Made available in DSpace on 2014-10-09T12:44:53Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:59:46Z (GMT). No. of bitstreams: 1 07160.pdf: 4424646 bytes, checksum: 4938889fd9a885e62dfeaafc99b1274d (MD5) / Dissertacao (Mestrado Profissionalizante em Lasers em Odontologia) / IPEN/D-MPLO / Instituto de Pesquisas Energeticas e Nucleares, IPEN/CNEN-SP; Faculdade de Odontologia, Universidade de Sao Paulo

Philosophiae Doctor - PhD / Cape Town includes two vegetable farming areas within the city limits, the Joostenbergvlakte/Kraaifontein area and the Philippi area. Both areas supply produce to local markets and further afield. Sporadically, high levels of cadmium, copper, lead and zinc have been found to occur in some of the soils, irrigation water resources and crops. To find the sources of specifically Cd, Pb and Zn to these agricultural systems, extensive analysis of several heavy metals in inputs such as fertilizers, agrochemicals and supplementary water resources to these farming areas was undertaken. Heavy metal concentrations in soils, irrigation water resources and crops were also determined. Two mitigation techniques that could be used to remediate Cd, Pb and Zn contamination were investigated. The first mitigation method included immobilization of heavy metals as phosphate complexes by using a triple super phosphate fertilizer, while the second method involved mobilisation and thus leaching of heavy metals away from plant roots using EDTA. These mitigation methods were tested in a pot experiment using cabbage as the experimental crop and soil from these areas as growth medium. A survey of common farming practices in these two areas and farmers willingness to use remediation methods was conducted. / South Africa

В данной работе проведено исследование переработки мышьяксодержащих шламов нейтрализации отработанных электролитов с целью селективного извлечения ценных металлов (медь, никель). Для определения химического и фазового анализа техногенного многокомпонентного сырья применены методы спектрофотометрии (AAС) и рентгенофазовой дифрактоскопии. Предложен выщелачивающий комплексообразующий реагент Трилон Б и обоснован его выбор. Проведены литературный обзор современных методов переработки, лабораторные исследования. Исследованы и оптимизированы процессы выщелачивания шламов водным раствором Трилона Б, очистки полученного трилонатного раствора от металлов-примесей, регенерации растворителя. Так же в диссертации выбрана оптимальная схема переработки гидроксидных шламов и отражено эколого-экономическое обоснование выбранной технологии переработки. / In this paper, research arsenic-containing slimes of neutralization of waste electrolytes was carried out to selectively extract valuable metals (copper, nickel). The method of Atomic Absorption Spectroscopy (AAS), X-ray Diffraction (XRD) was applied. The chemical and phase analysis of multicomponent manmade waster was carried out, the leaching chelating reagent Trilon B was offered and its choice is reasonable. A review of modern methods of processing and laboratory studies were carried out. The processes of leaching of slimes by aqueous solution of Trilon B, purification of the obtained trilonate solution from metal-impurities and solvent regeneration were studied and optimized. Also, in the thesis the optimal scheme of processing of hydroxide sludges was chosen and the ecological and economic justification of the chosen technology of processing was represented.

