PANI-PAAMPSA can thus rearrange from a “compact coil” to an “extended chain” conformation upon exposure to DCA. Efficient charge transport is thus enabled through such “extended chain” PANI-PAAMPSA structure. DCA-treated PANI-PAAMPSA exhibits an average conductivity of 48 S/cm. The DCA treatment is not only specific to PANI-PAAMPSA. This treatment can also enhance the conductivity of commercially-available poly(ethylene dioxythiophene) that is doped with poly(styrene sulfonic acid), or PEDOT-PSS. Specifically, DCA-treated PEDOT-PSS exhibits a conductivity of 600 S/cm; this conductivity is the highest among polymer acid-doped conducting polymers reported so far. PANI-PAAMPSA can effectively function as anodes in organic solar cells (OSCs) whose active layer is a blend of poly(3-hexylthiophene), P3HT, and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Specifically, the OSCs with PANI-PAAMPSA anodes exhibit an average short circuit current density of 1.95 mA/cm², open circuit voltage of 0.52 V, fill factor of 0.38, and efficiency of 0.39 %. The use of DCA-treated PANI-PAAMPSA as anodes increases device performance (i.e., short circuit current density and thereby efficiency) of OSCs by approximately two and a half fold. The OSCs with DCA-treated PANI-PAAMPSA anodes exhibit short circuit current density and efficiency as high as 4.95 mA/cm² and 0.97 %, respectively. We demonstrated several factors that govern the electrical conductivity of polymer acid-doped conducting polymers. Design rules, such as those illustrated in this study, can enable the development of conducting polymers that is not only easily processible from aqueous dispersions, but also sufficiently conductive for electronic applications, and should bring us closer to the realization of low-cost organic and polymeric electronics. / text

L’objectif de ce projet était de développer une formulation liquisolide (LS) de clozapine ayant des propriétés de dissolution améliorées et évaluer sa stabilité et ainsi que sa robustesse à la modification d’excipients. Le propylène glycol (PG), la cellulose microcrystalline (MCC) et le glycolate d’amidon sodique (SSG) ont été utilisés respectivement en tant que véhicule liquide non volatile, agent de masse et agent désintégrant pour la préparation de comprimés LS. Le dioxyde de silicium colloïdal (CSD), le silicate de calcium (CS) et l'aluminométasilicate de magnésium (MAMS) ont été choisis comme agents d’enrobage sec. La caractérisation complète des mélanges et des comprimés a été effectuée. Le taux de libération des comprimés LS était statistiquement supérieur à celui des comprimés réguliers. La surface spécifique des matériaux d’enrobage avait un effet sur les propriétés d’écoulement des mélanges et la taille des particules des matériaux d’enrobage a eu un effet sur la vitesse de dissolution. Le ratio support/enrobage du mélange de poudres (valeur de R) était un paramètre important pour les systèmes LS et devait être plus grand que 20 afin d’obtenir une meilleure libération du médicament. La formulation choisie a démontré une stabilité pour une période d’au moins 12 mois. La technique LS s’est avéré une approche efficace pour le développement de comprimés de clozapine ayant des propriétés de dissolution améliorées. Les comprimés oro-dispersibles (ODT) sont une formulation innovante qui permettent de surmonter les problèmes de déglutition et de fournir un début d'action plus rapide. Dans l’optique d’améliorer les propriétés de dissolution, un essai a été effectué pour étudier la technique LS dans la formulation des ODT de clozapine. Le PG, la MCC, le CSD et la crospovidone (CP) ont été utilisés respectivement en tant que véhicule liquide non volatile, agent de masse, agent d’enrobage sec et agent superdésintégrant pour la préparation de comprimés oro-dispersibles liquisolides (OD-LST). Le mannitol a été choisi comme agent de masse et agent édulcorant. La saccharine de sodium a été utilisée comme agent édulcorant. La caractérisation complète des comprimés a été effectuée. Le taux de libération des OD-LSTs était statisquement supérieur comparativement aux comprimés ODTs. La formulation choisie a démontré une stabilité pour une période d’au moins 6 mois. Il a été conclu que des ODT de clozapine peuvent être préparés avec succès en utilisant la technologie LS dans le but d’améliorer la désintégration et le taux de dissolution de la clozapine dans la cavité orale. / The objective of this research was to develop a liquisolid (LS) formulation of clozapine with improved dissolution properties and evaluate its robustness