A pulsed-beam fourier transform microwave spectrometer was used to measure the rotational spectra of iodine heptafluoride, iodine pentafluoride, and the weakly bound complex, HCl...NNO. For IF7, only five rotational transitions were observed, and no resolvable hyperfine structure was detected. Based on this data, the A, B, and C rotational constants were determined to be 1746(3) MHz, 1732.0(8) MHz, and 1553.0(2) MHz, respectively. The existence of a pure rotational spectrum confirms that this molecule undergoes polar distortions. Twenty-two hyperfine components of the IF5 spectrum were recorded. The B rotational constant for this molecule was determined to be 2727.421(3) MHz, and the quadrupole coupling constant was found to be 1069.35(13) MHz. Though the work is still in progress on HCl...NNO, nine transitions have been recorded. In addition, five transitions have been recorded for an apparent trimer species composed of HCl, NNO, and an as yet unidentified third species.

No description available.

The Atmospheric Chemistry Experiment (ACE) is a satellite mission for remote sensing of the Earth's atmosphere using the solar occultation technique. The primary instrument on this satellite is the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). ACE-FTS retrievals are described with a focus on the creation of <em>a priori</em> temperature and pressure profiles. ACE-FTS measurements are then used to investigate the chemistry, transport and trends of chlorine, fluorine and water in the stratosphere, leading to an improved understanding of processes affecting both stratospheric ozone depletion and global climate change. <br /><br /> Total chlorine (Cl_TOT) in the stratosphere is determined using ACE-FTS measurements of eleven chlorine-containing species, supplemented by both other measurements and models, to determine Cl_TOT as a function of altitude in five latitude zones. All resulting Cl_TOT profiles are nearly linear, with a slight slope. Mean Cl_TOT for 2004 is determined to be 3. 65 ppbv for both the northern and southern midlatitudes (with a precision and estimated accuracy of ??0. 09 and ??0. 13 ppbv, respectively). A slightly lower value of mean Cl_TOT is determined for the tropics and slightly higher values at high latitudes. Total fluorine (F_TOT) in the stratosphere is also determined primarily from ACE-FTS measurements using a similar approach, resulting in stratospheric F_TOT profiles which are nearly linear with mean values ranging from 2. 50 to 2. 59 ppbv for each latitude zone (with a precision of 0. 04-0. 07 ppbv and an estimated accuracy of 0. 15 ppbv). The observed slopes and pattern of latitudinal variation are evidence of the beginning of a decline in global stratospheric chlorine and of the continuing increase in global stratospheric fluorine levels. <br /><br /> The abundance of water in the stratosphere is investigated for the northern hemisphere midlatitudes in 2004 using ACE-FTS measurements. Potential water is determined as [H₂O]+2[CH₄] and from [H₂O] versus [CH₄] correlations, resulting in a value of 7. 14??0. 05 ppmv, which is used to determine a value of 3. 65??0. 15 ppmv for the mean abundance of water entering the stratosphere. Both values are compared directly with historical data from the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument (1985-1994) and show a negligible change, implying that the increases observed by ATMOS and other long-term measurements from that time period have not continued. <br /><br /> The removal of stratospheric water in the Arctic vortex is investigated using ACE-FTS measurements. Using derived quantities from a meteorological data assimilation, northern hemisphere occultations from early 2004 are classified as vortex, vortex edge or extravortex. [CH₄] versus [N₂O] correlations are used to further classify the extravortex occultations as tropical, subtropical or midlatitude. Comparisons between profiles of [N₂O], [CH₄] and [H₂O] inside and outside the Arctic vortex, give estimates of upper stratospheric and lower mesospheric descent rates, indicating that descent in the winter 2004 Arctic vortex was rapid, with evidence of descent at higher altitudes than in past years. <br /><br /> The dehydration of air in the tropical tropopause layer and mechanisms for the entry of water vapor into the stratosphere are investigated by an analysis of ACE-FTS profiles of temperature, water vapor and [HDO]/[H₂O]. Month-to-month comparisons for 2004 and 2005 reveal a clear pattern of seasonal variation and a correlation between minimum temperature and maximum HDO depletion. Further interpretation indicates that the gradual dehydration mechanism accompanied by lofting of ice particles in the tropical troposphere is the most likely explanation for the observed seasonal variation and the shape of the [HDO]/[H₂O] profiles.

