Este estudo comparou a ingestão de flúor (F) de crianças de 2 a 6 anos residentes em área fluoretada (Bauru-SP, 0,6-0,8 ppm F) e não fluoretada (Pirajuí-SP), avaliada através do método da dieta duplicada associado à escovação simulada e do Questionário de Freqüência Alimentar semi-quantitativo (QFAsq) associado a questionário para estimativa de ingestão de F a partir do dentifrício. Inicialmente, o QFAsq foi aplicado em 398 crianças residentes no município de Pirajuí-SP. Posteriormente, foram avaliadas subamostras de 25 crianças residentes em Bauru e 24 residentes em Pirajuí. Nestas subamostras, a quantidade de F ingerida através da dieta foi determinada pelo QFAsq e também pela dieta duplicada, considerando seus diferentes constituintes (água, outros líquidos e sólidos). A ingestão de F através do dentifrício foi determinada pelo questionário para estimativa da ingestão de dentifrício e pela escovação simulada. O F foi analisado por eletrodo, depois de difusão facilitada por hexametildiloxano ou após tamponameno com TISAB. A analise estatística foi feita utilizando o software GraphPad InStat, aplicando os testes t pareado, t não pareado, Wilcoxon pareado, Mann-Whitney e estatística de correlação (p<0.05). O QFAsq aplicado à amostra de 398 crianças de Pirajuí encontrou valores de ingestão total de F significativamente menores que os relatados previamente para crianças residentes em Bauru (Miziara, 2006). Na subamostra de crianças avaliadas, a média (±DP, mg) da ingestão de F estimada a partir do QFAsq e da dieta duplicada, considerando-se a dieta total foi de 0,420±0,087 e 0,805±0,190 (Bauru) e 0,227±0,072 e 0,144±0,050 (Pirajuí), sendo a diferença entre os métodos significativa em ambos os municípios. Somente foi obtida uma correlação significativa entre os dois métodos no caso dos sólidos, para ambos os municípios. Considerando a estimativa da ingestão de F a partir do dentifrício obtida pela aplicação do questionário e pela escovação simulada, as médias (±DP, mg) compiladas (Bauru mais Pirajuí) foram 0,611±0,452 e 0,784±0,737, respectivamente, não havendo diferença e nem correlação significativas entre os métodos. Através da utilização dos questionários, foi possível detectar diferença significativa na ingestão total de F entre Bauru e Pirajuí. Entretanto, o mesmo não ocorreu quando se utilizou o método da dieta duplicada associado à escovação simulada. Face aos resultados obtidos, o QFAsq associado a um questionário para estimativa da ingestão de F a partir do dentifrício parece ter um bom potencial para utilização a nível epidemiológico, para se avaliar o risco de grupos de crianças à fluorose dentária. Alguns parâmetros do QFAsq podem ser melhor trabalhados para uma análise mais fidedigna, principalmente com relação à freqüência de ingestão de água e outros líquidos. Em adição, a aplicabilidade desses questionários a nível individual para detecção de risco à fluorose dentária ainda precisa ser melhor estudada. / This study compared the fluoride (F) intake of 2-6-year-old children, living in fluoridated (Bauru-SP, 0,6-0,8 ppm F) and non-fluoridated (Pirajuí-SP) areas. The methods used were the duplicate diet associated to simulated toothbrushing and the semi-quantitative food frequency questionnaire (sqFFQ) associated to a questionnaire for estimation of F intake from dentifrice. Initially, the sqFFQ was applied to 398 children living in Pirajuí. In another phase, subsamples of 25 children living in Bauru and 24 living in Pirajuí were evaluated. In these subsamples the F intake from diet was determined using the sqFFQ as well as the duplicate diet method, considering the different constituents of the diet (water, other liquids and solids). The F intake from the dentifrice was determined using the questionnaire for estimation of F intake, as well as simulated toothbrushing. F was analyzed with the electrode, following hexamethyldisiloxanefacilitated diffusion or after buffering with TISAB. For statistical analysis, the GraphPad InStat software was used. The applies tests were paired and unpaired t tests, paired Wilcoxon test, Mann-Whitney test and correlation analysis (p<0.05). The sqFFQ, when applied to the sample constituted by 398 children living in Pirajuí, found values of total F intake significantly lower when compared to previous data reported by Miziara (2006) for children living in Bauru. In the subsample of evaluated children, the mean (±SD, mg) F intakes estimated by the sqFFQ and duplicate diet (total diet) were 0.420±0.087 and 0.805±0.190 (Bauru) and 0.227±0.072 and 0.144±0.050 (Pirajuí), respectively. The difference between the methods was significant for both municipalities. For both municipalities, a significant correlation between the methods was obtained in