xvi, 280 p. : ill. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Doppler-limited, steady-state, linear absorption spectra of 127 I 2 (diatomic iodine) near 675 nm were recorded with an internally-referenced wavelength modulation spectrometer, built around a free-running diode laser using phase-sensitive detection, and capable of exceeding the signal-to-noise limit imposed by the 12-bit data acquisition system. Observed I 2 lines were accounted for by published spectroscopic constants. Pressure broadening and pressure shift coefficients were determined respectively from the line-widths and line-center shifts as a function of buffer gas pressure, which were determined from nonlinear regression analysis of observed line shapes against a Gaussian-Lorentzian convolution line shape model. This model included a linear superposition of the I 2 hyperfine structure based on changes in the nuclear electric quadrupole coupling constant. Room temperature (292 K) values of these coefficients were determined for six unblended I 2 lines in the region 14,817.95 to 14,819.45 cm -1 for each of the following buffer gases: the atoms He, Ne, Ar, Kr, and Xe; and the molecules H 2 , D 2 , N 2 , CO 2 , N 2 O, air, and H 2 O. These coefficients were also determined at one additional temperature (388 K) for He and CO 2 , and at two additional temperatures (348 and 388 K) for Ar. Elastic collision cross-sections were determined for all pressure broadening coefficients in this region. Room temperature values of these coefficients were also determined for several low- J I 2 lines in the region 14,946.17 to 14,850.29 cm -1 for Ar. A line shape model, obtained from a first-order perturbation solution of the time-dependent Schrödinger equation for randomly occurring interactions between a two-level system and a buffer gas treated as step-function potentials, reveals a relationship between the ratio of pressure broadening to pressure shift coefficients and a change in the wave function phase-factor, interpreted as reflecting the "cause and effect" of state-changing events in the microscopic domain. Collision cross-sections determined from this model are interpreted as reflecting the inelastic nature of collision-induced state-changing events. A steady-state kinetic model for the two-level system compatible with the Beer-Lambert law reveals thermodynamic constraints on the ensemble-average state-changing rates and collision cross-sections, and leads to the proposal of a relationship between observed asymmetric line shapes and irreversibility in the microscopic domain. / Committee in charge: David Herrick, Chairperson, Chemistry; John Hardwick, Advisor, Chemistry; Jeffrey Cina, Member, Chemistry; David Tyler, Member, Chemistry; Michael Raymer, Outside Member, Physics

This thesis deals with the importance of milk as a natural source of iodine in human nutrition. The thesis provides a data of the consumption of milk and milk products and their contribution to the protection needs iodine for students and employees of the University of South Bohemia in Ceske Budejovice. The experiment includes a total of 60 people (20 men and 40 women). Empirical data wasobtained within the grant project named GAJU 011/2013/Z and NAZV QH 81105. Data of consumption of milk and milk products were obtained through questionnaires. For men, average weekly consumption of milk was 826.5? 835.1 ml (118.1 ml per day) and for women 912.4? 783.9 ml (130.3 ml per day). Average consumption of yogurt for men was 361.0? 401.4 g per week (51.6 g per day), for woman 428.4? 338.8 g per week (61.2 g per day) and average consuption of cheese was for men 263.0? 240.5 g per week (37.6 g per day) and for woman was 260.2? 226.5 per week (37.2 g per day). Through the milk and milk products tested, men average 81.6 g of iodine per day, woman adopted 93.4 g. According to the results, the amout of consumed milk and milk products was lower than the nationwide average, but still covered more than half of daily iodine needs. The thesis presents the data of the iodine concentration in urine for students and employees of the University of South Bohemia in Ceske Budejovice (n=62) as an indicator of iodine supply to the organism. The average iodine content in urine of all subjects (men and women) was 230.4? 171.3 gl-1, for men (n=21) reached 244.6? 195.2 gl-1, for women was 223.2? 159.8 gl-1. Results of the average iodine content in urine reflected the physiological range, i.e. for the students and employees of the University of South Bohemia was supply of iodine in organism sufficient. The thesis also provides information about the amount of iodine in asamples of cow´s milk on a selected farm (n=50) of the Jihocesky region, the Plzensky region and Vysocina during the years 2011 - 2013. Samples of cow´s milk were obtained in collaboration with the Central Laboratory of dairy Madeta a.s in Ceske Budejovice and Veterinary Centre s.r.o Susice. In 2011, the average concentration of iodine was 321,0? 337.8 gl-1, in 2012 was concentration of iodine 298.8? 290.8 gl-1 and in 2013 was 234.7? 116.1 gl-1 also otherwise: in all years was it was determined that there was an abundance of iodine. The highest values (315.6? 305.1 gl-1) of iodine was in the Jihocesky region. In Vysocina a lower average level of the iodine was detected (9.5 %), as well as in the Plzensky region where the amount of iodine in milk was lower by 53.7 %, compared to the South Bohemia region and 48.8 % compared to the Vysocina region.