to excipient modifications as well as its stability. Propylene glycol (PG), microcrystalline cellulose (MCC) and sodium starch glycolate (SSG) were employed as non-volatile liquid vehicle, carrier material and disintegrant respectively for preparing LS compacts. Colloidal silicon dioxide (CSD), calcium silicate (CS) and magnesium aluminometasilicate (MAMS) were selected as coating materials. Complete characterisation of the blends and tablets was performed. The drug release rates of LS compacts were distinctly higher as compared to regular tablets. The specific surface areas of coating materials had an effect on the flow properties of the blends and the particle sizes of coating materials affected the dissolution rate. The carrier : coating ratio of the powder system (R value) was an important parameter for LS systems and had to be larger than 20 to obtain enhanced drug release. The selected formulation demonstrated stability for a period of at least 12 months. The LS technique was an effective approach to prepare clozapine tablets with enhanced dissolution properties. Orally disintegrating tablets (ODT) constitute an innovative dosage form that overcomes the problems of swallowing and provides a quick onset of action. In view of enhancing dissolution properties an attempt has been made to study LS technique in formulation of ODT of clozapine. PG, MCC, CSD and crospovidone (CP) were employed as non-volatile liquid vehicle, carrier material, coating material and superdisintegrant respectively for preparing orally disintegrating liquisolid tablets (OD-LST). Mannitol was selected as a carrier material and sweetening agent. Sodium saccharin (SS) was employed as a sweetening agent. Complete characterisation of the tablets was performed. The drug release rates of OD-LSTs were distinctly higher as compared to regular ODTs. The selected formulation demonstrated stability for a period of at least 6 months. It was concluded that the ODT of clozapine can be successfully prepared using LS technology in order to improve disintegration and dissolution rate of clozapine in oral cavity.

O uso de efluente de estação de tratamento de esgoto (EETE) na agricultura irrigada pode ser uma estratégia alternativa de fornecimento de água e nutrientes para culturas agrícolas. Entretanto se realizado por longos períodos pode adicionar grandes quantidades de sódio ao solo o que poderia levar a degradação de suas propriedades e impacto em aspectos agronômicos de capim Tifton 85. Esse trabalho consistiu de dois objetivos: i) avaliar os efeitos da irrigação com efluente rico em sódio durante mais de oito anos em propriedades químicas e físico-hídricas de um Argissolo Vermelho. Para isso foram estabelecidos três tratamentos avaliados nas profundidades de 0,05-0,15 (P1), 0,25-0,35 (P2) e 0,70-0,80 m (P3): SI - cultivo de capim sem adubação e sem irrigação; A100 - cultivo irrigado com água de abastecimento sódica e adubado com 520,0 kg ha-1 ano-1 de nitrogênio; E66 - cultivo irrigado com EETE e adubado com 343,2 kg ha-1 ano-1 de nitrogênio. Foram determinados: pH do solo (em água e CaCl2), condutividade elétrica do extrato aquoso do solo (CE1:1), concentração de sódio (Na+), potássio (K+), cálcio (Ca2+), magnésio (Mg2+), alumínio (Al3+), carbono (C) e nitrogênio (N) do solo, com posterior cálculo de soma de bases (SB), capacidade de troca catiônica (CTC), saturação por bases (V) e percentagem de sódio trocável (PST); densidade do solo (?), argila dispersa em água (ADA), condutividade hidráulica do solo saturado (Ksat), curva de retenção da água no solo (CR), porosidade do solo (?) e distribuição do tamanho dos poros; ii) avaliar os efeitos da irrigação com efluente rico em sódio durante mais de oito anos em aspectos agronômicos de capim Tifton 85. Para alcançar o segundo objetivo foi estabelecido além do SI, A100 e E66, mais quatro tratamentos: A0 - cultivo de capim sem adubação e irrigado com água de abastecimento sódica; E0, E33 e E100 - cultivo de capim irrigado com EETE e adubado com 0, 171,6 e 520,0 kg ha-1 ano-1 de nitrogênio, respectivamente. Foram determinados: produtividade de massa seca estacional (MS-Estacional), anual (MS-Anual) e acumulação estacional e anual de nitrogênio (N-MS), potássio (K-MS) e sódio (Na-MS) no tecido vegetal de capim Tifton 85. Houve alterações nas propriedades químicas e físico-hídricas do solo em função dos tratamentos e profundidades. Na P1 o E66 aumentou a CE1:1, a densidade do solo, o conteúdo de água residual e diminuiu a concentração de Mg2+ e conteúdo de água de saturação. Já o A100 reduziu a concentração