Sabe-se que o flúor causa alterações químicas e celulares no osso, dependendo da dosagem e do tempo de exposição a esse elemento. Já foi demonstrado que alterações clínicas importantes, como a osteoporose, osteopetrose e esclerose óssea, podem ser geradas pela ingestão de flúor. Sabe-se que o flúor pode guiar os osteoblastos ao crescimento, sob doses e tempos de exposição específicos. A sensibilidade dos tecidos mineralizados ao fluoreto responde a mecanismos genéticos inerentes a cada população. Dentro de uma mesma espécie, diferentes linhagens apresentam um comportamento distinto frente a esse fármaco. Durante várias décadas, os estudos com fluoretos resumiram-se ao fluoreto de sódio, amplamente utilizado na prevenção das cáries dentárias. Recentemente, outras fontes de fluoretos como TiF4 e SnF2 têm sido buscadas, com intuito de potencializar as vantagens desse elemento. Porém não existem estudos ainda sobre o efeito do AlF3 sobre o tecido ósseo até a presente data. Desse modo, achamos oportuno investigar seu papel, quando administrado a células ósseas e para tal, investigamos a viabilidade e padrão de atividade das fosfatases desse sal (AlF3) quando administrado às células da linhagem pré-osteblástica MC3T3, em comparação ao NaF. Além disso, sabendo que diferentes células apresentam comportamento distinto ao tratamento com fluoretos, estudamos o papel do NaF quando administrado a duas linhagens celulares de camundongos com densidades ósseas distintas e com diferentes susceptibilidades ao fluoreto: C3H/HeJ e C57BL/6J (C3H e C57, alta e baixa densidades ósseas, respectivamente). As células também foram avaliadas quanto à viabilidade celular e ao perfil das fosfatases. Todos os resultados foram submetidos à Análise de Variância a três critérios e nos permitiu identificar que entre os sais de fluoreto, apenas o NaF promoveu alterações na viabilidade celular das células MC3T3. O AlF3 não exerceu influência na atividade da fosfatase alcalina quando consideramos as células pré-osteoblásticas, no entanto, o efeito desse fluoreto sobre a atividade das fosfatases ácidas totais e ácida resistente ao tartarato ocorre de modo dicotômico. Quando consideramos uma população celular heterogênea, coletada de calvária, como foi o caso das linhagens C3H e C57, verificamos que o NaF interferiu tanto sobre a proliferação, quanto a atividade das fosfatases de modo bastante distinto para ambas linhagens celulares. Assim concluimos que o NaF é capaz de exercer efeitos mais diversificados em diferentes tipos celulares, alterando viabilidade celular e atividade de enzimas; em contrapartida, o AlF3 produz efeitos mais especifícos e delimitados em pré-osteoblastos. / It is well known that fluoride causes chemical and cellular alteration on bone tissue, depending on the dosage and time of exposure to this element. Several studies have been conducted to show that some bone diseases, such as osteoporosis, osteopetrosis and esclerosis, can occur as a consequence of the excessive fluoride uptake. Fluoride can lead osteoblast to proliferate, under certain conditions as time and dosage. The same way, excessive dosages of fluoride can alter protein activity in osteoblasts, by changing the expression of retated genes. Sensitivity of mineralized tissues to fluoride depends on a genetic background inherent to each population. Within the same specie, different lineages present distint behavior to the ingestion of this íon. Over several decades, many researches focused on the study of NaF as the only source of fluoride, once it is wide spread used to the prevention of dental caries. More recently, different sources of fluoride have been assessed, like TiF4 e SnF2</sub, with the main aim to enhance biochemical and physical benefits of this element. Despite of this, none of these formulations have been tested to evaluate their effect on the bone tissue. Thus, we believe it is advisable to investigate viability and phosphatases activities of pre-osteoblast MC3T3 cells treated with Aluminium fluoride, compared to NaF treatments. Besides this, facing the knowledge that different cell lines have distinct behavior when treated with fluoride, we used two inbred strains of mice with distint mineral bone densities, C3H/HeJ (C3H, high bone density) and C57BL/6J (C57, low bone density), to assess the viability and phosphatases activities after the treatment with NaF. Overall results were tested by 3 way- Anova. AlF3 did not exibit influence over on alkaline phosphatase when pre-osteoblast cells are considered, but the effect of this fluoride salt on the activity of total and tartarate resistant acid phosphatases ocurrs on a dicotomic way. When we consider a mixed cell population, collected from calvária as for the C3H and C57 assays, NaF did interfered as with the proliferation rate as phosphatase activities on a very distinct fashion between the two lineages. Thus, it is possible to conclude that NaF is able to exert variable effects in different cell types and enzyme activities; on the other hand, AlF3 effects are more specific and surrounded in pre-osteblastic cells.