The thesis deals with the evaluation of the impact of different quantities and forms of iodine in ration dairy cows on the concentration of hormones of the thyroid in the blood plasma. The experiment was done with a herd of Red cows breeding in the conversion to breed in the breeding of Holstein dairy cows in Klatovy. Iodine was given in both inorganic and organic form. Before experimenting, the value of total and free forms of hormones was very low. During the experiment, increased concentrations of hormones in connection with the intake of inorganic iodine, the significant deviations showed free forms of thyroid hoemones. Nevertheless, the addition of organic iodine was not fully substituted for the reduction of inorganic iodine content. The thesis also discusses the assessment of the thyroid status by Czech red cattlebreeding on the school farm. The aim was to compare the activity of the thyroid gland in high-yield dairy cows breeding in a barn environment and cattle on pasture reared cattle. For red cattle reared on pasture, there were characteristically higher concentration levels of total and free hormones compared with high yield dairy cows. Nevertheless, in comparison with the reference value,there was a concentration of TT4 for Czech red cattlelower, it coresponded well as dairy cows, rather lower iodine supply. In connection with the rise (higher content) TT4, possibly fT4, there was a similar tendency for the TT3 and fT3, so we can´t assume a deeper state of iodine deficiencies and its associationwith an underactive thyroid gland.

This thesis comprises three projects focused on the use of the combination of catalytic copper and iodonium salts towards the functionalisation of alkenes. Chapter 2 details the development of an enantioselective and regiodivergent allylic amide arylation procedure using a specific copper(II)-bisoxazoline pre-catalyst and hexafluorophosphate diaryliodonium salts. The regioselectivity of the process was discovered to be controlled by the electronic properties of the iodane employed, allowing enamide production to be biased with electron-poor iodonium salts and oxazines to be produced with electron-rich analogues. An overall scope of 38 compounds was collaboratively elaborated, with 20 synthesised personally. All products were generated in useful yields and high levels of enantioselectivity. Chapter 3 describes efforts towards the application of a copper-catalysed oxy-alkenylation procedure to the production of the macrolidal natural product (-)-lyngbyaloside B. It is proposed that an elaborate homoallylic carbamate may be coupled with a complex polyoxygenated alkenyl(aryl)iodonium salt as a fragment coupling for polyketide synthesis. Following extensive investigations, it was discovered that the challenging vinyl-iodonium salt could be synthesised in good yields and then coupled with the desired homoallylic carbamate, albeit in limited yield and low d.r. Chapter 4 presents initial studies towards a computational understanding of the copper-catalysed arylation of alkenes with iodonium salts. Evidence is presented to suggest that two functionalisation modes are energetically accessible, allowing the production of regioisomeric arylated products.