The main electrophilic source used in radiolabelling is [18F]F2, which is highly reactive, toxic and requires specialist equipment for safe handling. The Gouverneur group has initiated a research programme focused on the preparation of new stable and easy-to-handle N-18F reagents. In the development of [18F]radiolabelling reactions it would be extremely valuable to develop a library of selective N-18F reagents possessing reactivity tailored to the desired chemical transformation. The aim of this thesis is to further assess the scope of electrophilic N- 18F reagents in new transformations for the construction of C-18F bonds.

This thesis has focussed on three main projects, all concerning electrophilic fluorination and fluorocyclization methodology. To begin with we considered the development of a novel fluoro-carbocyclization reaction, which combined the use of substrates of relatively low reactivity and rarely used carbon nucleophiles. Two major and common problems with electrophilic fluorination are the choice of a suitable reaction solvent and an appropriate fluorine source. These challenges were encountered and overcome to furnish a large library of cyclized products in excellent yields starting from indene and dihydronaphthalene class substrates. Our attempts to extend this methodology to an asymmetric variant using literature protocol for asymmetric fluorination were unsuccessful due to insufficient reactivity, which prompted us to investigate a new class of chiral reagents. Using the structural core of the widely used achiral reagent Selectfluor™, we prepared a variety of novel reagents which displayed greater fluorinating power than what is currently available in the literature. Finally, by combining the methodology for fluoro-carbocyclization with our selection of chiral reagents we were able to successfully achieve an unprecedented metal-free asymmetric fluoro-carbocyclization.

The first part of this work was to synthesise partially fluorinated reactive compounds and then to study their reactivity towards nucleophiles and electrophiles. These reactive compounds were obtained in a two step process from both cyclopentane and adamantane and in a three step process for cyclopentanol. The first step was the free radical addition of the cycloalkanes, cycloalcohol to hexafluoropropene via thermal and/or radiochemical alkylations. For the cyclic alkane derivatives, the second step was a stereospecific dehydrofluorination of the fluorocarbon chain, whereas for the cyclic alcohol, a dehydration and then dehydrofluorination were performed to give the conjugated diene. Finally, the fluoroalkene reactivity was studied via nucleophilic and electrophilic addition reactions. The second part of my work was to study the free radical addition of tertiary amines to hexafluoropropene, an example is illustrated below.

O tecido ósseo é o maior sítio de acúmulo de flúor (F) do nosso organismo. Parte do F ingerido pode transitar através de um mecanismo de estado estacionário entre cristais da superfície óssea e plasma, ou quando da remodelação óssea, mantendo constantes os níveis plasmáticos algum tempo após a diminuição da ingestão de F. O objetivo deste estudo foi avaliar o período de tempo para que o F acumulado no osso de ratos, após uma exposição aguda, seja removido. Três grupos experimentais com 10 ratos Wistar (70 dias de idade) receberam, por via gástrica, dose única de 50 mg F/Kg peso corporal (como NaF) e 3 grupos controle, também com 10 animais cada, receberam água deionizada. A eutanásia dos animais ocorreu após 30, 90 ou 180 dias da administração de F. Os ratos foram anestesiados, sangue e fêmures removidos e analisados quanto à concentração de F. Para o fêmur, foi analisado o F solúvel em ácido removido por biópsia da superfície óssea, além do F presente no osso total, após calcinação. As cinzas e o plasma foram analisados para o F com o eletrodo, após difusão facilitada por HMDS. Os dados foram analisados pelo teste de Kruskal-Wallis, seguido pelo teste de Dunn (p<0,05). Os níveis plasmáticos de F do grupo controle foram constantes ao longo do tempo, e similares aos do grupo experimental eutanasiado aos 30 dias. Para os grupos experimentais eutanasiados após 90 e 180 dias, houve uma redução significativa nos níveis plasmáticos de F em relação ao grupo controle. A concentração de F na superfície do fêmur para o grupo experimental foi significativamente maior em relação ao grupo controle no tempo de eutanásia de 30 dias apenas, sendo que para os demais períodos experimentais, apesar de a concentração de F ser maior no grupo experimental quando comparado ao controle, esta diferença não foi estatisticamente significativa. Para ambos os grupos pôde ser observado um aumento nos níveis de F na superfície óssea longo do tempo. Para o osso total, o grupo experimental apresentou concentrações similares de F nos diferentes tempos de morte, e estes níveis foram similares aos encontrados para o grupo controle, no tempo de eutanásia de 180 dias. O grupo controle, nos tempos de morte 30 e 90 dias, apresentou valores significativamente menores quando comparado às demais situações. Os dados sugerem que o F incorporado à superfície óssea de ratos a partir de uma exposição aguda não é irreversivelmente ligado, mas vai sendo perdido ao longo do tempo, parecendo ser completamente perdido entre 90 e 180 dias após a exposição. Já os níveis de F incorporados no osso total 30 dias após uma ingestão aguda subletal não parecem ser perdidos ao longo do tempo. A não ocorrência de aumento ao longo do tempo nos níveis de F no osso total do grupo experimental sugere que existe um limite para a incorporação de F no osso total, provavelmente relacionado ao número de sítios possíveis para ligação irreversível do F. / Bone is the major site for fluoride (F) accumulation in the body. Part of the ingested F can transit between bone surface crystals and plasma, through a steady-state mechanism, which can also occur during bone remodeling. This could maintain constant plasma F levels for some time after the F intake is reduced. The aim of this study was to evaluate the lag time required to remove F accumulated in bone of rats after acute exposure. Three experimental groups, containing ten 70-day-old Wistar rats each, received, by gastrogavage, a single dose of 50 mgF/Kg body weight (as NaF), while 3 control groups received deionized water. The animals were euthanized 30, 90 or 180 days after F administration. The animals were anesthetized, blood and femurs were collected and analyzed for F. F on the femur surface was removed through an acid biopsy and F in whole bone was analyzed after ashing. Ash and plasma F were analyzed with the electrode following HMDS-facilitated diffusion. Data were analyzed by Kruskal-Wallis and Dunn\'s tests (p<0.05). Plasma F levels in control group were constant along time and similar to the levels found for the experimental group euthanized after 30 days. For the experimental groups euthanized after 90 and 180 days, a significant reduction in plasma F levels in respect to control was found. F in bone surface for the experimental group was significantly higher than for the control group only 30 days after F administration. For the other experimental times, despite F concentration was higher in the experimental group when compared to control, this difference was not significant. For both groups an increase in bone surface F levels along time was seen. For whole bone, the experimental group had similar F concentrations for all times of euthanasia and these levels were similar to those found for control group 30 days after F administration. Control group, 30 and 90 days after F administration had values significantly lower when compared to the other situations. Data suggest that F incorporated into bone surface of rats after acute exposure does not seem to be irreversibly bound and is lost along time. It seems to be completely lost between 90 and 180 days after F administration. On the other hand, F levels incorporated in whole bone 30 days after acute exposure to F do not seem to be lost along time. The lack of increase in whole bone F levels in the experimental group along time suggests that there is a limit for F uptake in whole bone, probably related to the number sites available to bind F irreversibly.

O tecido ósseo é o maior sítio de acúmulo de flúor (F) do nosso organismo. Parte do F ingerido pode transitar através de um mecanismo de estado estacionário entre cristais da superfície óssea e plasma, ou quando da remodelação óssea, mantendo constantes os níveis plasmáticos algum tempo após a diminuição da ingestão de F. O objetivo deste estudo foi avaliar o período de tempo para que o F acumulado no osso de ratos, após uma exposição aguda, seja removido. Três grupos experimentais com 10 ratos Wistar (70 dias de idade) receberam, por via gástrica, dose única de 50 mg F/Kg peso corporal (como NaF) e 3 grupos controle, também com 10 animais cada, receberam água deionizada. A eutanásia dos animais ocorreu após 30, 90 ou 180 dias da administração de F. Os ratos foram anestesiados, sangue e fêmures removidos e analisados quanto à concentração de F. Para o fêmur, foi analisado o F solúvel em ácido removido por biópsia da superfície óssea, além do F presente no osso total, após calcinação. As cinzas e o plasma foram analisados para o F com o eletrodo, após difusão facilitada por HMDS. Os dados foram analisados pelo teste de Kruskal-Wallis, seguido pelo teste de Dunn (p<0,05). Os níveis plasmáticos de F do grupo controle foram constantes ao longo do tempo, e similares aos do grupo experimental eutanasiado aos 30 dias. Para os grupos experimentais eutanasiados após 90 e 180 dias, houve uma redução significativa nos níveis plasmáticos de F em relação ao grupo controle. A concentração de F na superfície do fêmur para o grupo experimental foi significativamente maior em relação ao grupo controle no tempo de eutanásia de 30 dias apenas, sendo que para os demais períodos experimentais, apesar de a concentração de F ser maior no grupo experimental quando comparado ao controle, esta diferença não foi estatisticamente significativa. Para ambos os grupos pôde ser observado um aumento nos níveis de F na superfície óssea longo do tempo. Para o osso total, o grupo experimental apresentou concentrações similares de F nos diferentes tempos de morte, e estes níveis foram similares aos encontrados para o grupo controle, no tempo de eutanásia de 180 dias. O grupo controle, nos tempos de morte 30 e 90 dias, apresentou valores significativamente menores quando comparado às demais situações. Os dados sugerem que o F incorporado à superfície óssea de ratos a partir de uma exposição aguda não é irreversivelmente ligado, mas vai sendo perdido ao longo do tempo, parecendo ser completamente perdido entre 90 e 180 dias após a exposição. Já os níveis de F incorporados no osso total 30 dias após uma ingestão aguda subletal não parecem ser perdidos ao longo do tempo. A não ocorrência de aumento ao longo do tempo nos níveis de F no osso total do grupo experimental sugere que existe um limite para a incorporação de F no osso total, provavelmente relacionado ao número de sítios possíveis para ligação irreversível do F. / Bone is the major site for fluoride (F) accumulation in the body. Part of the ingested F can transit between bone surface crystals and plasma, through a steady-state mechanism, which can also occur during bone remodeling. This could maintain constant plasma F levels for some time after the F intake is reduced. The aim of this study was to evaluate the lag time required to remove F accumulated in bone of rats after acute exposure. Three experimental groups, containing ten 70-day-old Wistar rats each, received, by gastrogavage, a single dose of 50 mgF/Kg body weight (as NaF), while 3 control groups received deionized water. The animals were euthanized 30, 90 or 180 days after F administration. The animals were anesthetized, blood and femurs were collected and analyzed for F. F on the femur surface was removed through an acid biopsy and F in whole bone was analyzed after ashing. Ash and plasma F were analyzed with the electrode following HMDS-facilitated diffusion. Data were analyzed by Kruskal-Wallis and Dunn\'s tests (p<0.05). Plasma F levels in control group were constant along time and similar to the levels found for the experimental group euthanized after 30 days. For the experimental groups euthanized after 90 and 180 days, a significant reduction in plasma F levels in respect to control was found. F in bone surface for the experimental group was significantly higher than for the control group only 30 days after F administration. For the other experimental times, despite F concentration was higher in the experimental group when compared to control, this difference was not significant. For both groups an increase in bone surface F levels along time was seen. For whole bone, the experimental group had similar F concentrations for all times of euthanasia and these levels were similar to those found for control group 30 days after F administration. Control group, 30 and 90 days after F administration had values significantly lower when compared to the other situations. Data suggest that F incorporated into bone surface of rats after acute exposure does not seem to be irreversibly bound and is lost along time. It seems to be completely lost between 90 and 180 days after F administration. On the other hand, F levels incorporated in whole bone 30 days after acute exposure to F do not seem to be lost along time. The lack of increase in whole bone F levels in the experimental group along time suggests that there is a limit for F uptake in whole bone, probably related to the number sites available to bind F irreversibly.