Este estudo teve como objetivo avaliar do efeito da aplicação tópica de um verniz e solução experimental de TiF4, comparando-os ao verniz e solução de NaF, sobre o processo de des-remineralização do esmalte dentário in situ. Para tal, 132 blocos de esmalte bovino (4x4mm) foram selecionados pela microdureza de superfície, sendo que em metade deles foi produzida lesão de cárie artificial em solução desmineralizante (pH 5,0, 6 dias). Na seqüência, foi determinada a microdureza de superfície pós-lesão. A outra metade dos blocos permaneceu hígida. Onze voluntários participaram de 3 fases cruzadas (14 dias cada, washout de 7 dias), boca-dividida e cegas, nas quais utilizaram aparelhos palatinos com 4 amostras de esmalte por fase (2 hígidas e 2 desmineralizadas), sendo que cada tipo de amostra recebeu um tipo de tratamento (verniz ou solução). Em todas as amostras permitiu-se o acúmulo de placa dentária. Em uma fase (Fase A), foram aplicados agentes a base de NaF a 5,42% (2,45% F- e pH 5,0), em outra fase (Fase B), foram utilizados agentes a base de TiF4 a 4% (2,45% F- e pH 1,0), e na última fase (Fase C) foram utilizados agentes placebos (verniz sem flúor pH 5,0 e sem tratamento). Os tratamentos foram realizados in vitro (verniz-6 h e solução-1 minuto). Durante o período in situ, os voluntários aplicaram solução de sacarose a 20%, 8x5min ao dia, sobre os blocos hígidos, para provocar a desmineralização. Já para os blocos desmineralizados nenhum procedimento foi realizado, para permitir a remineralização. A microdureza de superfície final foi realizada, para o cálculo da porcentagem de variação de microdureza de superfície, assim como a microdureza longitudinal e microradiografia transversal, para o cálculo das perdas de microdureza e volume mineral integradas, respectivamente. Os dados foram submetidos à ANOVA-RM/ Tukey-Kramer, teste t pareado e ANOVA a dois critérios/Bonferroni (p<0,05). Houve uma redução significativa da desmineralização superficial e um aumento significativo da remineralização superficial do esmalte in situ pelos tratamentos com verniz e solução de TiF4, em comparação aos controles. Pôde-se constatar ainda que os tratamentos com o verniz de NaF, verniz de TiF4 e solução de TiF4 foram efetivos na redução da desmineralização subsuperficial in situ. No entanto, observou-se que o protocolo experimental não permitiu uma adequada remineralização de subsuperfície in situ. Com base nos resultados, pode-se concluir que o verniz e a solução de TiF4 parecem ser promissores na prevenção da desmineralização, porém em relação à remineralização mais estudos in situ são necessários. / The aim of this study was to evaluate the effect of the experimental TiF4 varnish and solution, comparing with NaF solution and varnish, on dental enamel de-remineralization in situ. For that, 132 bovine enamel samples (4x4 mm) were selected using surface microhardness, and half of them were submitted to artificial caries lesion formation using a demineralizing solution (pH 5.0, 6 days). The surface microhardness after the demineralization was measured. The other half of the samples remained sound. Eleven volunteers took part in this cross-over, split-mouth and double-blind study performed in 3 phases of each 14 days (washout of 7 days). Four enamel samples were worn in palatal appliances (2 sound and 2 demineralized), being each type of sample submitted to one treatment (varnish or solution). The dental plaque accumulation was allowed on all samples. In phase A, 5.42% NaF varnish/solution was applied (2.45% F-, pH 5.0); in phase B, 4% TiF4 varnish/solution was used (2.45% F-, pH 1.0) and at the last phase (phase C) the placebo treatments were performed (placebo varnish pH 5.0 and no-treatment). The treatments were performed in vitro (varnish-6h and solution-1min). During the in situ phase, the volunteers dripped a solution containing 20% weight/volume (w/v) sucrose on the sound samples for 5 min, 8 times a day, to provoke demineralization. While on the demineralized samples nothing was done, in order to allow remineralization. The final surface microhardness was analyzed for the calculation of the % of surface microhardness change, as well as the cross-sectional hardness and the transversal microradiography, for the calculation of the integrated loss of microhardness and mineral volume, respectively. The data were submitted to RM-ANOVA/ Tukey-Kramer, t test and 2-way ANOVA/ Bonferroni (p<0.05). There was a significant reduction of the surface enamel demineralization and increase of surface remineralization by the treatments with TiF4 varnish and solution compared to control in situ. The treatments with NaF varnish, TiF4 varnish and solution were able to reduce the subsurface demineralization in situ. However, the experimental protocol did not allow the subsurface remineralization in situ. Based on the results, it can be concluded that the TiF4 varnish and solution seem to be promising products for preventing demineralization, but for the remineralization more studies need to be conducted.