de K+ e Mg2+, o conteúdo de água de saturação e aumentou a densidade do solo e o conteúdo de água residual. Na P2 o E66 aumentou o pH-H2O e a CE1:1, o conteúdo de água de saturação e o conteúdo residual. O A100 aumentou o pH-H2O, o Na+, o PST, a argila dispersa em água, o conteúdo de água de saturação e o conteúdo residual e diminuiu o C e N. Na P3 o E66 aumentou apenas o pH-H2O e o conteúdo de água residual e reduziu o conteúdo de água de saturação. O A100 aumentou o conteúdo de água de saturação, o conteúdo de água residual e a mesoporosidade. As propriedades do solo da P2 parecem ser as mais afetadas pelos efeitos do sódio decorrentes, principalmente, do uso de irrigação com água sódica. As produtividades de MS e acumulação de N-MS e K-MS foram superiores nos tratamentos E66, E100 e A100 e não foram reduzidas ao longo destes anos. A acumulação de Na-MS foi proporcional à produtividade, mas o capim passou a acumular um pouco menos sódio. Na estação chuvosa a MS de capim representou cerca de 72% da MS-Anual, sendo influenciada fortemente pelo período de estacionalidade. / The use of treated sewage effluent (TSE) in irrigated agriculture can be an alternative strategy to supply water and nutrients to crops. However if applied for long periods of time, it can add large amounts of sodium to the soil, resulting in soil properties degradation and impacts on agronomic aspects Tifton 85 Bermudagrass. The objectives of this work were: i) evaluate the effect of irrigation with sodium rich effluent for more than eight years on chemical, physical and hydraulic properties of an Ultisol. For this were established three treatments (WI - growing grass without fertilization or irrigation ; FW100 - irrigation with sodic fresh water supply and fertilized with 520.0 kg ha-1 year-1 nitrogen; E66 - irrigation with TSE and fertilized with 343.2 kg ha-1 year-1 nitrogen) The effects were evaluated at different depths (D1: 0.5-0.15, D2: 0.25-0.35 and D3: 0.70-0.80 m), determining: soil pH (in water and CaCl2), soil electrical conductivity of the aqueous extract (EC1:1) sodium concentration (Na+), potassium (K+), calcium (Ca2+), magnesium (Mg2+), aluminum (Al3+), soil carbon (C) and soil nitrogen (N), with subsequent calculation of sum of bases (SB), cation exchange capacity (CEC), base saturation (V) and exchangeable sodium percentage (ESP); bulk density (?), water dispersible clay (WDC), saturated hydraulic conductivity (Ksat), soil water retention curve (SWRC), soil porosity (?) and pore size distribution. Another objective was to evaluate the effect of irrigation with sodium rich effluent for more than eight years on agronomic aspects of Tifton 85 Bermudagrass. In addition to WI, FW100 and E66 treatments were established another four treatments (FW0 - growing grass without fertilizer and irrigated with sodic water supply; E0, E33 and E100 - growing grass irrigated with TSE and fertilized with 0, 171.6 and 520.0 kg ha-1 year-1 nitrogen, respectively) and determined the productivity of seasonal dry matter (Seasonal-DM), annual (Annual-DM) and nitrogen (N-DM), potassium (K-DM) and sodium (Na-DM) seasonal accumulation and annual in the plant tissue of Tifton 85 Bermudagrass. There were changes in chemical, physical and hydraulic soil properties as a function of treatments and depths. In the D1 the E66 treatment increased CE1:1, the bulk density, the residual water content and decreased the concentration of Mg2+, water content at saturation. FW100 reduced the concentration of K+ and Mg2+, the water content at saturation and increased soil bulk density and residual water content. In the D2, the E66 treatment increased pH-H2O and CE1:1, the water content at saturation and residual water content. The FW100 increased pH-H2O, Na+, ESP, water dispersible clay , the content of water saturation and residual contents and decreased C and N. In the D3 the E66 only increased the pH-H2O and residual water content and reduced water content saturation. The FW100 increased the water content at saturation point, residual water content and mesoporosity. The soil properties of D2 aparently are more affected than other depths by the effects of sodium, mainly from the use of irrigation water with sodium. The DM, N-DM and, K-DM were higher in the treatments E66, E100 and FW100 and there were not observed reductions over the years. The accumulation Na-DM was proportional to productivity, but the grass began to accumulate less sodium. In the rainy season the grass DM accounted for approximately 72% of Annual-DM, being strongly influenced by seasonality period.