the case of solids only. Considering the estimation of F intake from dentifrice obtained by the application of the questionnaire and simulated toothbrushing, the compiled (Bauru plus Pirajuí) means (±SD, mg) were 0.611±0.452 and 0.784±0.737, respectively. The difference as well as the correlation between the methods were not significant. By using the questionnaires, it was possible to detect a significant difference in the total F intake between Bauru and Pirajuí. However, the same did not occur when using the method of duplicate diet associated with simulated toothbrushing. Due to the results obtained, it seems that the sqFFQ associated to a questionnaire for estimation of F intake from dentifrice has a good potential for use at epidemiological level in order to evaluate the risk of groups of children to dental fluorosis. Some parameters of the sqFFQ need to be better addressed for a more precise analysis, mainly with respect to the frequency of water and other liquids intake. In addition, the applicability of these questionnaires at the individual level for the detection of risk to dental fluorosis requires further studies.

A erosão em dentina radicular tem se intensificado e novas terapias foram introduzidas para possibilitar a diminuição da sintomatologia dolorosa. O objetivo deste estudo foi avaliar o efeito da associação do verniz fluoretado aos lasers de Er:YAG ou Nd:YAG na permeabilidade da dentina radicular erodida. Sessenta fragmentos de dentina radicular bovina (2 x 2 x 2 mm) foram submetidos a um desafio erosivo inicial, por meio da imersão em ácido cítrico a 0,3% (pH= 3,2) por duas horas. A seguir, os espécimes foram divididos aleatoriamente em seis grupos (n=10) de acordo com o tratamento: verniz fluoretado, verniz fluoretado + laser de Er:YAG, verniz fluoretado + laser de Nd:YAG, verniz placebo (sem flúor, controle), verniz placebo + laser de Er:YAG, verniz placebo + laser de Nd:YAG. Após 24 horas do emprego do verniz, foram aplicados os lasers de Er:YAG (100 mJ e 3 Hz) ou de Nd:YAG (70 mJ e 15 Hz). Novos desafios erosivos utilizando o mesmo ácido, durante cinco dias, quatro vezes ao dia, por um minuto foram realizados após o tratamento da dentina. Para análise da permeabilidade os espécimes foram submetidos à coloração histoquímica. Os espécimes foram seccionados e analisados por microscopia óptica. A permeabilidade relativa foi quantificada pela relação entre a profundidade de penetração dos íons cobre e espessura da dentina. Os dados obtidos foram analisados através da ANOVA a dois critérios e a interação entre os fatores laser e verniz não foi significativa (p= 0,858), bem como para o fator verniz (p= 0,768). Constatou-se efeito significativo para o fator laser (p< 0,001), sendo que os valores de permeabilidade na dentina radicular irradiada com os lasers Er:YAG ou Nd:YAG não diferiram entre si e ambos foram inferiores àqueles observados para o grupo não irradiado. Pode-se concluir que lasers de Er:YAG e Nd:YAG podem controlar a permeabilidade da dentina radicular erodida, independentemente da aplicação de verniz. / The prevalence of root dentine erosion has increased and new therapies were introduced to minimize painful symptoms. This study evaluated the combined effect of fluoride varnish to Er:YAG and Nd:YAG lasers irradiation in controlling the permeability of eroded root dentine. Sixty fragments of bovine slabs (2 x 2 x 2 mm) were subjected to an erosive challenge, through immersion in citric acid 0.3% (pH= 3.2) during two hours. Then, the specimens with pre-formed lesions were divided in six groups (n=10) according to the respective treatment: fluoride varnish, fluoride varnish + Er:YAG laser, fluoride varnish + Nd:YAG, placebo varnish (F-free, control), placebo varnish + Er:YAG laser, placebo varnish + Nd:YAG laser. Twenty-four hours after varnish application, specimens were irradiated with Er:YAG laser (100 mJ, 3 Hz) or Nd:YAG laser (70 mJ and 15 Hz). After surface treatment, further erosive challenges were performed with the same acid during 1 min, 4 times a day, for 5 days. Specimens were sectioned and subjected to optical microscopic. The relative permeability was quantified by the ratio between the depth of penetration of copper ions and the thickness of dentin. Two-way ANOVA demonstrated no significant interaction between laser and varnish (p= 0,858), as well as for varnish (p= 0,768). There was significant effect of laser (p< 0,001), and permeability values of irradiated dentine had no difference when comparing both tested lasers and both of them were lower than that observed for non-irradiated group. It may be concluded that Er:YAG and Nd:YAG lasers can control the permeability of root dentin eroded, regardless of fluoride varnish application.