Apesar de diversos estudos demonstrarem resultados promissores da utilização da solução de AmF/NaF/SnCl2 na inibição da progressão da lesão de erosão dental, medidas que visam melhorar ainda mais sua eficácia são fundamentais. Sendo assim, este estudo in vitro e in situ se propôs a avaliar se o efeito protetor dessa solução pode ser potencializado pelo aumento da frequência de uso. Para tanto, foram obtidas, a partir de terceiros molares humanos hígidos, sessenta amostras de esmalte dental humano para o estudo in vitro (4 X 4 X 1 mm), e noventa e seis para o in situ (3 X 3 X 1 mm). Após a formação de lesão erosiva incipiente nas amostras in vitro, (ácido cítrico a 1%, pH 4,0, durante 3 minutos), estas foram divididas nos 5 grupos de tratamentos (n=12): G1 - água destilada (controle negativo); G2 - solução de NaF (controle positivo) 1x/dia; G3 - solução de NaF (controle positivo) 2x/dia; G4 - solução de AmF/NaF/SnCl2 1x/dia; G5 - solução de AmF/NaF/SnCl2 2x/dia. As amostras foram então submetidas a 5 dias de ciclagem erosiva através de 6 imersões diárias de 2 minutos em solução de ácido cítrico (0,05M, pH 2.6). Ao final da ciclagem erosiva, foi realizada a determinação do desgaste de superfície por meio de Perfilometria óptica. Para realização do desafio erosivo in situ, as amostras também foram submetidas à formação da lesão incipiente, com a mesma metodologia do in vitro. Doze voluntários participaram do estudo in situ e cruzado, dividido em quatro fases de 5 dias cada, os quais utilizaram um dispositivo removível inferior unilateral contendo 2 amostras de esmalte dental humano erodido, que foram trocadas a cada fase. As amostras foram divididas em 4 grupos de tratamentos (n=12), os mesmos utilizados na etapa in vitro, com exceção do grupo da solução de NaF 2x/dia. Durante a fase experimental in situ o dispositivo contendo as amostras foi submetido à ciclagem erosiva (ex vivo) semelhante à etapa in vitro. Ao final de cada fase experimental in situ, as amostras foram removidas do dispositivo e analisadas através de perfilometria, e foram consideradas as médias das amostras em duplicata para a análise estatística. A ANOVA mostrou que o desgaste superficial foi afetado pelos tratamentos avaliados tanto in vitro quanto in situ (p?0,001), com nível de significância de 5%. No estudo in vitro, o teste de Tukey demonstrou que não houve diferença entre os grupos de aplicação do NaF 1 (16,21 ±1,56) ou 2 vezes (15,39 ±1,01), que apresentaram redução limitada no desgaste quando comparado ao grupo da água destilada (20,36 ±1,56); já entre os grupos da solução AmF/NaF/SnCl2 houve diferença entre aplicação 1 (10,40 ±2,36) e 2 vezes (7,27 ±3,29), e que apesar de ambos demonstrarem redução significativa da perda de substrato, o aumento da frequência aumentou este potencial anti-erosivo. Na parte in situ, a solução de NaF não demonstrou capacidade de reduzir o desgaste, e apesar de não ter havido diferença significante entre os grupos AmF/NaF/SnCl2 1 (2,64 ±1,55) e 2 vezes (1,34 ±1,16), esta solução foi eficaz na redução do desgaste erosivo em comparação aos grupos NaF (4,59 ±2,13) e água destilada (4,55 ±2,75). A solução de AmF/NaF/SnCl2 demostrou se eficaz em proteger o esmalte da progressão da erosão dental, e o aumento da frequência potencializou seu efeito anti-erosivo tanto in vitro, quanto in situ. / Although several studies have shown promising results using the AmF/NaF /SnCl2 solution in inhibiting the progression of dental erosion, measures to further improve its effectiveness are fundamental. Thus, this in vitro and in situ study aimed to evaluate if the protective effect of this solution can be enhanced by increasing the frequency of use. Human enamel samples were obtained from sound human third molars; sixty for the in vitro study (4 x 4 x 1 mm), and ninety-six for the in situ (3 X 3 X 1 mm) study. After the formation of incipient erosive lesions, the in vitro samples (1% citric acid, pH 4.0, for 3 minutes), were divided into 5 treatment groups (n = 12): G1 - distilled water (negative control); G2 - NaF solution (positive control) 1x/day; G3 - NaF solution (positive control) 2x/day; G4 - AmF/NaF/SnCl2 solution 1x/day; G5 - AmF/NaF/SnCl2 solution 2x/day. The samples were then subjected to 5 days of erosive cycling through 6 daily immersions (2 minutes each) in citric acid solution (0.05 M, pH 2.6). At the end of erosive cycling, surface wear was determined by means of optical profilometry. To perform the in situ erosive challenge, the samples were also subjected to the formation of incipient lesion with the same methodology of the in vitro study. Twelve volunteers participated in the crossover in situ study - divided into four phases of 5 days each - and used a unilateral lower removable device containing 2 samples of eroded human enamel, which were changed at each phase. The samples were divided into 4 treatment groups (n = 12), the same considered for the in vitro phase, with the exception of the group of NaF solution 2x/day. During the in situ experimental phase, the device containing the sample was subjected to the erosive cycling (ex vivo), similar to the in vitro phase. At the end of each in situ experimental phase, the samples were removed from the device and analyzed by profilometry, and the average of duplicate samples were considered for statistical analysis. The ANOVA showed that the surface wear was affected by treatments evaluated in both in vitro and in situ (p?0,001) studies. In the in vitro study, the Tukey test showed no difference between the application of groups of NaF 1 (16.21 ±1.47) or 2 times (15.39 ±1.01), which showed limited reduction in wear compared to the distilled water group (20.36 ±1.56). Among the groups of AmF/NaF/SnCl2 solution, there was no difference between 1 (10.40 ±2.36) and 2 application times (7.27 ±3.29), and, although both demonstrated significantly reduced tissue loss, increasing the frequency has increased its anti-erosive potential. In the in situ phase, the NaF solution did not reveal the ability to reduce surface wear, and although there was no significant difference between the AmF/NaF/SnCl2 1 (2.64 ±1.55) and 2 times groups (1.34 ±1.16), this solution was effective in reducing the erosive wear compared to groups NaF (4.59 ±2.75) and distilled water (4.55 ±2.75). The AmF/NaF/SnCl2 solution shown to be effective in protecting the enamel progression of dental erosion, and increasing the frequency potentiate its anti-erosive effect both in vitro and in situ.