O uso de efluente de estação de tratamento de esgoto (EETE) na agricultura irrigada pode ser uma estratégia alternativa de fornecimento de água e nutrientes para culturas agrícolas. Entretanto se realizado por longos períodos pode adicionar grandes quantidades de sódio ao solo o que poderia levar a degradação de suas propriedades e impacto em aspectos agronômicos de capim Tifton 85. Esse trabalho consistiu de dois objetivos: i) avaliar os efeitos da irrigação com efluente rico em sódio durante mais de oito anos em propriedades químicas e físico-hídricas de um Argissolo Vermelho. Para isso foram estabelecidos três tratamentos avaliados nas profundidades de 0,05-0,15 (P1), 0,25-0,35 (P2) e 0,70-0,80 m (P3): SI - cultivo de capim sem adubação e sem irrigação; A100 - cultivo irrigado com água de abastecimento sódica e adubado com 520,0 kg ha-1 ano-1 de nitrogênio; E66 - cultivo irrigado com EETE e adubado com 343,2 kg ha-1 ano-1 de nitrogênio. Foram determinados: pH do solo (em água e CaCl2), condutividade elétrica do extrato aquoso do solo (CE1:1), concentração de sódio (Na+), potássio (K+), cálcio (Ca2+), magnésio (Mg2+), alumínio (Al3+), carbono (C) e nitrogênio (N) do solo, com posterior cálculo de soma de bases (SB), capacidade de troca catiônica (CTC), saturação por bases (V) e percentagem de sódio trocável (PST); densidade do solo (?), argila dispersa em água (ADA), condutividade hidráulica do solo saturado (Ksat), curva de retenção da água no solo (CR), porosidade do solo (?) e distribuição do tamanho dos poros; ii) avaliar os efeitos da irrigação com efluente rico em sódio durante mais de oito anos em aspectos agronômicos de capim Tifton 85. Para alcançar o segundo objetivo foi estabelecido além do SI, A100 e E66, mais quatro tratamentos: A0 - cultivo de capim sem adubação e irrigado com água de abastecimento sódica; E0, E33 e E100 - cultivo de capim irrigado com EETE e adubado com 0, 171,6 e 520,0 kg ha-1 ano-1 de nitrogênio, respectivamente. Foram determinados: produtividade de massa seca estacional (MS-Estacional), anual (MS-Anual) e acumulação estacional e anual de nitrogênio (N-MS), potássio (K-MS) e sódio (Na-MS) no tecido vegetal de capim Tifton 85. Houve alterações nas propriedades químicas e físico-hídricas do solo em função dos tratamentos e profundidades. Na P1 o E66 aumentou a CE1:1, a densidade do solo, o conteúdo de água residual e diminuiu a concentração de Mg2+ e conteúdo de água de saturação. Já o A100 reduziu a concentração de K+ e Mg2+, o conteúdo de água de saturação e aumentou a densidade do solo e o conteúdo de água residual. Na P2 o E66 aumentou o pH-H2O e a CE1:1, o conteúdo de água de saturação e o conteúdo residual. O A100 aumentou o pH-H2O, o Na+, o PST, a argila dispersa em água, o conteúdo de água de saturação e o conteúdo residual e diminuiu o C e N. Na P3 o E66 aumentou apenas o pH-H2O e o conteúdo de água residual e reduziu o conteúdo de água de saturação. O A100 aumentou o conteúdo de água de saturação, o conteúdo de água residual e a mesoporosidade. As propriedades do solo da P2 parecem ser as mais afetadas pelos efeitos do sódio decorrentes, principalmente, do uso de irrigação com água sódica. As produtividades de MS e acumulação de N-MS e K-MS foram superiores nos tratamentos E66, E100 e A100 e não foram reduzidas ao longo destes anos. A acumulação de Na-MS foi proporcional à produtividade, mas o capim passou a acumular um pouco menos sódio. Na estação chuvosa a MS de capim representou cerca de 72% da MS-Anual, sendo influenciada fortemente