The duodenal epithelium is regularly exposed to HCl, digestive enzymes, bacteria and toxins, and sometimes also to ethanol and drugs. The imbalance of aggressive factors in the intestinal lumen and mucosal barrier function increases the risk of tissue injury and inflammation. The key components of the duodenal barrier function include mucosal permeability, bicarbonate transport and the secretion or absorption of fluids. This thesis aims to elucidate the role of melatonin, neuropeptide S (NPS) and short chain fatty acids (SCFAs) in the regulation of intestinal mucosal barrier function and motility in the anesthetized rat in vivo and in tissues of human origin in vitro. Melatonin was found to reduce ethanol-induced increases in paracellular permeability and motility by a neural pathway within the enteric nervous system involving nicotinic receptors. In response to luminal exposure of ethanol, signs of mild mucosal edema and beginning of desquamation were observed in a few villi only, an effect that was not influenced by melatonin. Melatonin did not modify increases in paracellular permeability in response to luminal acid. NPS decreased basal and ethanol-induced increases in duodenal motility as well as bethanechol stimulated colonic motility in a dose-dependent manner. Furthermore, NPS was shown to inhibit basal duodenal bicarbonate secretion, stimulate mucosal fluid absorption and increase mucosal paracellular permeability. In response to luminal exposure of acid, NPS increased bicarbonate secretion and mucosal paracellular permeability. All effects induced by the administration of NPS were dependent on nitrergic pathways. In rats, administration of NPS increased the tissue protein levels of the inflammatory biomarkers IL-1β and CXCL1. Immunohistochemistry showed that NPS was localized at myenteric nerve cell bodies and fibers, while NPSR1 and nNOS were only confined to the myenteric nerve cell bodies. Perfusing the duodenal segment with the SCFAs acetate or propionate reduced the duodenal mucosal paracellular permeability, decreased transepithelial net fluid secretion and increased bicarbonate secretion. An i.v. infusion of SCFAs reduces mucosal paracellular permeability without any effects on mucosal net fluid flux. However, it significantly decreased bicarbonate secretion. Luminal SCFAs changed the duodenal motility pattern from fasting to feeding motility while i.v. SCFAs was without effect on motility. The systemic administration of glucagon-like peptide-2 (GLP-2) induced increases in mucosal bicarbonate secretion and fluid absorption. An i.v. GLP-2 infusion during a luminal perfusion of SCFAs significantly reduced the duodenal motility. In conclusion, the results in the present thesis show that melatonin, NPS and SCFAs influence the neurohumoral regulation of intestinal mucosal barrier function and motility. Aberrant signaling in response to melatonin, NPS and to luminal fatty acids might be involved in the symptom or the onset of disease related to intestinal dysfunction in humans. / <p>Research funders and strategic development areas:</p><p>- Bengt Ihre Foundation (grant SLS-177521)</p><p>- Socialstyrelsen(grant SLS-176671)</p><p>- Erik, Karin, and Gösta Selanders Foundation</p><p>- Emil and Ragna Börjesson Foundation</p><p>- Uppsala University </p><p>- Ministry of Education of Malaysia</p><p>- Universiti Malaysia Sabah, Malaysia</p>

Characterising the geochemistry and speciation of major contaminant radionuclides is crucial in order to understand their behaviour and migration in complex environmental systems. Organic complexing agents used in nuclear decontamination have been found to enhance migration of radionuclides at contaminated sites; however, the mechanisms of the interactions in complex environments are poorly understood. In this work, radionuclide speciation and sorption behaviour were investigated in order to identify interactions between four key radionuclides with different oxidation states (Cs(I) and Sr(II) as important fission products; Th(IV) and U(VI) as representative actinides), three anthropogenic organic complexing agents with different denticities (EDTA, NTA and picolinic acid as common co-contaminants), and natural sand (as simple environmental solid phase). A UV spectrophotometric and an IC method were developed to monitor the behaviour of EDTA, NTA and picolinic acid in the later experiments. The optimised methods were simple, applied widely-available instrumentation and achieved the necessary analytical figures of merit to allow a compound specific determination over variable background levels of DOC and in the presence of natural cations, anions and radionuclides. The effect of the ligands on the solubility of the radionuclides was studied using a natural sand matrix and pure silica for comparison of anions, cations and organic carbon. In the silica system, the presence of EDTA, NTA and, to a lesser extent, picolinic acid, showed a clear net effect of increasing Th and U solubility. Conversely, in the sand system, the sorption of Th and U was kinetically controlled and radionuclide complexation by the ligands enhanced the rate of sorption, by a mechanism identified as metal exchange with matrix metals. Experiments in which excess EDTA, NTA and picolinic acid (40 – 100 fold excess) were pre-equilibrated with Th and U prior to contact with the sand, to allow a greater degree of radionuclide complex formation, resulted in enhanced rates of sorption. This confirmed that the radionuclide complexes interacted with the sand surface more readily than uncomplexed Th or U. Overall this shows that Th and U mobility would be lowered in this natural sand by the presence of organic co-contaminants. In contrast, the complexation of Sr with the complexing agents was rapid and the effect of the ligands was observed as a net increase on Sr solubility (EDTA, picolinic acid) or sorption (NTA). As expected, Cs did not interact with the ligands, and showed rapid sorption kinetics. Finally, ESI-MS was used to study competitive interactions in the aqueous Th-Mn-ligand ternary system. Quantification presented a challenge, however, the careful approach taken to determine the signal correction allowed the competitive interactions between Mn and Th for EDTA to be studied semi-quantitatively. In an EDTA limited system, Th displaced Mn from the EDTA complex, even in the presence of a higher Mn concentration, which was consistent with the higher stability constant of the Th-EDTA complex.