L’uranium hexafluoré (UF6), seul composé d’uranium volatil à basse température, est utilisé industriellement pour enrichir isotopiquement l’uranium afin de produire du combustible nucléaire. Cette thèse s’intéresse à trois problématiques rencontrées industriellement lors de la production d’UF6 : Celui-ci est synthétisé par l’action de fluor gazeux sur du tétrafluorure d’uranium (UF4) à haute température. Selon les conditions, cette réaction peut s’accompagner de la formation de fluorures dont la composition se situe entre UF4 et UF6, appelés fluorures d’uranium intermédiaires tels que UF5, U2F9 et U4F17 et qui viennent polluer les installations industrielles. Cette thèse permet de compléter le diagramme d’Agron qui définit les zones de stabilité des fluorures intermédiaires en fonction de la température et de la pression en UF6. Elle montre l’importance de la morphologie du solide utilisé et confirme la formation d’un nouveau fluorure intermédiaire de formule U4F19. Les fluorures d’uranium peuvent aussi former des composés en présence de polluants tels que les métaux alcalins. Les composés formés de fluorures de métaux alcalins (NaF et KF) et de tétrafluorure d’uranium ont été synthétisés. Leur fluoration par le fluor gazeux (F2) et l’UF6 a montré une oxydation de l’uranium jusqu’au degré d’oxydation V ou VI. Dans ce dernier cas de l’UF6 gazeux est produit ; mais la dissociation totale de l’uranium et de son fluorure alcalin n’a pas été observée. Enfin l’hexafluorure d’uranium est un puissant agent de corrosion notamment parce qu’il peut se dismuter et libérer du fluor. Une étude de fluoration par le fluor gazeux (F2) sur des nuances d’aciers inoxydables enrichis ou non en nickel et monel (70% Ni, 30% Cu) permet de mettre en évidence la faible résistance de ces aciers. Seul le monel présente une résistance accrue, confirmée par des essais de corrosion par UF6 qui mettent en évidence l’importance de la couche de passivation NiF2, formée par F2 avant l’attaque par UF6. Pour terminer, des études structurales réalisées à partir de diffraction des rayons X sur monocristal de composés uranifères utilisés au cours de ces études (UF4, UF5, Na7U6F31, Na7U2F15) permettent d’affiner la connaissance de ces composés. / Uranium hexafluoride (UF6), the only uranium compound volatile at low temperature, is used industrially for isotopical enrichment of uranium to produce nuclear fuel. This dissertation addresses three problems encountered industrially in the production of UF6 : It is synthesized by the action of fluorine gas (F2) on uranium tetrafluoride (UF4) at high temperature. Depending on conditions, this reaction may be accompanied by the formation of fluorides whose composition is between UF4 and UF6, called intermediate uranium fluorides such as UF5, U2F9 and U4F17 which pollute industrial facilities. This dissertation will complete Agron’s diagram which defines the stability zones of intermediate fluorides as a function of temperature and pressure of UF6. It shows the importance of the morphology of the solid used and confirms the formation of a new fluoride intermediate which formula is U4F19. The uranium fluorides can also form compounds in the presence of contaminants such as alkali metals. The compounds formed of alkali metal fluorides (NaF and KF) and uranium tetrafluoride were synthesized. Their fluorination with fluorine gas (F2) and UF6 showed an oxidation of uranium to the oxidation state V or VI. In the latter case, the UF6 gas is produced, but the total dissociation of uranium from its alkali fluoride was not observed. Finally uranium hexafluoride is a powerful agent of corrosion in particular because it can dismute and release fluoride. A study of fluorination by fluorine gas (F2) on stainless steel grades enriched or not in nickel and Monel (70% Ni, 30% Cu) is used to highlight the low resistance of steels. Only monel has a high resistance, confirmed by corrosion tests by UF6 that highlight the importance of the passivation layer NiF2, formed by F2 before the attack by UF6. Finally, structural studies carried out using X-ray diffraction on single crystal of uranium compounds used in these studies (UF4, UF5 Na7U6F31, Na7U2F15) enhance the knowledge of these compounds.

The research described in this thesis is directed toward the efficient, enantioselective synthesis of chiral products that have useful functionality. This goal was pursued through catalytic asymmetric hydrogenation, a reaction class that selectively introduces one or two stereocenters into a molecule in an atom-efficient step. This reaction uses a small amount (often &lt;1 mol%) of a chiral catalyst to impart stereoselectivity to the product formed. Though catalytic asymmetric hydrogenation is not a new reaction type, there remain many substrate classes for which it is ineffective. The present thesis describes efforts to extend the reaction to some of these substrates classes. Some of the products synthesized in these studies may eventually find use as building blocks for the production of chiral pharmaceuticals, agrochemicals, or flavouring or colouring agents. However, the primary and immediate aim of this thesis was to develop and demonstrate new catalysts that are rapid and effective in the asymmetric hydrogenation of a broad range of compounds. Paper I describes the design and construction of two new, related chiral iridium compounds that are catalysts for asymmetric hydrogenation. They each contain an N,P-donating phosphinooxazoline ligand that is held together by a rigid bicyclic unit. One of these iridium compounds catalyzed the asymmetric hydrogenation of acyclic aryl imines, often with very good enantioselectivities. This is particularly notable because acyclic imines are difficult to reduce with useful enantioselectivity. The second catalyst was useful for the asymmetric hydrogenation of two aryl olefins. In Paper II, the class of catalysts introduced into Paper I is expanded to include many more related compounds, and these are also applied to the asymmetric hydrogenation of prochiral imines and olefins. By studying a range of related catalysts that differ in a single attribute, we were able to probe how different parts of the catalyst affect the yield and selectivity of the hydrogenation reactions. Whereas iridium catalysts had been applied to the asymmetric hydrogenation of imines and largely unfunctionalized olefins prior to this work (with varied degrees of success), they had not been used to reduce fluoroolefins. Their hydrogenation, which is discussed in Paper III, was complicated by concomitant defluorination to yield non-halogenated alkanes. To combat this problem, several iridium-based hydrogenation catalysts were applied to the reaction. Two catalysts stood out for their ability to produce chiral fluoroalkanes in good enantioselectivity while minimizing the defluorination reaction, and one of these bore a phosphinooxazoline ligand of the type described in Papers I and II. Enol phosphinates are another class of olefins that had not previously been subjected to iridium-catalyzed asymmetric hydrogenation. They do, however, constitute an attractive substrate class, because the product chiral alkyl phosphinates can be transformed into chiral alcohols or chiral phosphines with no erosion of enantiopurity. Iridium complexes of the phosphinooxazoline ligands described in Papers I and II were extremely effective catalysts for the asymmetric hydrogenation of enol phosphinates. They produced alkyl phosphinates from di- and trisubstituted enol phosphinate, β-ketoester-derived enol phosphinates, and even purely alkyl-substituted enol phopshinates, in very high yields and enantioselectivities.