Submitted by Luciana Abrão de Oliveira Restini Oliveira (luciana.abraonutri@gmail.com) on 2016-04-29T15:05:13Z No. of bitstreams: 1 Tese Luciana Abrão.pdf: 758211 bytes, checksum: 66d580b56d5bc28949f49defc70b57eb (MD5) Bitstreams deleted on 2016-10-27T11:27:33Z: restini_lao_dr_arafcf.pdf,. Added 1 bitstream(s) on 2016-10-27T11:28:05Z : No. of bitstreams: 1 000866332.pdf: 560429 bytes, checksum: 981780d89948d032bb6ebac21b1396ec (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-05-02T18:12:48Z (GMT) No. of bitstreams: 1 restini_lao_dr_arafcf.pdf: 758211 bytes, checksum: 66d580b56d5bc28949f49defc70b57eb (MD5) / Made available in DSpace on 2016-05-02T18:12:48Z (GMT). No. of bitstreams: 1 restini_lao_dr_arafcf.pdf: 758211 bytes, checksum: 66d580b56d5bc28949f49defc70b57eb (MD5) Previous issue date: 2015-12-04 / A ingestão adequada de iodo durante a gestação é essencial para a síntese dos hormônios tireoidianos, que são importantes para as funções fisiológicas da mãe e para uma adequada maturação do sistema nervoso central do feto. Os efeitos da deficiência e/ou excesso de iodo são evidentes em todas as idades e se manifestam desde a fase fetal. O presente estudo teve como objetivo avaliar a excreção urinária de iodo, a função tireoidiana, e concentração séricas de antioxidantes e marcadores do estresse oxidativo em gestantes. Participaram do estudo 191 gestantes e 62 mulheres não gestantes que foram avaliadas segundo o estado nutricional e foram realizadas análises de iodo na urina, marcadores de estresse oxidativo e função tireoidiana. A partir das análises realizadas, foi observada insuficiência de iodo em 81 gestantes. Não houve alteração nas concentrações de TSH para 89% das gestantes. Os valores de anti-TPO foram superiores para o grupo controle em comparação com o grupo gestante (64,5% e 12,6%, respectivamente). Para o anti-TG, o grupo controle também apresentou valores maiores (11,6%). Não houve alteração significativa nos anticorpos quanto à sua classificação em relação aos valores de TSH e iodúria. A avaliação do estresse oxidativo revelou níveis de AOPP superiores para as gestantes e maiores níveis dos antioxidantes CAT e SOD. A classificação de iodúria com relação aos marcadores de estresse oxidativo revelou menores níveis de α-tocoferol para as gestantes com insuficiência de iodo. Sendo assim, os resultados sugerem que a insuficiência de iodo não foi capaz de induzir alterações nos níveis de TSH e anticorpos e que mulheres grávidas com excreção urinária de iodo adequada apresentaram melhor perfil do antioxidante α-tocoferol, indicando que o iodo pode desempenhar um papel significativo na capacidade antioxidante durante a gestação. / Adequate intake of iodine during pregnancy is essential for synthesis of thyroid hormones, which are important for the physiological functions of the mother and proper maturation of the central nervous system of the fetus. The effects of disability and/or over are evident in all ages and manifest in the fetal stage. This study aimed to evaluate the urinary excretion levels of iodine, thyroid function and markers of oxidative stress in pregnant women. The study enrolled 191 pregnant women and 62 non-pregnant women who were evaluated according to the nutritional status and were held iodine analysis in urine, thyroid function and oxidative stress markers. From the analyzes, iodine deficiency was observed in 81 pregnant women. There was no change in TSH concentrations to 89% of pregnant women. The anti-TPO levels were higher in the control group compared to the pregnant group (64,5% and 12,6%, respectively). For anti-TG, the control group also showed higher values (11,6%). There was no significant change in antibodies and their classification about TSH levels and urinary iodine. Evaluation of oxidative stress revealed AOPP levels greater for pregnant women and higher levels of antioxidants SOD and CAT. Urinary iodine classification with respect to oxidative stress markers showed lower levels of α-tocopherol for pregnant women with iodine insufficiency. Thus, the results suggest that iodine deficiency was not able to induce altered levels of TSH and antibodies and pregnant women with urinary excretion of appropriate iodine showed a better profile of the α-tocopherol antioxidant, indicating that the iodine may play a role significant antioxidant capacity during pregnancy.