Le but de ce travail de mémoire était d'explorer des moyens pour augmenter la perméabilité des biofilms de Streptococcus mutans aux macromolécules en utilisant des agents potentiellement perturbateurs de la structure des biofilms. L’acide éthylènediamine tétraacétique (EDTA) ainsi que l’acide acétylsalicylique (aspirine) sont les agents perturbateurs choisis. Le changement de perméabilité des biofilms de S. mutans a été déterminé en mesurant les coefficients de diffusion globale du polyéthylène glycol (PEG) et de diffusion locale de dextrans. Les coefficients de diffusion globale ont été mesurés par spectroscopie infrarouge avec un échantillonnage par réflexion totale atténuée (ATR) alors que la spectroscopie par corrélation de fluorescence (SCF) a été utilisée pour la mesure des coefficients de diffusion locale. Les résultats ont démontré que l’incorporation de l’EDTA à une concentration de 7.5 (m/v) % dans la solution de diffusion permet d’améliorer les propriétés de transport du PEG dans les biofilms en augmentant sa pénétrabilité et son coefficient de diffusion globale. Par contre, aucune variation n’a été constatée dans la valeur du coefficient de diffusion locale de dextran fluorescent. Cette différence peut être expliquée, entre autres, par l'échelle des mesures et la nature différente des molécules diffusantes. L’aspirine n’a démontré aucun effet sur le transport du PEG à travers les biofilms de S. mutans. La pénétration accrue du PEG en présence de l’EDTA a été corrélée aux tests de viabilité des cellules bactériennes. En effet, la combinaison de la pénicilline G (PenG) avec l’EDTA 2 (m/v) % a eu comme effet l’augmentation du pouvoir biocide d’un facteur 3. De plus, les images de microscopie à épifluorescence et de microscopie confocale à balayage de laser ont démontré que les bactéries dans le cœur des microcolonies sont plus affectées par la PenG lorsque le milieu contient de l'EDTA. A la lumière des résultats obtenus, il s’avère que l’incorporation d'agents perturbateurs de la structure des biofilms est une option sérieuse à considérer dans l’éradication des biofilms microbiens. Plus d’études devront être effectuées afin d’investiguer l’effet d’autres molécules possédant les propriétés perturbatrices de la structure des biofilms sur la résistance de ces derniers aux agents antimicrobiens. / The aim of this study was to investigate the role of biofilm structure disrupting potential agents in the biofilm permeability to macromolecules. The effect of ethylenediamine tetraacetic (EDTA) and acetylsalicylic acid (aspirin), two potential disrupting agents, on the diffusion of poly (ethylene glycol) (PEG) and dextran in Streptococcus mutans biofilms was investigated. Attenuated total reflection (ATR) infrared spectroscopy was used to measure the global diffusion coefficients, while the local diffusion coefficients were measured using fluorescence correlation spectroscopy (FCS). On one hand, the results showed that EDTA, at a concentration of 7.5 (w/v) %, increased PEG penetrability and global diffusion coefficient in biofilms. No effect was noticed for the local diffusion coefficient of fluorescent dextran molecules. This difference was associated with, amongst others, the scale of the measurements and the different nature of the diffusing species. On the other hand, aspirin had no effect on the S. mutans biofilm permeability for PEG. The enhanced penetration of PEG in the presence of EDTA was correlated with bacterial cell viability. The bactericidal effect of penicillin G (PenG) alone and in combination with EDTA, was assessed for the biofilms. The results showed that antibiotic effect of PenG was improved by a factor of 3 when the antibiotic was used in combination with EDTA compared to the same antibiotic used alone. Moreover images obtained by epifluorescence microscopy and laser scanning confocal microscopy indicated that the bacteria in the core of the microcolonies were more affected by PenG when the milieu contained EDTA. These results revealed that the use of disrupting agents of biofilm structure is a promising approach to eradicate biofilms showing resistance to classical antimicrobial agent treatments. More studies should be done to investigate the effect of others potentials disrupting agents on the biofilm permeability to macromolecules.

The novel compound, [Rh2(N-{2,4,6-CH3}C6H2)COCH3)4] was synthesized. Crystal structures of [Rh2(N-{2,4,6-CH3}C6H2)COCH3)4]·2NCC6H5 and Ba1.5[Fe(C10H13N2O7)][Co(CN)6]·9H2O were determined employing a Rigaku Mercury375R/M CCD (XtaLAB mini) diffractometer with graphite monochromated Mo-Kα radiation. For [Rh2(N-{2,4,6-CH3}C6H2)COCH3)4]·2NCC6H5, the space group was P-421c(#114) with unit cell dimensions: a =11.0169(14)Å, c =21.499(3)Å, V = 2609.4(6)Å3. Each rhodium had approximately octahedral coordination and was bound to another rhodium atom, two nitrogens (trans to each other), two oxygens (trans to each other), and one benzonitrile nitrogen (trans to rhodium). For Ba1.5[Fe(C10H13N2O7)][Co(CN)6]·9H2O the space group was: P-1(#2) with unit cell dimensions: a=13.634Å, b=13.768Å, c=17.254Å and α=84.795°, β=87.863°, γ=78.908°, V=3164.5Å3. The iron atom (nearly octahedral) was coordinated to one chelating ligand (derived from ethylenediaminetetraacetic acid) and the nitrogen of a cyanide ligand. The carbon of the cyanide ligand was bound to cobalt (octahedral). Thus, the cyanide ligand serves as a bridge between the two metals.

<p>This thesis is a summary of five papers with focus on adsorption processes of various monocarboxylates and aminocarboxylates at the water/goethite interface. Interaction of organic acids at the water/mineral interfaces are of importance in biogeochemical processes, since such processes have potential to alter mobility and bioavailability of the acids and metal ions.</p><p>In order to determine the coordination chemistry of acetate, benzoate, cyclohexanecarboxylate, sarcosine, MIDA (methyliminediacetic acid), EDDA (ethylenediamine-N,N’-diacetic acid) and EDTA (ethylenediamine-N,N’-tetraacetic acid) upon adsorption to the goethite (alpha-FeOOH) surface, a combination of quantitative measurements with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized.</p><p>Over the pH range studied here (pH 3- 9) all ligands, except for sarcosine, have been found to form surface complexes with goethite. In general, theses were characterized as outer sphere surface complexes i.e. with no direct interaction with surface Fe(III) metal ions. Furthermore, two types of different outer-sphere complexes were identified, the solvent-surface hydration-separated ion pair, and hydration-shared ion pair. For the monocarboxylate surface complexes distinction between these two could be made. At high pH values the solvent-surface hydration-separated ion pair was the predominating complex, while at low pH the surface complex is stabilized through the formation of strong hydrogen bonds with the goethite surface. However, it was not possible to clearly separate between the two outer-sphere complexes for coordination of the aminocarboxylates with the surface of goethite. Additionally, EDDA also formed an inner-sphere surface complex at high pH values. The EDDA molecule was suggested to coordinate to the surface by forming a five membered ring with an iron at the goethite surface, through the amine and carboxylate groups.</p><p>Contrary to the other ligands studied, EDTA significantly induced dissolution of goethite. Some of the dissolved iron, in the form of the highly stable FeEDTA- solution complex, was indicated to re-adsorb to the mineral surface as a ternary complex. Similar ternary surface complexes were also found in the Ga(III)EDTA/goethite system, and quantitative and spectroscopic studies on adsorption of Ga(III) in presence and absence of EDTA showed that EDTA considerably effects speciation of gallium at goethite surface.</p><p>The collective results in this thesis show that the affinity of these ligands for the surface of goethite is primarily governed by their chemical composition and structure, and especially important are the types, numbers and relative position of functional groups within the molecular structure.</p>

Waste water containing high concentrations of dissolved metals were delivered to the environmental company SAKAB. After standard treatment procedure, involving regulation of pH and addition of flocculation agents, the water still contained nickel concentrations of 26 mg/l. Since SAKAB’s regulatory concentration limit value for nickel in outgoing water is 0.5 mg/l, further treatment was necessary. According to the supplier of the water, a complexing agent similar to EDTA had been added to the water. The aim of this study was to decrease concentrations of nickel, zinc and copper. One part of this study was the precipitation experiments as hydroxide, sulphide and adsorption to hydrous ferric oxide. The other part was adsorption to natural, organic materials such as peat, wood chips and one commercial bark compost. Adsorption to hydrous ferric oxide was the most efficient of the precipitation experiments. When 2000 mg FeCl3 was added to 100 ml waste water and pH of the solution was adjusted to pH 8, a decrease up to 74 % of total nickel concentrations was achieved. Most efficient of the adsorption experiments were the one with commercial bark compost which decreased nickel concentrations in solution up to 94 % after 20 hours of agitation.