pelo período de estacionalidade. / The use of treated sewage effluent (TSE) in irrigated agriculture can be an alternative strategy to supply water and nutrients to crops. However if applied for long periods of time, it can add large amounts of sodium to the soil, resulting in soil properties degradation and impacts on agronomic aspects Tifton 85 Bermudagrass. The objectives of this work were: i) evaluate the effect of irrigation with sodium rich effluent for more than eight years on chemical, physical and hydraulic properties of an Ultisol. For this were established three treatments (WI - growing grass without fertilization or irrigation ; FW100 - irrigation with sodic fresh water supply and fertilized with 520.0 kg ha-1 year-1 nitrogen; E66 - irrigation with TSE and fertilized with 343.2 kg ha-1 year-1 nitrogen) The effects were evaluated at different depths (D1: 0.5-0.15, D2: 0.25-0.35 and D3: 0.70-0.80 m), determining: soil pH (in water and CaCl2), soil electrical conductivity of the aqueous extract (EC1:1) sodium concentration (Na+), potassium (K+), calcium (Ca2+), magnesium (Mg2+), aluminum (Al3+), soil carbon (C) and soil nitrogen (N), with subsequent calculation of sum of bases (SB), cation exchange capacity (CEC), base saturation (V) and exchangeable sodium percentage (ESP); bulk density (?), water dispersible clay (WDC), saturated hydraulic conductivity (Ksat), soil water retention curve (SWRC), soil porosity (?) and pore size distribution. Another objective was to evaluate the effect of irrigation with sodium rich effluent for more than eight years on agronomic aspects of Tifton 85 Bermudagrass. In addition to WI, FW100 and E66 treatments were established another four treatments (FW0 - growing grass without fertilizer and irrigated with sodic water supply; E0, E33 and E100 - growing grass irrigated with TSE and fertilized with 0, 171.6 and 520.0 kg ha-1 year-1 nitrogen, respectively) and determined the productivity of seasonal dry matter (Seasonal-DM), annual (Annual-DM) and nitrogen (N-DM), potassium (K-DM) and sodium (Na-DM) seasonal accumulation and annual in the plant tissue of Tifton 85 Bermudagrass. There were changes in chemical, physical and hydraulic soil properties as a function of treatments and depths. In the D1 the E66 treatment increased CE1:1, the bulk density, the residual water content and decreased the concentration of Mg2+, water content at saturation. FW100 reduced the concentration of K+ and Mg2+, the water content at saturation and increased soil bulk density and residual water content. In the D2, the E66 treatment increased pH-H2O and CE1:1, the water content at saturation and residual water content. The FW100 increased pH-H2O, Na+, ESP, water dispersible clay , the content of water saturation and residual contents and decreased C and N. In the D3 the E66 only increased the pH-H2O and residual water content and reduced water content saturation. The FW100 increased the water content at saturation point, residual water content and mesoporosity. The soil properties of D2 aparently are more affected than other depths by the effects of sodium, mainly from the use of irrigation water with sodium. The DM, N-DM and, K-DM were higher in the treatments E66, E100 and FW100 and there were not observed reductions over the years. The accumulation Na-DM was proportional to productivity, but the grass began to accumulate less sodium. In the rainy season the grass DM accounted for approximately 72% of Annual-DM, being strongly influenced by seasonality period.