In September 2000 water fluoridation became mandatory in South Africa. Since then water service providers like Umgeni Water (UW), a bulk water supply authority in the KwaZulu-Natal (KZN) province of South Africa began the process of implementing the legislation. This study was undertaken to establish the spatio-temporal variations of fluoride concentrations in surface and ground waters within the Umgeni Operational Area, to establish whether these waters would require fluoridation or defluoridation to meet a fluoride concentration of 0.70 mglf, and to assess the potential impacts of water fluoridation. Baseline fluoride concentrations of surface and ground water: It was concluded that the fluoride concentration of all sample types (rivers, dams, water works raw and final waters, wastewater influent and effluents, and boreholes), except pollution point sources, is less than O.S; mglR, 50 percent of the time. Some rivers (Mshazi, KwaNyuswa, KwaNgcolosi,·Mshwati and the MgoShongweni) exhibited high fluoride concentrations, while someboreholes also exhibited high fluoride concentrations. Temporal Variations and Seasonality: There are seasonal variations in the fluoride concentrations for surface waters, with higher fluoride concentrations in winter than in summer (64 out of 125 occasions). This low fluoride concentration in summer can be attributed to the dilution effects caused by rainfall runoff. Identification of "Hot Spots": "Hot Spots", sites where the fluoride concentration exceeds 1 mglR are present within the study area, for surface and borehole water. For surface water, the MgoShongweni exhibited fluoride concentrations in excess of 1mglRat least 75% of the time. The KwaNgcolosi and Mshwati exhibited fluoride concentrations In excess of 1mglR at least 25% of the time, while the Mshazi and the KwaNyuswa exhibited fluoride concentrations in excess of 1mglR only 5% of the time. The storm water discharge below AECI had high fluoride concentrations in excess of 1mg/R at least 20% of the time and the concentrations exceeded the fluoride concentration for seawater (1.4 mglf) at least 5% of the time. Of the 286 boreholes sampled, 17 boreholes (6% of all boreholes sampled) had fluoride levels in excess oft mglf . The impacts of long term consumption of water from these boreholes could range from slight mottling of the dental enamel in sensitive individuals (boretioles JD26, C29, H19, CB7, 112/1, 69/5, Thembeni 108 and EC (Thembeni 105, Keats Drift boreholes 1 and 2). Spatial patterns and possible sources of high fluoride concentrations: With respect to spatial patterns, relatively high concentrations of fluoride (300 IJglR to 1000 IJglR) can be found in surface water in the Msunduzi river, the Mgeni river downstream of the Msunduzi confluence and along the coastal belt. No spatial patterns are evident with respect to borehole water. For surface water, high fluoride concentrations in the Mshazi, KwaNyuswa and the KwaNgcolosi streams (inflows to the Inanda dam) appear to be associated with the catchment geology. The ~igh fluoride concentrations in Mshwati and the MgoShongweni are most likely as a result of industrial activities in the respective catchments. For borehole water, high fluoride concentrations may be attributed to catchment geology. Additional fluoride dosaqe ' at water treatment works: Since the fluoride concentrations at the water works were low (mean ranging between 0.5 mglf to 0.38 mglf) , fluoride would need to be added to meet the fluoride standard of 0.7 mgl£ . For most of the water works, the additional fluoride (sodium fluoride) requirement to meet the fluoride standard of 0.7 mgl£, ranged from 1.201 kglMRto 1.555 kg/MR. For the water works, Imfume and Umzinto, the additional fluoride , requirement is 0.768 kg/MR and 0.109 kg/MR respectively. In final water, the fluctuations in fluoride concentrations observed would translate to continuous testing being required to maintain optimal dosing of fluoride. Comparison of influent and effluent fluoride concentrations at wastewater works: There was no evidence of fluoride removal at the Mpophomeni Wastewater Works . There was evidence of 22.4% fluoride removal at the DarvHI Wastewater Works possibly due to the activated sludge treatment process at the wastewater works. Future fluoride levels in surface water that will receive return flows: Once water fluoridation is implemented, the Darvill Wastewater Works would receive fluoridated return flows, and discharge its fluoride rich effluent into the Msunduzi river. The average monthly fluoride road discharged from Darvill Wastewater Works would increase from 0.23 tons to 1.46 tons, an additional 1.23 tons per month on the aquatic environment of the Msunduzi river. The sludge fluoride load, disposed to land, could increase from 4 056 tons/month to 27 863 tons/month, which implies an increase in the fluoride runoff potential from the sludge-lands to the Msunduzi river. Number of people in sensitive groups that could be affected by water fluoridation: A significant number of people in KZN could be sensitive to water fluoridation. This has been estimated to be at least one third of KZN's population that are HIV infected. Recommendations were made and the most important ones are as follows: In the light of the large number of people, one-third the population of KZN, that is HIV positive and therefore could be sensitive to fluoridated water, it is recommended that the South African legislation mandating water fluoridation be withdrawn. Examination of the most recent literature indicated a significant lack of confidence in the best available studies that researched the safety and efficacy of water fluoridation. In the light of this it is recommended that the South African Department of Health re-examine and withdraw its legislation that mandates water fluoridation. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 2002.