Este estudo foi realizado utilizando quatro experimentos que objetivaram: (1) Avaliar a quantidade de flúor (F-) liberada por vernizes; (2) Avaliar a quantidade de F- fraca e fortemente aderido ao esmalte dentário após uso dos vernizes; avaliar a capacidade do verniz de prevenir a (3) desmineralização do esmalte por cárie e (4) a progressão da desmineralização por erosão. Vernizes fluoretados (5,63%), contendo ou não glicerofosfato de cálcio (CaGP) a 1%, 5% e 10% foram elaborados e comparados a vernizes controle sem F-, e outros contendo apenas F- (a [2,26%] ou a [5,63%]). Placas de acrílico foram utilizadas para a avaliação da quantidade de F- liberada pelos vernizes. Um total de 72 dentes humanos foram utilizados para obter 2 amostras (a e b) de cada dente e verificar a quantidade de F- fraca e fortemente aderida ao esmalte (a) após receber o verniz fluoretado e (b) sem receber verniz. Ainda, 60 dentes bovinos foram aplanados e alisados para verificar o efeito preventivo dos vernizes em desafio cariogênico in vitro. E 108 dentes humanos foram aplanados e alisados para verificar o efeito dos vernizes na progressão da erosão in vitro. O verniz contendo F- (5,63%) e 1% CaGP foi o que liberou mais flúor ao meio (p<0,05), e esse mesmo verniz e o verniz contendo F- 5,63% promoveram uma maior quantidade de flúor fraca e fortemente aderida ao esmalte dentário (p<0,01). Entretanto esses aspectos não foram determinantes quando se verificou o efeito preventivo, pois o verniz contendo F- (2,26%) foi o que apresentou melhor efeito preventivo ao diminuir significantemente a desmineralização por cárie (p<0,05) e erosão (p<0,01) in vitro, sendo que os vernizes contendo CaGP não apresentaram esse mesmo efeito. O uso dos vernizes não foi capaz de remineralizar o esmalte que sofreu amolecimento (softening) após um desafio erosivo. Frente ao exposto, pode-se concluir que apesar do verniz de glicerofosfato de cálcio associado ao flúor promover maior liberação de flúor ao meio e maior quantidade de flúor fraca e fortemente aderida ao esmalte dentário, o mesmo não apresentou efeito preventivo favorável frente aos desafios ácidos. Portanto, o uso do glicerofosfato de cálcio de maneira combinada ao flúor na forma de verniz não apresentou efeito preventivo significativo em esmalte submetido a desafios cariogênicos e erosivos in vitro. / This study was carried out in four experiments, which aimed at: (1) assess the amount of fluoride (F-) released by the varnishes; (2) assess the amount of loosely and firmly bound F- to dental enamel after the use of varnishes; assess the ability of the varnishes to prevent (3) enamel demineralization from caries and (4) the progression of demineralization from erosion. Fluoride (5,63%) varnishes containing or not calcium glycerophosphate (CaGP) (1%, 5% or 10%) were made and compared to control varnish with no F-, and varnishes containing only F- (either 2.26% or 5.63%). Acrylic plates were used to assess the amount of F- released from the varnishes. A total of 72 human teeth were used to obtain 2 enamel samples per tooth (a and b) to assess the amount of loosely and firmly bound F- to enamel, before (b) and after (a) varnish application. Still, 60 bovine teeth were flattened and treated to assess the preventive effect of the varnishes after in vitro cariogenic challenge. Also, 108 human teeth were treated to assess the effect of the varnishes on the progression of dental erosion in vitro. The varnish containing F (5.63%) and 1% CaGP released more fluoride to the medium (p<0.05), and this same varnish together with the varnish containing F-5.63% promoted a greater quantity of loosely and firmly bound fluoride to dental enamel (p<0.01). However, these aspects were not determinants in the prevention, due to the fact that the varnish containing F (2.26%) showed better preventive effect when it decreased in vitro enamel demineralization from caries (p<0.05) and erosion (p<0.01), but the varnishes containing CaGP did not show the same effect. The use of the varnishes was not able to remineralize enamel which had already suffered softening from an erosive challenge. In view of these results, it may be concluded that, although the varnish containing CaGP with fluoride promoted greater amounts of fluoride released to the medium and greater amounts of loosely and firmly bound fluoride to dental enamel, the CaGP-F varnish did not show a preventive effect after acidic challenges. Therefore, the use of calcium glycerophosphate together with fluoride in varnishes did not show a significant preventive effect for enamel submitted to cariogenic and erosive challenges in vitro.