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Agradecemos a compreensão. on 2016-09-02T20:28:27Z (GMT) / Submitted by FERNANDO KASSIS CARVALHO null (kassis@fca.unesp.br) on 2016-09-05T12:44:17Z No. of bitstreams: 1 Tese V15 CARVALHO, F.K...pdf: 1222042 bytes, checksum: 739b1439b95a7990d14a578862e4d136 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-09-05T16:34:41Z (GMT) No. of bitstreams: 1 carvalho_fk_dr_bot.pdf: 1222042 bytes, checksum: 739b1439b95a7990d14a578862e4d136 (MD5) / Made available in DSpace on 2016-09-05T16:34:41Z (GMT). No. of bitstreams: 1 carvalho_fk_dr_bot.pdf: 1222042 bytes, checksum: 739b1439b95a7990d14a578862e4d136 (MD5) Previous issue date: 2016-06-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O objetivo desta pesquisa foi avaliar a interferência de três tipos de formulações de inseticidas e fungicidas na tensão superficial, viscosidade e espectro de gotas de caldas de pulverização. O experimento foi conduzido na forma de um fatorial 2 x 3, duas classes de produtos fitossanitários e três tipos de formulações, em um delineamento experimental inteiramente casualizado. Quando recomendados em bula, adjuvantes foram adicionados às caldas de pulverização, sendo analisados separadamente daqueles tratamentos sem adjuvantes. Cada tipo de formulação foi representado por cinco produtos comerciais. As formulações utilizadas foram concentrado emulsionável (EC), suspensão concentrada (SC) e granulado dispersível (WG). As concentrações das caldas foram simuladas para uma taxa de aplicação de 50 L ha-1 e as pulverizações foram realizadas utilizando-se a ponta XR 8003VS, na pressão de 200 kPa. A formulação WG resultou nos maiores valores de tensão superficial (TS) e percentual do volume aplicado composto por gotas menores do que 100 µm (%<100 µm), e os menores valores de diâmetro mediano volumétrico (DMV). O acréscimo de adjuvantes à base de óleo mineral e vegetal aumentou o DMV e reduziu a amplitude relativa do espectro de gotas (AR), TS e o %<100 µm comparado aos mesmos tratamentos sem adjuvantes. A formação de emulsões, decorrentes do uso dos adjuvantes ou de formulações EC, foi mais eficaz em reduzir o %<100 µm, AR e a TS e em aumentar o DMV do que aquelas que formaram dispersões, representadas pelas formulações WG e SC de inseticidas e fungicidas. A formulação dos produtos comerciais deve ser considerada como fator para o planejamento da segurança ambiental e qualidade das aplicações, uma vez que existe um padrão de interferência das formulações de inseticidas e fungicidas avaliadas na AR, DMV, DV01, esfericidade e %<100 µm. / The objective of this study was to evaluate the interference of tree types of formulations of insecticides and fungicides on surface tension, viscosity, and droplet size spectra of spray solutions. It was conducted in a 2 x 3 factorial design, two classes of pesticides and tree types of formulations, in a completely randomized experiment. When it was prescribed on the label, adjuvants were mixed on the spray solution, but these treatments were analyzed apart from those without adjuvants. Each type of formulation was represented by five commercial products. The selected formulations types were emulsifiable concentrate (EC), suspension concentrate (SC) and water dispersible granules (WG). The concentrations of the spray solutions were calculated supposing a spray rate of 50 L ha-1 and the applications were done using a XR 8003VS nozzle, at operating pressure of 200 kPa. The WG formulation resulted on the highest surface tension (ST) and percentage of droplets smaller than 100 µm (%<100 µm), and the lowest volume median diameter (VMD). The use of mineral and vegetal oils increased the VMD and decreased the relative Span, ST and %<100 µm, compared with the respective treatments without adjuvants. The formation of emulsions, resulted from using the adjuvants or EC formulations, on the spray solutions were more efficient on decreasing the %<100 µm, RS, and ST, and on increasing VMD than those formulations that resulted on the formation of dispersions, represented by WG and SC formulations of insecticides and fungicides. Formulations of commercial pesticides may be considered an aspect for planning the protection of the environment and the quality of spray applications, once it exists a pattern of interference of the studied formulations of insecticides and fungicides on relative Span, VMD, DV01, sphericity and %<100 µm. / CAPES: 99999.003632/2015-06