The aim of this study was to evaluate the influence of different endodontic irrigants on the cohesive and flexural strength of the root dentin. One hundred of bovine incisor roots were selected, instrumented and randomly divided into 10 experimental groups (n = 10), according to the irrigation solution used: Control - physiological solution; N1 - sodium hypochlorite 1.0%; N5 - sodium hypochlorite 5.25%; N1EDTA - sodium hypochlorite 1.0% associate to EDTA 17%; N5EDTA - sodium hypochlorite 5.25% associate to EDTA 17%; Sclx chlorhexidine gluconate solution 2.0%; Gclx - chlorhexidine gluconate gel 2.0%; SclxEDTA - chlorhexidine gluconate solution 2.0% associate to EDTA 17%; GclxEDTA - chlorhexidine gluconate gel 2.0% associate to EDTA 17% and EDTA - EDTA 17%. The roots were axially sectioned in two halves. Half of them were used for the microtensile cohesive strength test: six 1.0mm thick slices were trimmed to produce hourglass shaped samples with a test area of 1mm2. The other halves were used in a 3-point bend flexural strength by means of dentine bars with 1X1X12 mm. Each sample remained two hours in contact with the irrigant solutions, except for EDTA, which remained for five minutes. After irrigants treatment, samples were rinsed with distilled water, and tested. Specific devices for each test were used, in a universal testing machine with a load cell of 20Kgf, and a crosshead speed of 0.5 mm/minute. Date were recorded and statistically analyzed with one-way ANOVA and Tukey test. Significant reduction in the ultimate cohesive strength and flexural strength was verified only for the groups that used sodium hypochlorite irrespective of the concentration and additional solution, differing significant from the group control. The use of chlorhexidine and EDTA separately did not cause alteration in the mechanical properties of root dentine. / O objetivo desse estudo foi avaliar a influência de diferentes irrigantes endodônticos na resistência coesiva e flexural da dentina radicular. Cem raízes de incisivos bovinos foram selecionadas, instrumentadas e divididas aleatoriamente em 10 grupos experimentais (n= 10), de acordo com a substância irrigadora utilizada: Controle - solução fisiológica; N1 - hipoclorito de sódio a 1,0%; N5 - hipoclorito de sódio a 5,25% ; N1EDTA - hipoclorito de sódio a 1,0% associado à EDTA a 17%; N5EDTA - hipoclorito de sódio a 5,25% associado à EDTA a 17%; Sclx - solução de gluconato de clorexidina a 2,0%; Gclx - gel de gluconato clorexidina a 2,0%; SclxEDTA - solução de gluconato clorexidina 2,0% associado à EDTA a 17%; GclxEDTA - gel de gluconato clorexidina a 2,0% associado à EDTA a 17% e EDTA - EDTA a 17%. As raízes foram axialmente seccionadas em duas metades. Uma metade foi utilizada para ensaio de microtração, da qual foram obtidas seis fatias de 1,0mm de espessura que receberam constrições na face externa, determinando área de teste de 1mm2. A outra metade foi utilizada no ensaio de flexão de 3-pontos, da qual foi extraída uma barra de dentina com dimensões de 1X1X12 mm. Cada amostra permaneceu duas horas em contato com a substância irrigante endodôntica com exceção do EDTA, que atuou por cinco minutos. Após o tratamento com os irrigantes, procedeu-se a lavagem com água destilada, e em seguida executados os ensaios mecânicos. Foram utilizados dispositivos específicos para cada ensaio, acoplados à máquina de ensaio mecânico, utilizando célula de carga de 20Kgf, com velocidade de 0,5 mm/minuto até a fratura da amostra. Os dados obtidos foram submetidos à análise de variância e teste Tukey. Verificou-se redução significativa na resistência máxima coesiva e flexural apenas para os grupos que empregaram o hipoclorito de sódio independe da concentração e associação com outra substância, diferindo estatisticamente do grupo controle. O uso de clorexidina e EDTA isoladamente não alterou as propriedades mecânicas da dentina radicular. / Mestre em Odontologia