The aluminum oxide growth rate for aluminum protected with 2.4 nm of aluminum fluoride has been determined. We show that a 2.4 nm aluminum fluoride layer does not prevent aluminum from oxidation but does significantly retard the oxide growth – decreasing the oxide layer thickness from 1 nm in less than an hour to 0.9 nm over 116 hours. Additionally, the optical constants for aluminum oxide growing under an aluminum fluoride barrier layer have been determined – showing an increase in absorption at high energies for Al2O3 forming at room temperature as compared to highly ordered Al2O3 formed at high temperatures.

Objective: To determine risk factors for cavitated caries incidence and extent of cavitated caries among adolescents. Methods: Three hundred and three Iowa Fluoride Study (IFS) subjects met inclusion criteria for interval between dental examination and the responses from the IFS (ages 13.5 to 17.0) and the Block Kids Food Frequency (ages 13.0 to 17.0) questionnaires, respectively. The analyses focused on the outcome variables of net cavitated caries incidence and net cavitated caries increment counts, respectively. The independent IFS questionnaire variables related to demographics, fluorides, oral hygiene, beverage intakes, dental visits, sealants and previous caries incidence variables, respectively, whereas, Block's questionnaire variables related to intakes of solid foods and beverages, respectively. Two sets of analyses, logistic and negative binomial regression analyses, were conducted to assess the associations between risk factors and net cavitated caries incidence and increment counts from 13 to 17, respectively. Results: In multivariable logistic regression analyses, significant (p<0.05) negative associations were found between age 13 to 17 net cavitated caries incidence and greater frequency of consumption of vegetables, greater brushing frequency and greater frequency of sugar-free beverage consumption. Additionally, significant (p<0.05) positive associations were found between age 13 to 17 net cavitated caries incidence and both net cavitated caries incidence from 9 to 13 and frequency of consumption of solid-foods in the combined category of presumed moderate cariogenicity. The significant interaction effect showed that the effect of the presence/ absence of sealants varied for girls vs. boys. In multivariable negative binomial analyses assessing the association between net cavitated caries increment count from 13 to 17 and risk factors, significant (p<0.05) positive associations were found with greater intake of foods predominant in starch, presence of sealants, greater baseline age, cavitated caries increment count from 9 to 13, and greater frequency of consumption of foods predominant in added sugar, respectively. Significant (p<0.05) negative associations were found between net cavitated caries incidence and greater frequency of consumption of foods predominant in fiber and natural sugar and greater daily fluoride intake from water. However, daily fluoride intake from water was not statistically significant with the significant interaction effect included between baseline age and net cavitated caries increment count from 9 to 13 (dichotomized as Y/N). Conclusion: Presence of sealants, frequency of consumption of vegetables and previous cavitated caries incidence from 9 to 13 were associated with outcomes of incidence and extent of cavitated caries observed among IFS adolescents. The differences in findings for risk factors for incidence and extent of cavitated caries are due in part to the nature of the outcome variables (count vs. dichotomous), emphasizing the need to consider both outcomes in future studies of adolescent caries.