Master of Science / Department of Animal Sciences and Industry / Michael Tokach / In 3 experiments, 4,720 pigs were used to determine the effects of: 1) dietary fat and feeding duration on growth performance and fat quality in finishing pigs; or 2) a novel protease or 3) increasing levels of Zn amino acid complex (ZnAA) or ZnO on finishing pig performance. Experiment 1 tested the effects of feeding tallow, soybean oil, or a blend of the two for various feeding durations (d 0 to 42, 42 to 84, or 0 to 84). Overall, pigs fed added fat for the entire 84 d had improved G:F compared to those fed a control diet. Additionally, pigs fed additional fat for the entire study had improved ADG and G:F as well as increased d 84 BW compared to pigs fed additional fat for 42 d. Increasing the feeding duration of soybean oil lowered monounsaturated fatty acids and increased polyunsaturated fatty acid concentrations while these values remained relatively unchanged by the addition of tallow. There were feeding period by fat source interactions for fatty acid composition and iodine value for belly and backfat, but not jowl fat, indicating a longer turnover rate for jowl fat compared to belly or backfat. In Exp. 2, adding a protease to a nutrient deficient diet increased ADFI and tended to increase ADG compared to pigs fed a negative control diet. There were no differences observed in ADG, ADFI, or G:F between pigs fed a positive control diet, formulated to 90% of the pigs SID lysine requirement, and those fed a negative control diet plus the protease, which would suggest the release values attributed to the enzyme were accurate. In Exp. 3, supplementing additional Zn from either ZnAA or ZnO at 25, 50, or 75 ppm in finishing diets for commercial finishing pigs was evaluated. Overall, no differences were observed in ADFI, but a Zn source by level interaction was observed for ADG and G:F, as pigs fed increasing ZnO were observed to have similar performance, while pigs fed added levels of 25 and 50 ppm Zn from ZnAA had decreased performance compared to those fed the highest level of ZnAA.

En cas d'accident grave sur un réacteur à eau sous pression, l'évaluation de la quantité d'iode susceptible d'être rejetée dans l'environnement revêt une grande importance du fait de la radiotoxicité et du caractère volatil de cet élément. Le rejet d'iode du cœur du réacteur endommagé et son transport dans les différentes parties du réacteur jusqu'à l'enceinte de confinement, ont été largement étudiés, en particulier dans les expériences Phébus-FB. A ce jour, les connaissances acquises et les modèles utilisés ne permettent pas de rendre compte complètement du comportement de l'iode observé lors d'essais à grande échelle. Une hypothèse est que l'iode gazeux proviendrait du circuit primaire à cause de processus qui limiteraient la formation d'iodure de césium. La formation d'iodure de césium pourrait être limitée à cause de limitations cinétiques ou à la présence d'éléments qui piégeraient le césium (molybdène, bore). Des expériences de laboratoire dans un montage spécialement conçu reproduisent la chimie de mélanges CsI/MoO3 et CsI/H3BO3 sous vapeur d'eau entre 1600°C (température et 150°C. Les aérosols et les gaz présents à 150°C sont piégés séparément. Les analyses des phases condensées et aérosols par MEBE-EDX, microspectrométrie Raman, ICP-MS et XPS ont permis d'identifier des particules d'aérosols submicroniques collectés à 150°C. Les analyses des gaz piégés en solution par ICP-MS et spectroscopie UV-visible traduisent l'existence d'iode gazeux pour les deux systèmes étudiés {Cs, I, Mo, O, H} et {Cs, I, B, O, H}. La modélisation de la chimie et du transport des espèces gazeuses et particulaires pour les deux systèmes dans la ligne expérimentale a été réalisée à l'aide du code de calcul SOPHAEROS développé à l'IRSN. Les résultats expérimentaux ont ainsi pu être comparés aux résultats des simulations. / In case of a severe accident on a nuclear reactor, radioactive iodine may be released into the environment, impacting significantly the radiological consequences. Determination of the amount released, and of the physical state of iodine (gaseous form or solid aerosol form), is thus a major issue. The release of iodine from the damaged reactor core and its transport in the different parts of the reactor up to the reactor containment, have been extensively studied, particularly in the Phébus-FP large scale experiments. Phébus-FP results notably showed that a significant fraction of iodine under gaseous form can reach the containment. The models used in severe accident