Orientador: Lídia Parsekian Martins / Resumo: Objetivo: avaliar a ação de adesivo nanoparticulado com capacidade de liberação de flúor na prevenção de lesões de mancha branca (LMB) em pacientes sob tratamento ortodôntico. Materiais e Métodos: em 37 indivíduos, submetidos a tratamento ortodôntico, foram aplicados um adesivo ortodôntico convencional (Transbond XT) e um adesivo nanoparticulado com a capacidade de liberar flúor (Opal Seal), em um design split mouth. Antes da colagem e ao fim do tratamento, os pacientes foram submetidos a exame clínico e fotografias intrabucais. Durante o período de avaliação também foram realizadas avaliações mensais da quantidade de adesivo presente, visto por luz UV-A. Para comparação dos adesivos utilizamos uma ANOVA Multifatorial, sendo o score ao final do tratamento como variável dependente. No estudo da concordância entre os métodos de avaliação, foi realizado o Coeficiente de Correlação Ordinal de Spearman e a Análise de Concordância de Bland-Altman. Para o tempo de permanência do adesivo Opal Seal, utilizamos uma curva de sobrevivência, e na comparação do índice de descolagem utilizamos também uma curva de sobrevivência e a Análise de Sobrevivência de Kaplan-Meier. Resultados: Não houve diferença entre os adesivos testados, qualquer que fosse o método de avaliação utilizado, de forma que a formação de manchas brancas não difere entre os adesivos (p=0,581). Não houve um dente que fosse mais afetado por LMB em relação aos demais dentes avaliados (p=0,861). Não houve diferença entre os ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Objective: Evaluate the action of nanoparticulate adhesive with fluoride release capacity in the prevention of white spot lesions (WSL) in patients under orthodontic treatment. Materials and methods: In 37 individuals undergoing orthodontic treatment, a conventional orthodontic adhesive (Transbond XT) and a nanoparticulate adhesive with the ability to release fluoride (Opal Seal) were applied in a split mouth design. Before bonding and at the end of treatment, patients were submitted to clinical examination and intraoral photographs. During the evaluation period, monthly assessments of the amount of adhesive present were also performed, as seen by UV-A light. To compare the adhesives, we used multifactorial ANOVA, with score at the end of treatment as dependent variable. In the study of the concordance between the evaluation methods, the ordinal Spearman correlation coefficient and the Bland-Altman concordance analysis were performed. For the remain time of the Opal Seal adhesive, a survival curve was used, and in the comparison of the debonding index, the survival curve and the Kaplan-Meier survival analysis were also used. Results: There was no difference between the tested adhesives, whatever the evaluation method used, so that the formation of WSL does not differ between the adhesives (p= 0.581). There was no tooth that was more affected by WSL in relation to the other teeth evaluated (p= 0.861). There was no difference between the methods of evaluation (P = 0,581) and th... (Complete abstract click electronic access below) / Doutor

Sulfur trioxide (SO₃) adds to fluoroolefins of the form RCF=CF₂, (where R = F, SF₅, CF₃, CF₃OCF₂, CF₂=CF(CF₂)₂, CF₃(CF₂)₃O, CF₃O(CF₂)₂OCF₂, or CH₂ClCHClCH₂), yielding the fluorinated [beta]-sultones, RCFCF₂OSO₂. In the case of CF₃(CF₂)₃OCF=CF₂, a reverse addition occurs, giving the sultone, CF₃(CF₂)₃CF₂2OCFCF₂SO₂O. The fluoro [beta]-sultones are capable of undergoing different reactions, such as rearrangement, hydrolysis, esterification, and polymerization. These reactions, will result in the formation of compounds containing the fluorosulfonyl grouping (SO₂F); it is this group that yields the corresponding sulfonic acid upon base/acid treatment. The addition of sodium bisulfite to CF₃CF= CF₂ and CF₃(CF₂)₄CF=CF₂ in the presence of (C₆H₅CO)₂O₂ and Na₂B₄O₇·10H₂O was also studied to produce the corresponding sulfonic acid hydrates of the general formula, R[subscript f]CFHCF₂SO₃H·nH₂O. These acids were prepared, and thus, tested as possible fuel cell electrolytes. Infrared, ¹H and ¹⁹F nuclear magnetic resonance and mass spectra, as well as elemental analyses, will be presented in order to support the proposed structures for the resulted compounds.