Submitted by Milena Rubi (milenarubi@ufscar.br) on 2017-08-16T14:49:46Z No. of bitstreams: 1 ARAUJO_Diego_2016.pdf: 24101509 bytes, checksum: 492307eea8861ce7d88418638e6b6051 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-08-16T14:49:53Z (GMT) No. of bitstreams: 1 ARAUJO_Diego_2016.pdf: 24101509 bytes, checksum: 492307eea8861ce7d88418638e6b6051 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-08-16T14:50:00Z (GMT) No. of bitstreams: 1 ARAUJO_Diego_2016.pdf: 24101509 bytes, checksum: 492307eea8861ce7d88418638e6b6051 (MD5) / Made available in DSpace on 2017-08-16T14:50:07Z (GMT). No. of bitstreams: 1 ARAUJO_Diego_2016.pdf: 24101509 bytes, checksum: 492307eea8861ce7d88418638e6b6051 (MD5) Previous issue date: 2016-06-06 / Não recebi financiamento / Water sludge is a solid waste produced during the water treatment. The volume of sludge produced in a water treatment plant can reach tons of material per month, depending of the quantity of water treated in the plant. Water sludge characteristics can vary depending of the water source and chemical products used in the water treatment. This material is rich in iron oxides, alum oxides, minerals and humic substances. Nowadays all this waste doesn’t have an application, being usually discharged in landfills, after a drying process, or into rivers. On the other hand, fluoride: an ion commonly founded in water samples from drilled wells. According to the current potability standard, administrative order number 2914/11 from Brazilian Govern Health Department, fluoride is necessary for water quality, being indispensable to avoid caries, primarily in children. However, in high concentrations – above 1,5 mg F?.L-1 –, fluoride causes health problems to the consumers, as dental fluorosis and skeletal fluorosis. Moreover, in a high concentration level, fluoride interferes or even hinders the application of this water to public supply, because most of the disposable technologies for fluoride removal have a high financial cost. That said, this work was planned to look for and combine a solution for both problems: utilization for water sludge and an alternative to fluoride removal with low cost. For this purpose, fluoride removal tests were done using fluoride standard samples in a jar-test equipment. These experiments were lead in different pH, to verify the pH influence in the fluoride removal process on the water sludge surface. After the experiments with the fluoride standard samples, a groundwater sample from the city of Capela do Alto, São Paulo state, was used to verify the efficiency of the material in a raw water sample with high fluoride, 2,8 ± 0,02 mg F?.L-1. The maximum adsorption result reached in fluoride standard sample was 0,36 ± 0,02 mg F?/g sludge, in pH 4. The minimum adsorption capacity was reached in pH 6, 0,30 ± 0,02 mg F?/g sludge. In the experiment with groundwater (pH 8,3), the maximum adsorption was 0,34 ± 0,02 mg F?/g sludge, showing the low pH influence in the fluoride adsorption onto water sludge. / O lodo de ETA é um resíduo sólido gerado durante o processo de tratamento da água, cujo volume gerado em uma estação de tratamento pode chegar a toneladas por mês, dependendo da quantidade de água tratada. Apesar de suas características variarem de acordo com a fonte de água utilizada e produtos empregados no tratamento da água, este material é rico em óxidos de ferro, de alumínio, minerais e materiais húmicos. Atualmente todo esse resíduo não possui um uso, sendo frequentemente descartado em aterros sanitários após processo de secagem ou lançado in natura nos corpos d’água. Outra questão comum da área de saneamento, o fluoreto: um íon comumente encontrado em amostras de águas subterrâneas. De acordo com o padrão de potabilidade vigente, Portaria 2914/11 do Ministério da Saúde, o fluoreto é necessário para a qualidade da água, sendo indispensável no combate às cáries, principalmente em crianças. Entretanto, quando em concentrações acima da máxima permitida, 1,5 mg F?.L-1, pode acarretar em problemas de saúde aos usuários do manancial, como fluorose dentária e óssea. Por este motivo, a concentração deste íon acima dos limites estabelecidos, pode inviabilizar o uso desta água para abastecimento público, visto que muitas das tecnologias utilizadas para sua remoção apresentam um alto custo. Sendo assim, este trabalho foi elaborado como forma de unir e buscar uma solução para ambos os problemas: uso para o lodo de ETA e alternativa de remoção de fluoreto à baixo custo. Para tanto, realizou-se ensaios de remoção em jar-test (teste de jarros) com padrões de fluoreto. Esses testes foram conduzidos em diferentes valores de pH, a fim de que se verificasse o grau de influência deste parâmetro no processo de adsorção do fluoreto pelo lodo de ETA. Após os testes em soluções padronizadas, utilizou-se uma amostra de água com concentração de fluoreto acima da permitida, 2,80 ± 0,02 mg F?.L-1, de um poço da cidade de Capela do Alto, estado de São Paulo, para se verificar o rendimento adsortivo do lodo em uma amostra de água in natura. Utilizando-se a solução padrão, o valor máximo de adsorção obtido foi de 0,36 ± 0,02 mg F?/g de lodo em pH 4. O menor rendimento, experimento em pH 6, foi de 0,30 ± 0,02 mg F?/g de lodo. No ensaio com a amostra de água de poço (pH 8,3), alcançou-se uma adsorção de 0,34 ± 0,02 mg F?/g de lodo. Os resultados sinalizam uma alternativa aos adsorventes utilizados atualmente, que alia eficiência de processo e reuso de um rejeito sólido com pouca, ou nenhuma, utilização.