codes did not (and still does not) fully account for this iodine speciation. A likely explanation is that iodine keeps a gaseous form up to the containment due to some processes that limit the formation of caesium iodide in the reactor coolant system (RCS) (caesium iodide was assumed to be the dominant form of iodine in the RCS). Caesium iodide formation would be limited due to chemical kinetic limitations and due to the presence of other elements (molybdenum or boron) responsible for “trapping” the caesium. An experimental research program has been developed with the aim to study the chemical behaviour of iodine during its transport in the RCS, with presence of steam, caesium and molybdenum or boron. Experiments are compared to calculations performed with the IRSN severe accident code ASTEC where a chemical kinetic model has been implemented

Made available in DSpace on 2014-06-11T19:23:04Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-07-24Bitstream added on 2014-06-13T20:10:32Z : No. of bitstreams: 1 perrella_fa_me_sjc.pdf: 553745 bytes, checksum: 194275e9381abab548acc726f59f78f0 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O objetivo desse estudo foi avaliar o efeito do iodo-povidine (10%), irrigado subgengivalmente, como adjunto ao tratamento mecânico periodontal convencional (raspagem e alisamento radicular). Foram selecionados 29 indivíduos portadores de periodontite crônica, divididos aleatoriamente em dois grupos; Grupo Controle (RAR) – constituído de 15 pacientes que receberam tratamento periodontal manual e posterior irrigação com solução fisiológica (NaCl 0,9%) e; Grupo Experimental (RAR-I) – Constituído de 14 pacientes que receberam tratamento periodontal convencional e posterior irrigação com iodo-povidine (PVP-I 10%). Foram avaliados parâmetros clínicos (Índice Gengival (IG), Índice de Placa (IP), Sangramento à sondagem (SS), Supuração (Sup), Profundidade de Sondagem (PS), Nível de Inserção Clínico (NIC) e microbiológicos (método checkerboard DNA-DNA hybridization), no início e após 30 e 90 dias do tratamento periodontal. Observamos a melhora em todas as variáveis clínicas, pós-tratamento convencional, quando comparados aos dados iniciais da doença periodontal (p<0,05). A adição de iodo-povidine não mostrou ganho terapêutico significativo na maioria dos parâmetros clínicos utilizados quando comparados aos valores obtidos do Grupo Controle. Os resultados microbiológicos indicam que ambas as terapias reduziram a contagem e proporção dos patógenos periodontais, sendo que, aos 30 dias, o Grupo RAR-I exibiu maior redução na proporção do complexo vermelho (38%) comparado com o Grupo RAR (20%). Entretanto, aos 90 dias, não foram observadas diferenças significantes estatisticamente entre os grupos. Dessa forma, conclui-se que a adição do PVP-I como agente de irrigação subgengival não trouxe benefícios adicionais ao tratamento da periodontite crônica. / The aim of the study was to evaluate the effect of povidone-iodine (10%), irrigated subgingivally as adjunct to periodontal mechanical treatment (scaling and root planning). We used 29 individuals with chronic periodontitis, randomly divided into two groups; Control Group (RAR) - consisting of 15 patients who received conventional periodontal treatment and later irrigation with saline solution (NaCl 0,9%) and; Experimental Group (RAR-I) - Consisting of 14 patients who received conventional periodontal treatment and later with irrigation-povidone-iodine (PVP-I 10%). We evaluated clinical parameters (Gingival Index (IG), Plaque Index (IP), Bleeding on Probing (SS), Suppuration (Sup), Probing depth (PS), Clinical Attachment Level (NCI) and Microbiological (method checkerboard DNA - DNA hybridization) at the beginning and after 30 and 90 days of periodontal treatment. Noticed the improvement in all clinical variables, post-conventional treatment, as compared to the initial data of periodontal disease (p <0.05). Even the addition of PVP-I did not showed significant therapeutic gain in most clinical parameters used when compared to levels obtained from the control group. The microbiological results indicate that both therapies reduced the proportion of counting and periodontal pathogens, and, at 30 days, the RAR-I Group showed further reduction in the proportion of the red complex (38%) compared with the RAR group (20%). Meanwhile, the 90 days, no statistically significant differences were found between the groups. Thus it appears that the addition of PVP-I as an agent of subgingival irrigation has not brought additional benefits in the treatment of chronic periodontitis.