A COMPARISON OF THE ANTIMICROBIAL EFFICACY OF SILVER DIAMINE FLUORIDE AND SILVER NITRATE: AN IN VITRO STUDY By: Nicholas L Luke, D.D.S. A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Dentistry at Virginia Commonwealth University. Virginia Commonwealth University, May 2018 Thesis Advisor: William O. Dahlke Jr., D.M.D. Pediatric Dentistry, Department Chair Purpose: To determine the antimicrobial efficacy of SDF and SN/NaF. Methods: Three bacterial species were combined to create an in vitro biofilm. Treatment was completed with SN, SN/NaF, SDF, SDF½ or untreated (control). Results: The untreated group demonstrated significantly higher growth than all other treatment groups across the study. On the BHI-plates (1-day), there were significant differences between all treatments except SDF and SDF½. On the BHI-plates (3-days), SN/NaF was not significantly different from SDF or SDF½. On the L-MRS-plates (1-day), both SN treatment groups yielded significantly higher growth than the SDF groups. On the L-MRS-plates (3-days), SN yielded significantly higher growth than SN/NaF, SDF, and SDF½. Conclusion: SDF is more effective than SN/NaF, with the exception of BHI-plates (3-days) only and SN/NaF is more effective than SN on primarily S. mutans and L. acidophilus. There is evidence of a possible antimicrobial tolerance of oral bacteria to silver.

Durch die Verwendung der fluorolytischen Sol-Gel Synthese ist es möglich, röntgenamorphe bzw. partiell nanokristalline Metallhydroxidfluoride und Metallfluoride zu erhalten. Diese Verbindungen unterscheiden sich in ihren Eigenschaften stark von „klassisch“ hergestellten, kristallinen Metall(hydroxid)fluoriden. In der vorliegenden Promotionsarbeit wurden deshalb in vier aufeinander folgenden Kapiteln sowohl die Synthese und Charakterisierung von Aluminium– und Magnesium(hydroxid)fluoriden beschrieben als auch die Auswirkung dieser Verbindungen auf das Phasentransformationsverhalten von böhmitischen Xerogelen zu Korund sowie ihre Wirksamkeit als Sinterhilfsmittel bei der Korundkeramikherstellung untersucht. / The application of the fluorolytic sol-gel method with aqueous hydrofluoric acid enables the synthesis of X-ray amorphous or rather partially nanocrystalline metal hydroxide fluorides and metal fluorides. These compounds strongly differ in their characteristics from “classically” manufactured, crystalline metal hydroxide fluorides. In the present dissertation both, the synthesis and characterisation of aluminium and magnesium hydroxide fluorides were described and the effect of these compounds on the phase transformation behaviour from pseudoboehmites to corundum was examined as well as their effectiveness as sintering aid during the corundum ceramics production.

This PhD thesis deals with the activation of diorganozinc compounds by asymmetric catalysts in the framework of their enantioselective addition on carbon oxygen and carbon nitrogen double bonds. The properties of several new catalysts systems were investigated. Several chiral sulfonamido alcohols derived from (S)-leucinol and (1S) 3 aminoisoborneol were synthesized to cover a range of electronic and steric properties. These were evaluated in the addition of Et2Zn to N phosphinoyl and N sulfonyl-imines, but they did not provide any acceptable yields or enantioselectivities while used in stoichiometric quantities. Their catalytic properties were also investigated for the addition of Et2Zn to benzaldehyde. Unfortunately, only modest enantiocontrol (max. 47% ee) could be obtained with 10mol% of chiral ligand. We investigated another approach based on the possible activation of the nucleophilicity of dialkylzinc compounds towards benzaldehyde by fluoride anion. The combination of stoichiometric amount of an inorganic fluoride salt and a substoichiometric amount of a phase transfer catalyst (10mol% of crown ether 18 C 6) provided non-negligible rate acceleration. However, an asymmetric version of this catalytic system was not considered. Following our discovery of the activation provided by the fluoride anion, metal fluoride complexes were tapped as potential catalysts. In particular, copper(I) fluoride complex, (Ph3P)3CuF, was shown to accelerate the reaction on benzaldehyde. After screening a range of ligands, the combination of (Ph3P)3CuF and chiral BINAP in catalytic amounts (1mol%) was found to catalyze efficiently the Et2Zn addition on aromatic aldehydes. Yields were good but enantiocontrol was modest (49-63% ee). An improved copper fluoride-based catalyst was developed by combining a copper salt, a fluoride source and a chiral diphosphine ligand. Optimization of this second generation catalyst was carried out (copper source, fluoride source, chiral ligand, relative stoichiometries of catalyst's precursors, catalyst's loading, solvent, temperature) and applied to a range of aldehydes (upto 87% ee). A mechanism was proposed based on literature data and experimental observations. The influence of the counterion was then thoroughly explored by assessing the catalytic potential of various copper complexes in combination with chiral BINAP in the Et2Zn addition to benzaldehyde. Copper(II) diketonates provided good enantiocontrol (upto 88% ee) which could be improved even further by using optically active copper diketonates in a matched combination with chiral BINAP (upto 91% ee). This new system was applied to control the addition of Et2Zn to a range of aldehydes with a low catalyst loading (0.5mol%). A mechanism was proposed to explain a series of experimental observations. / Cette dissertation traite de l'activation de composés diorganozinciques par des catalyseurs asymétriques dans le cadre de leur addition énantiosélective sur des doubles liaisons carbone-oxygène et carbone-azote. Les propriétes de divers catalyseurs originaux ont été investiguées. Plusieurs sulfonamidoalcools chiraux dérivés du (S)-leucinol et du (1S) 3 aminoisoborneol ont été synthétisés pour couvrir un domaine de propriétés électroniques et stériques. Ceux-ci ont été testés lors l'addition du Et2Zn sur les N phosphinoyl et N-sulfonyl-imines, mais ils n'ont pas fourni de rendements et excès énantiomériques intéressants malgré leur utilisation en quantité stoechiométrique. Leurs propriétés catalytiques ont également été examinées dans le cadre de l'addition de Et2Zn au benzaldéhyde. Malheureusement, un faible contrôle de l'énantiosélectivité (max. 47% ee) est obtenu en présence de 10mol% de ligand chiral. Une autre approche abordée concerne l'influence de l'anion fluorure sur la nucléophilie des composés dialkylzincs envers le benzaldehyde. La combinaison de quantités stoechiométriques d'un sel fluoré inorganique et d'une quantités sub stoechiométrique d'un agent de transfert de phase (10mol% éther couronne 18 C 6) conduit à un accroissement non négligeable de la vitesse de réaction. Toutefois, le développement d'une version asymétrique de ce système n'a pas été considéré. A la suite de notre découverte de l'activation due à l'anion fluorure, les complexes métalliques fluorés ont été examinés en tant que catalyseurs potentiels. En particulier, le complexe du cuivre, (Ph3P)3CuF, accélère la réaction d'addition du Et2Zn sur le benzaldéhyde. Après un criblage de divers ligands, la combinaison de (Ph3P)3CuF et de la diphosphine chirale BINAP en quantité catalytique (1mol%) conduit à une catalyse efficace de l'addition du Et2Zn sur des aldéhydes aromatiques. Les rendements obtenus sont bons, par contre l'énantiosélectivité est modeste (49-63% ee). Une version améliorée de catalyseurs cuivre-fluorure a été obtenue en combinant un sel de cuivre, une source de fluorure et une diphosphine chirale. L'optimisation de divers paramètres de réaction a été effectuée (source de cuivre, origine de l'anion fluorure, ligand chiral, stoechiométries relatives des précurseurs du catalyseur, charge de catalyseur, solvant et température). Le catalyseur optimisé a été appliqué à divers aldéhydes (jusqu'à 87% ee). Un mécanisme réactionnel a été proposé sur la base d'arguments de la littérature et d'observations expérimentales. Le rôle du contre-ion a été exploré par un examen attentif de divers complexes du cuivre en combinaison avec la BINAP chirale en tant que catalyseurs de l'addition du Et2Zn sur le benzaldehyde. Les dicétonates du cuivre(II) ont conduit à une bonne énantiosélectivité (jusqu'à 88% ee) qui a pu être améliorée en utilisant des dicétonates du cuivre(II) optiquement actifs assortis avec le bon énantiomère de la BINAP (jusqu'à 91% ee). Ce nouveau système a été appliqué pour l'addition du Et2Zn sur divers aldéhydes avec une charge réduite en catalyseur (0.5mol%). Un mécanisme a été proposé afin de supporter les observations expérimentales.

According to WHO, the addition of fluoride to milk could be considered as an alternative to water fluoridation for community-based caries prevention in childhood. School-based schemes in developing as well as industrial countries have demonstrated substantial benefits on oral health, but there are limited data available on the local events in the oral cavity after consumption of fluoridated milk. The general aim of the present investigations was to investigate the concentration of fluoride obtained in saliva and dental plaque after ingestion of Fmilk and to explore the possible effects on the oral ecology. A series of controlled studies were performed in vivo in which samples of saliva and dental plaque were collected and analysed with respect to fluoride content, microbial composition and acidogenicity. An in vitro study evaluated the effect on enamel lesion formation. In paper I, significantly increased concentrations of fluoride (p&lt;0.05) were disclosed in saliva 15 minutes after drinking the fluoride-containing water or milk. In the plaque samples however, the F-increase remained significantly elevated still after 2 hours. The availability of fluoride from milk was generally somewhat lower than from water but the differences were not statistically significant in either plaque or saliva. In paper II, the fluoride concentration in plaque was further explored after a single intake or habitual consumption of fluoridated milk together with a regular meal. The results showed that cariesinhibiting levels of fluoride persisted up to 4 hours after intake. There were no significant differences between the single intakes when compared with repeated intakes. In paper III, the influence of fluoridated milk on the salivary microorganisms associated with dental caries was evaluated. No significant alterations of the microflora were found compared with baseline. There was a slight reduction in the proportion of mutans streptococci after 2 and 4 weeks during consumption with fluoridated milk but the difference failed to reach statistical significance. In paper IV it was demonstrated that fluoridated milk significantly (p&lt;0.05) could counteract the lactic acid formation in dental plaque as initiated with sucrose. In paper V, laser fluorescence technique was used to monitor the effect of fluoridated milk on enamel lesion formation in an experimental caries model. The results reinforced previous research and showed a hampering effect of fluoridated milk. No side effects were reported in any of the investigations. The findings of this thesis substantiate that milk is a suitable vehicle for fluoride administration and contribute to the understanding and possible explanations for the anti-caries properties of fluoridated milk. The main conclusions were: a) intake of fluoridated milk resulted in significantly elevated fluoride levels in saliva within the first 15 minutes and up to 4 hours in dental plaque when fluoridate milk was consumed together with meal, b) no significant alteration of the salivary microflora was disclosed after habitual intake of fluoridated milk but a delayed carbohydrate-mediated lactic acid formation in suspensions of dental plaque could be demonstrated, c) the fluoride concentrations in plaque were not negatively influence by the food intake, and d) the in vitro findings advocated that fluoride added to milk reduced enamel lesion formation as assessed by laser fluorescence technique in an experimental caries model.According to WHO, the addition of fluoride to milk could be considered as an alternative to water fluoridation for community-based caries prevention in childhood. School-based schemes in developing as well as industrial countries have demonstrated substantial benefits on oral health, but there are limited data available on the local events in the oral cavity after consumption of fluoridated milk. The general aim of the present investigations was to investigate the concentration of fluoride obtained in saliva and dental plaque after ingestion of Fmilk and to explore the possible effects on the oral ecology. A series of controlled studies were performed in vivo in which samples of saliva and dental plaque were collected and analysed with respect to fluoride content, microbial composition and acidogenicity. An in vitro study evaluated the effect on enamel lesion formation. In paper I, significantly increased concentrations of fluoride (p&lt;0.05) were disclosed in saliva 15 minutes after drinking the fluoride-containing water or milk. In the plaque samples however, the F-increase remained significantly elevated still after 2 hours. The availability of fluoride from milk was generally somewhat lower than from water but the differences were not statistically significant in either plaque or saliva. In paper II, the fluoride concentration in plaque was further explored after a single intake or habitual consumption of fluoridated milk together with a regular meal. The results showed that cariesinhibiting levels of fluoride persisted up to 4 hours after intake. There were no significant differences between the single intakes when compared with repeated intakes. In paper III, the influence of fluoridated milk on the salivary microorganisms associated with dental caries was evaluated. No significant alterations of the microflora were found compared with baseline. There was a slight reduction in the proportion of mutans streptococci after 2 and 4 weeks during consumption with fluoridated milk but the difference failed to reach statistical significance. In paper IV it was demonstrated that fluoridated milk significantly (p&lt;0.05) could counteract the lactic acid formation in dental plaque as initiated with sucrose. In paper V, laser fluorescence technique was used to monitor the effect of fluoridated milk on enamel lesion formation in an experimental caries model. The results reinforced previous research and showed a hampering effect of fluoridated milk. No side effects were reported in any of the investigations. The findings of this thesis substantiate that milk is a suitable vehicle for fluoride administration and contribute to the understanding and possible explanations for the anti-caries properties of fluoridated milk. The main conclusions were: a) intake of fluoridated milk resulted in significantly elevated fluoride levels in saliva within the first 15 minutes and up to 4 hours in dental plaque when fluoridate milk was consumed together with meal, b) no significant alteration of the salivary microflora was disclosed after habitual intake of fluoridated milk but a delayed carbohydrate-mediated lactic acid formation in suspensions of dental plaque could be demonstrated, c) the fluoride concentrations in plaque were not negatively influence by the food intake, and d) the in vitro findings advocated that fluoride added to milk reduced enamel lesion formation as assessed by laser fluorescence technique in an experimental caries model.

The recognition and capture of fluoride, cyanide and azide anions is attracting great deal of attention due to the negative effects of these anions on the environment and on human health. One of common methods used for the recognition and capture of these anions is based on triarylboranes, the Lewis acidity of which can be enhanced via variation the steric and electronic properties of the boron substituents. This dissertation is dedicated to the synthesis of novel boron-based anion receptors that, for the most part, feature an onium group bound to one of the aryl substituents. The presence of this group is shown to increase the anion affinity of the boron center via Coulombic effects. Another interesting effect is observed when the onium group is juxtaposed with the boron atom. This is for example the case of naphthalene-based compounds bearing a dimesitylboryl moiety at one of the peri-position and a sulfonium or telluronium unit at the other peri position. Fluoride anion complexation studies with these sulfonium or telluronium boranes, show that the boron-bound fluoride anion is further stabilized by formation of a B-F->Te/S bridge involving a lp(F)->sigma*(Te/S-C) donor acceptor interaction. Some of the sulfonium boranes investigated have been shown to efficiently capture fluoride anions from wet methanolic solutions. The resulting fluoride/sulfonium borane adducts can be triggered to release a "naked" fluoride equivalent in organic solution and thus show promise as new reagents for nucleophilic fluorination chemistry. Interestingly, the telluronium systems show a greater fluoride anion affinity than their sulfonium analogs. This increase is assigned to the greater spatial and energetic accessibility of the sigma* orbital on the tellurium atom which favors the formation of a strong B-F->Te interaction. This dissertation is concluded by an investigation of the Lewis acidic properties of B(C6Cl5)3. This borane, which has been reported to be non-Lewis acidic by other researchers, is found by us to bind fluoride, azide and cyanide anions in dichloromethane with large binding constants. This borane is also reactive toward neutral Lewis bases, such as p-dimethylaminopyridine, in organic solvents.