Made available in DSpace on 2015-05-14T12:55:59Z (GMT). No. of bitstreams: 1 Arquivototal.pdf: 9629705 bytes, checksum: 1ee5abbb0d5f91527d23dc1c13b2aa88 (MD5) Previous issue date: 2012-08-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aim of this randomized clinical trial was to evaluate the effect of pH and fluoride concentration in liquid dentifrices in the control of dental caries in early childhood, in non-fluoridated area. In addition, this study evaluated the influence of pH and fluoride concentration in toenails and in the fluoride uptake in plaque. The sample comprised 212 children aged 2-4 years old and was divided into three groups according to the liquid dentifrices used over 12 months: G1 (n = 39-Active/38-Inactive): 550&#956;gF/g-pH 4.5; G2 (n = 33-Active/35-Inactive): 1100&#956;gF/g-pH 7.0; G3 (n = 33- Active/34- Inactive): 550&#956;gF/g-pH 7.0. Clinical examination was performed at baseline and after 12 months of study, using the diagnostic criteria for caries activity (active, inactive) and surface integrity of the lesion (intact, surface discontinuity, cavity). The lesions that progressed or regressed and the net increment (progression - regression) were recorded for each child. Data were checked for normality and homogeneity using the Kolmogorov-Smirnov and Bartlett tests, respectively. The data failed the normality test, even after logarithmic transformation, and the effect of dentifrice on the progression of lesions in caries-inactive, as well as progression, regression, and net increment of injuries in children caries activity was evaluated by Kruskal-Wallis test. For toenails, the data failed the normality test and were analyzed by Kruskal-Wallis test, after logarithmic transformation, followed by Dunn´s test for individual comparisons. For the plaque, the data were analyzed by ANOVA and Bonferroni test for individual comparisons. In all cases, the level of significance was set at 5%. The acidic and neutral liquid dentifrice with low fluoride concentration showed to be effective for the control of dental caries since the results were similar to those found for conventional one (1100&#956;gF/g). Despite a numerical difference in caries increment after 12 months (G3> G2> G1), no statistical significant difference between groups. Fluoride concentrations in toenails were significantly lower when children used the liquid dentifrice with low concentration of fluoride and low pH (p<0.05).The reduction of pH was able to enhance the incorporation of fluoride in the plaque, and the levels of fluoride in the plaque is not decreased over time. It can be concluded that a low fluoride concentration dentifrice can be effective for controlling dental caries without increasing the risk of dental fluorosis in young children. / O objetivo do presente estudo clínico randomizado foi avaliar o efeito do pH e da concentração de flúor presente em dentifrícios líquidos no controle de cárie dentária em crianças na primeira infância, em área não fluoretada. Em adição, este estudo avaliou a influência do pH e da concentração de flúor nas unhas e na incorporação de flúor no biofilme dental. A amostra foi composta por 212 crianças na faixa etária de 2-4 anos de idade e foi dividida em 3 grupos de acordo com o dentifrício utilizado ao longo de 12 meses: G1 (n= 39-Ativos/38-Inativos): 550 ppmF- pH 4,5; G2 (n= 33-Ativos/35-Inativos): 1100 ppmF- pH 7,0; G3 (n= 33-Ativos/34-Inativos): 550 ppmF pH 7,0. O exame clínico foi realizado no baseline e após 12 meses de estudo, usando-se o critério de diagnóstico de atividade de cárie (ativa, inativa) e integridade da superfície da lesão (intacta, superfície com descontinuidade, cavidade). As lesões que progrediram ou regrediram e o incremento líquido (progressão - regressão) foram verificados para cada criança. Os dados foram verificados quanto à normalidade e homogeneidade usando os testes de Kolmogorov-Smirnov e Bartlett, respectivamente. Em função da não normalidade dos dados, mesmo quando estes foram submetidos à transformação logarítmica, o efeito dos dentifrícios sobre a progressão das lesões nas crianças cárie-inativas, bem como sobre a progressão, regressão e incremento líquido das lesões em crianças cárie-ativas foi avaliado pelo teste de Kruskal-Wallis. Para as unhas dos pés, os dados não atingiram padrão de normalidade, sendo analisados por Kruskal-Wallis, após transformação logarítmica, seguido pelo teste de Dunn, para comparações individuais. Para o biofilme dental, os dados foram analisados por ANOVA e teste de Bonferroni, para comparações individuais. Em todos os casos, o nível de significância foi fixado em 5%. Os dentifrícios líquidos acidulado e neutro com baixa concentração de flúor mostraramse eficazes para o controle da cárie dentária, já que os resultados foram semelhantes àqueles encontrados para o dentifrício convencional (1100ppmF). Apesar de uma diferença numérica no incremento de cárie após 12 meses (G3>G2>G1), não houve diferença estatisticamente significativa entre os grupos. Concentração de flúor nas unhas foi significantemente menor quando as crianças usaram os dentifrícios fluoretados de baixa concentração e baixo pH (p<0,05). A redução do pH foi capaz de aumentar a incorporação de flúor no biofilme dental, e os níveis de fluoreto no biofilme não diminuíram ao longo do tempo. Conclui-se que dentifrício líquido com baixa concentração de flúor pode ser eficaz para o controle da cárie dentária, sem aumentar o risco de fluorose dentária em crianças pequenas.

Made available in DSpace on 2015-05-14T12:56:02Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1634368 bytes, checksum: 15995bdf9c8fa3e54e6dbaeeb501003d (MD5) Previous issue date: 2014-02-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Objectives: To analyze the effect of NaF and TiF4 varnishes on nanohardness (N) and elastic modulus (E) of enamel surface after very short exposure time to simulation of drinking a can of soft drink; and evaluate the thickness and topography of protective layer formed, by atomic force microscopy (AFM). Methods: Thirty blocks of human enamel (4x4 mm) were divided into 3 groups (n=10): control, NaF varnish and TiF4 varnish. The specimens remained in artificial saliva for 24h, and the varnishes were applied only once. After 6h, specimens were submitted to erosive challenge (10 cycles: 5s in cola drink/5s in artificial saliva). The thickness of protective layer formed and the surface topography were evaluated by optical microscope and AFM. The data were subjected to Two-Way ANOVA, Tukey and Student s-t (&#945;=0.05). Results: The values shown for N and E (GPa) before and after erosive challenge differed statistically, only for control and TiF4 groups. After the erosive challenge, NaF group showed statistically higher values for N and E than those found for control and TiF4 groups. However, the thickness and depth of indentation values showed that N and E values found for TiF4 group were related to the protective layer formed. By AFM, both varnishes showed globular protective layer formation, and the thickness of layer was significantly higher for TiF4 than NaF group. Conclusions: NaF varnish was able to protect the nanomechanical properties of enamel after short erosive challenge, and TiF4 varnish showed a thick and homogeneous protective layer formation with nanomechanical properties. Keywords: tooth erosion; elastic modulus; fluorides; microscopy, atomic force / Objetivos: Analisar o efeito dos vernizes de NaF e TiF4 na nanodureza (N) e módulo de elasticidade (E) da superfície do esmalte após um curto tempo de exposição a bebida a base de cola, simulando a ingestão de uma lata de refrigerante, e também avaliar a espessura e topografia da camada protetora formada, por meio de microscópio de força atômica (AFM). Métodos: Trinta blocos de esmalte humano (4x4 mm) foram divididos em 3 grupos (n = 10): controle (sem verniz), verniz de NaF e verniz de TiF4. As amostras permaneceram em saliva artificial durante 24 horas, e os vernizes foram aplicados apenas uma vez. Após 6h os espécimes foram submetidos a desafio erosivo (10 ciclos: 5s em bebida a base de cola/5s em saliva artificial). A espessura da camada protetora formada e a topografia da superfície foram avaliadas por microscopia óptica e AFM. Os dados foram submetidos à ANOVA Two-Way, Tukey e T- Student (&#945; = 0,05). Resultados: Houve diferença estatística dos valores de N e E (GPa), antes e após o desafio erosivo, apenas para os grupos controle e TiF4. Após o desafio erosivo o grupo NaF mostrou estatisticamente maiores valores de N e E que os grupos controle e TiF4. No entanto, os valores da espessura e profundidade da indentação mostraram que os valores encontrados de N e E para o grupo TiF4 estavam relacionados com a camada protetora formada e não com o esmalte erodido. Ambos os vernizes mostraram, por meio de AFM, a formação de uma camada protetora globular, e a espessura da camada formada foi significativamente maior para o grupo TiF4 que NaF. O verniz de NaF foi capaz de proteger as propriedades nanomecânicas de esmalte após curto desafio erosivo e o verniz de TiF4 apresentou formação de camada protetora espessa e homogênea com propriedades nanomecânicas . Conclusões: O verniz de NaF foi capaz de proteger as propriedades nanomecânicas de esmalte após curto desafio erosivo e o verniz de TiF4 apresentou formação de camada protetora espessa e homogênea com propriedades nanomecânicas.

Made available in DSpace on 2015-05-14T12:56:07Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2499199 bytes, checksum: ba2f9cd3497696e4d2f7095983ffe2db (MD5) Previous issue date: 2009-12-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The aim of this study was to measure the bioavailability of fluoride in saliva and to observe the pattern of urinary fluoride excretion in children exposed to topical fluoride products of professional use. Seventeen children of 6- 12-years-old, both genders with active white spots on smooth surfaces, no cavities and needing fluoride treatment were included in the study. All volunteers (n=17) received toothbrushes and fluoridated toothpaste (1,100 ppm, 11 volunteers) and no fluoride (6 volunteers) eight days before fluoride a application. A wash-out period of 7 days was established before and after the exposure of neutral gel fluoride (9,000 ppm), foam (12,300 ppm) and varnish (22,600 ppm). Except for the varnish, the fluoridated gel (5g) and foam (1.5g) were applied in trays. /the products were applied for one minute covering all buccal surfaces. Saliva was collected in the following times: 0, 3, 6, 9, 15, 30, 45 and 60 minutes. Urine was collected covering the 24 hours of baseline and after application of the products covering 11 and 13 hours of collection to cover day and night periods as (7:00-18:00 h) and (18:00-7:00 h). Fluoride was measured with the aid of ion specific electrode ORION (9409BN) coupled to a potenciometer (720 A,ThermoOrion). Data statistical analyses were performed in SPSS v. 13.0 applying p< 0.05. The results indicated a higher concentration of fluoride in saliva after 3 minutes of using varnish, foam and gel, the values are 95.02 ± 82.2 ppmF, ppmF 41.0 ± 75.51 and 99.33 ± 59, 8 ppm F, respectively. The excretion of fluoride in urine was higher for varnish, foam and gel, the values are 1.1 ± 7.1 ppm F, 0.6 ± 0.3 ppm F and 0.6 ± 0.6 ppm F, respectively. It can be concluded that the highest values of salivary fluoride regardless the time of measurement were achieved by the fluoride varnish. For the urinary fluoride followed a similar trend showing higher values for the varnish and suggesting that this product can produce a high ingestion of fluoride. / O objetivo desse estudo foi de mensurar a concentração de flúor em saliva e na urina de crianças expostas a fluoretos tópicos de uso profissional. O delineamento desse estudo é clínico, aleatório e cruzado. Participaram 17 crianças com idades entre 6 e 12 anos, de ambos os sexos, com manchas brancas ativas em superfícies lisas, necessitando de fluorterapia. Escovas e dentifrícios foram fornecidos aos voluntários, onde n= 11 receberam dentifrício de 1.100 ppm e n= 6 dentifrício sem flúor. Os produtos fluoretados utilizados foram: gel neutro (9.000 ppm), espuma neutra (12.300 ppm) e verniz (22.600 ppm). As aplicações do gel (5g) e a espuma (1,5g) foram em moldeiras por 1 minuto e o verniz (0,5g) com pincel, cobrindo toda a superfície vestibular do dentes. As coletas de saliva foram feitas no dia da aplicação dos produtos fluoretados nos seguintes tempos: 0, 3, 6, 9, 15, 30, 45 e 60 minutos. As coletas de urina foram feitas por 24 horas. Sendo, 24 horas dividida em dois períodos: diurno ou 11horas (coleta das 7:00 h às 18:00 h) e período noturno ou de 13 horas (coleta das 18:00 h às 7:00 h). Nas análises das amostras de saliva e urina utilizou-se um eletrodo combinado íon-específico da ORION (9409BN) com eletrodo de referência (900200), ambos acoplados a um potenciômetro 720 A (ThermoOrion). Os dados foram digitados no SPSS v. 13.0, submetidos a testes estatísticos e considerados significativos com p< 0,05. Os resultados indicaram uma maior concentração de flúor na saliva após 3 minutos de uso do verniz, gel e espuma, os valores (ppmF) foram de 99,33 ± 59,8; 95,02 ± 82,2 e 75,51 ± 41,0, respectivamente. A excreção de flúor na urina foi maior para verniz, espuma e gel com valores (ppmF) de 1,1± 7,1; 0,6 ± 0,3 e 0,6± 0,6, respectivamente. Pode-se concluir que os valores mais elevados de flúor na saliva independentemente do tempo de medição foram obtidos com o verniz. Para a excreção do flúor seguiu uma tendência semelhante, apresentando valores mais elevados para o verniz e sugerindo que este produto pode produzir uma elevada ingestão de flúor.