Made available in DSpace on 2014-06-11T19:23:24Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-11-20Bitstream added on 2014-06-13T19:29:19Z : No. of bitstreams: 1 zaninetti_ra_me_jabo.pdf: 1868941 bytes, checksum: 35f5d09c9012f6e14fec157642a20088 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Na região Amazônica Sul - Ocidental encontram-se espécies cujos frutos encerram quantidade apreciável de óleo com valor econômico para diferentes aplicações industriais, como a produção de biodiesel. O presente trabalho teve como objetivo avaliar o potencial do óleo de tucumã (Astrocaryum aculeatum) para produção de biodiesel. Os frutos de tucumã foram colhidos em áreas ao longo das BR- 364 e BR-317 a aproximadamente 150 km de Rio Branco - AC. Dos frutos, avaliou-se a massa, e posteriormente foram despolpados com a finalidade de separá-los em: polpa (epicarpo + mesocarpo), castanha ou caroço (endocarpo) e amêndoas (semente retirado do interior do endocarpo), cujas massas também foram determinadas. A extração do óleo de cada fração foi feita por prensagem. Foram avaliados os teores de lipídios totais na amêndoa e na polpa, o rendimento aparente da prensa e as características físico-químicas e cromatográficas do óleo extraído. O valor médio de lipídios totais na amêndoa foi de 21,9%, enquanto que o valor médio de lipídios totais na polpa foi de 31,9%. Observou-se um rendimento aparente de 70-73%. Os valores médios de densidade, viscosidade, índice de acidez, índice de iodo, índice de peróxido e índice de saponificação foram, respectivamente, 0,903 ± 0,003 g cm-3; 76,3 ± 1,6 mm2 s-1; 7,11 ± 1,47 mg KOH g-1; 113,84 ± 3,28 g I2 10-2 g-1; 30,79 ± 0,39 meq kg-1; 211,38 ± 1,68 mg KOH g-1. Atrávez da cromatografia gasosa pode se determinar que 56,5% da fração dos ácidos graxo do óleo de tucumã foi constituída por ácidos graxos saturados. O tucumanzeiro é uma espécie que possui boa produtividade em óleo, mesmo em solos ácidos e com baixa fertilidade, apresentando potencial para ser utilizado como uma fonte adicional de renda pelas comunidades da Amazônia / In southwestern Amazonia, various plant species produce oil-rich fruits that have economic potential for the production of biodiesel. To evaluate the potential of oils extracted from tucumã palm fruits (Astrocaryum aculeatum), we collected fruits from pasture areas along the BR-364 and BR-317 highways, approximately 150-km from Rio Branco, Acre, Brazil, Fruits were weighed, depulped, and separated into three components: pulp (epicarp + mesocarp), nut or seed (endocarp), and kernel (extracted from the endocarp). Each component was weighed and subjected to oil extraction using a mechanical press. The oil obtained was analyzed for density and viscosity, as well as acidity, iodine, peroxide, and saponification values. The total lipids average content in the kernel was 21.9%, while the mean total lipids content in the pulp was 31.9%. An apparent yield of 70-73% was observed. Physicochemical data analyses revealed significant differences in viscosity and acidity index values among fruit samples. Average density, iodine, peroxide, and saponification values were 0.903 ± 0.003 g cm-3; 76.3 ± 1.6 mm2 s-1; 7,11 ± 1.47 mg KOH g-1; 113.84 ± 3.28 g I2 10-2 g-1; 30.79 ± 0.39 meq kg-1; 211.38 ± 1.68 mg KOH g-1, respectively. Through gas chromatography could determine that 56.5% of fat acids portion in the tucumã oil was saturated fat acids. The tucumã palm is a good oil producer specie, even in acid and low fertility soils, showing a potential to be used as an additional income to be used by the Amazonic communities

Made available in DSpace on 2014-10-09T12:32:09Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:54Z (GMT). No. of bitstreams: 1 11289.pdf: 2851934 bytes, checksum: 328e6c9804dcaae490bbe9287fd55516 (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP