Excess nitrogen (N) excretion from animal agriculture results in reduced air and water quality, and poses a risk to human health. Although the dairy industry utilizes milk urea N (MUN) to monitor protein feeding and N excretion, phenotypic diversity among cows may influence MUN and thus bias feed management. An initial study using data from 2 previously published research trials and a field trial, observed that cow had a significant effect on MUN variation. Regression models, utilized to predict MUN, corrected for dietary nutrients and some animal effects, and thus the observed effect of cow on MUN variation may reflect genetic selection decisions of animals with either poor or efficient urea transport. A second trial observed that MUN and PUN concentrations were positively correlated with gut urea clearance, providing evidence for differences in urea transport activity among cows. The presence of urea transport variation suggests that current protein recommendations may not estimate true requirements. A third trial observed that animals fed sub-NRC levels of RDP and RUP had reduced N intake and excretion of fecal N, urinary urea-N, and MUN. Animals maximized N efficiency and had no loss in milk production, suggesting a possible overestimation of RDP and RUP in the current NRC prediction model. The present project provides evidence for phenotypic variation among cows, which may be partially explained by differences in urea transport activity. Future work confirming genetic variation among urea transporters may provide an opportunity to improve feeding management if cow urea efficiency is known. / Master of Science

Formaldehyde emissions from non-structural wood composites are regulated and the regulation target is urea-formaldehyde (UF) resin. UF resins are hydrolytically unstable and constantly emit formaldehyde as a function of temperature and relative humidity. When heated, wood also generates formaldehyde, but this was of little concern until 2010 when formaldehyde regulations became much more demanding. This regulation motivated the industry to account for all formaldehyde sources, synthetic as from resin, and biogenic as from wood. This effort represents first steps towards quantifying biogenic and synthetic contributions to formaldehyde emissions in non-structural wood composites. It is possible to distinguish the 13C/12C isotope ratio of UF resins from the isotope ratio of plant biomass. Conditions during and after composite hot-pressing promote reactions that generate formaldehyde from wood and UF resin, and the kinetic isotope effect continuously lowers the product isotope ratios as a function of yield. If such isotope fractionation did not occur, it would be a simple matter to quantify contributions of wood and UF resin to formaldehyde emissions using static isotope ratios. Isotope fractionation, therefore, complicates the requirements for distinguishing biogenic and synthetic formaldehyde in wood composite emissions. Those requirements are 1) establish the reference carbon isotope ratios in wood and in UF resin (just the formaldehyde portion of UF), and 2) estimate the kinetic isotope effects in formaldehyde generation by wood and cured UF resin. The latter requirement fixes a range for the respective isotope ratios; the numerical ranges enable a simple model of the average isotope ratio for a mixture of biogenic and synthetic formaldehyde in wood composite emissions. Finally, the measured isotope ratio of captured emissions would be compared to the model. This work did not achieve all aspects of the requirements mentioned, but a solid foundation was established for future completion of the ultimate goals. In reference to requirement 1, the carbon isotope ratio of experimental Pinus taeda wood was accurately measured (including some isolated fractions) using isotope ratio mass spectroscopy (IRMS). IRMS of UF resin first requires removal of urea carbons- UF resin was subjected to acid hydrolysis and capture of the resin formaldehyde into aqueous ammonium hydroxide. This provided a nearly quantitative conversion (negligible isotope fractionation) of resin formaldehyde into hexamine for IRMS. Using this hexamine method, the formaldehyde carbon isotope ratios of two industrial UF resins were accurately measured, demonstrating basic feasibility for the project goal. Estimating the kinetic isotope effect (Requirement 2) required creation of a thermochemical reactor, where wood or cured UF resin was heated under N2 flow such that the emitted formaldehyde was easily captured. In this case, conversion of captured formaldehyde into hexamine was abandoned in favor of silica gel cartridges loaded with sodium bisulfite. Isolation and IRMS of the formaldehyde-bisulfite adduct were effective and considered easily transferable to industrial settings. This system was employed to measure fractionation in cured resin as a function of relative humidity, and in Pinus taeda wood as a function of relative humidity, temperature, and time. More information about isotope fractionation is required; but most notable was the fractionation behavior in wood where evidence was found for multiple formaldehyde generating reactions. Overall, this work established feasibility for the goals and laid the foundation for future efforts. / Master of Science / Home-interior products like cabinetry are often produced with wood composites adhesively bonded with urea-formaldehyde (UF) resin. UF resins are low cost and highly effective, but their chemical nature results in formaldehyde emission from the composite. High emissions are avoided, and the federal government has regulated and steadily reduced allowable emissions since 1985. The industry continuously improved UF technologies to meet regulations, as in 2010 when the most demanding regulations were implemented. At that time, many people were unaware that wood also generates formaldehyde; this occurs at very low levels but heating during composite manufacture causes a temporary burst of natural formaldehyde. Some wood types produce unusually high formaldehyde levels, making regulation compliance more difficult. This situation, and the desire to raise public awareness, created a major industrial goal: determine how much formaldehyde emission originates from the resin and how much originates from the wood. These formaldehyde sources can be distinguished by measuring the carbon isotope ratio, 13C/12C. This ratio changes and varies due to the kinetic isotope effect. Slight differences in 13C and 12C reactivity reveal the source as either petrochemical (synthetic formaldehyde) or plant-based (biogenic formaldehyde). This work demonstrates that achieving the industry goal is entirely feasible, and it provides the analytical foundation. The technical strategy is: 1) establish reference isotope ratios in wood and in UF resin, and 2) from the corresponding wood composite, capture formaldehyde emissions, measure the isotope ratio, and simply calculate the percentage contributions from the reference sources. However, a complication exists. When the reference sources generate formaldehyde, the respective isotope ratios change systematically in a process called isotope fractionation (another term for the kinetic isotope effect). Consequently, this effort developed methods to measure fractionation when cured UF resin and wood separately generate formaldehyde, with greater emphasis on wood. Isotope fractionation in wood revealed multiple fractionation mechanisms. This complexity presents intriguing possibilities for new perspectives on formaldehyde emission from wood and cured UF resin. In summary, this work demonstrated how source contributions to formaldehyde emissions can be determined; it established effective methods required to refine and perfect the approach, and it revealed that isotope fractionation could serve as an entirely novel tool in the materials science of wood composites.

Yes / The cocrystal of nitrofurantoin with urea (C8H6N4O5)·(CH4N2O), a non-ionic supramolecular complex, has been studied. Nitrofurantoin (NF) is a widely used antibacterial drug for the oral treatment of infections of the urinary tract. Characterization of the cocrystal of nitrofurantoin with urea (NF–urea) was performed spectroscopically by employing FT-IR, FT- and dispersive-Raman, and CP-MAS solid-state 13C NMR techniques, along with quantum chemical calculations. With the purpose of having a better understanding of H-bonding (inter- and intra-molecular), two different models (monomer and monomer + 3urea) of the NF–urea cocrystal were prepared. The fundamental vibrational modes were characterized depending on their potential energy distribution (PED). A combined experimental and theoretical wavenumber study proved the existence of the cocrystal. The presence and nature of H-bonds present in the molecules were ascertained using quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis. As the HOMO–LUMO gap defines the reactivity of a molecule, and this gap is more for the API than the cocrystal, this implies that the cocrystal is more reactive. Global descriptors were calculated to understand the chemical reactivity of the cocrystal and NF. Local reactivity descriptors such as Fukui functions, local softness and electrophilicity indices were analysed to determine the reactive sites within the molecule. The comparison between NF–urea (monomer) and NF showed that the cocrystal has improved overall reactivity, which is affected by the increased intermolecular hydrogen bond strength. The docking studies revealed that the active sites (C[double bond, length as m-dash]O, N–H, NO2, N–N) of NF showed best binding energies of −4.89 kcal mol−1 and −5.56 kcal mol−1 for MUL and 1EGO toxin, respectively, which are bacterial proteins of Escherichia coli. This cocrystal could potentially work as an exemplar system to understand H-bond interactions in biomolecules.

No description available.

Níveis elevados de proteína bruta (PB) na dieta de ruminantes têm sido associado com comprometimento na fertilidade devido, principalmente, a elevação da concentração do nitrogênio uréico plasmático (NUP). Objetivou-se no presente estudo avaliar o efeito do fornecimento de dietas contendo nitrogênio não-protéico (NNP) sem prévia adaptação, durante curto espaço de tempo e em diferentes fases do ciclo estral, a fêmeas bovinas superovuladas quanto à produção, qualidade e ao grau de desenvolvimento de embriões recuperados. Sessenta e oito vacas da raça Nelore com escore corporal de 7,56 e peso médio de 557,6 kg foram distribuídas em três tratamentos: controle (C), uréia antes do dia 0 (UA; fornecimento de dieta com uréia do dia -5 ao dia 0) e uréia depois do dia 0 (UD; fornecimento de dieta com uréia do dia 0 ao dia 5). As vacas foram mantidas em piquetes com pastagem de Brachiaria brizantha cv. Marandu e receberam diariamente, 3,0 kg/animal de concentrado durante 16 dias. Foram formulados dois concentrados, sendo que as dietas totais (concentrado + consumo estimado de pastagem) continham 12,0% (dieta controle) e 14,6% de PB (dieta com NNP). A diferença na PB entre as dietas foi o acréscimo de 100g/vaca/dia de uréia. Os animais foram sincronizados, superovulados e inseminados. Sete dias (dia 7) após a inseminação (dia 0), realizou-se a colheita e análise dos embriões quanto à qualidade a ao grau de desenvolvimento. Amostras de sangue foram coletadas nos dias -5, 0 e 5 para mensurações das concentrações de NUP, glicose, insulina e progesterona. Houve efeito significativo dos tratamentos sobre a concentração médias de NUP no dia -5 (C = 16,18ab, UA = 17,72a e UD = 14,47b mg/dL; P = 0,0007), no dia 0 (C = 18,95b, UA = 22,71a e UD = 21,15 ab mg/dL; P = 0,0010) e no dia 5 (C = 20,93a, UA = 19,08b e UD = 21,51a mg/dL; P = 0,0022). Quanto às concentrações de glicose, insulina e progesterona não houve efeito dos tratamentos. Não houve efeito significativo nem da inclusão da uréia e nem do momento da inclusão da uréia sobre o total de estruturas recuperadas, total de estruturas fecundadas e de embriões viáveis. Porém, houve efeito do momento de inclusão da uréia sobre a porcentagem de estruturas fecundadas em relação ao total de estruturas recuperadas (UA = 75,3 vs. UD = 50,7%) e sobre a porcentagem de embriões viáveis em relação ao total de estruturas recuperadas (UA = 73,2 vs. UD = 39,4%). O tratamento UD acarretou em menor capacidade de fecundação do oócito em relação ao tratamento UA, havendo redução de aproximadamente 32,7% na proporção de oócitos fecundados sobre o total de estruturas recuperadas deste tratamento. / High levels of crude protein (CP) in ruminant diets were associated with detrimental effect on fertility, mainly, due to the rise of plasmatic urea nitrogen (PUN) concentration. The aim of this study was to verify the effects of short term non-protein nitrogen feeding at different periods of the oestrus cycle in superovulated cows without previous adaptation on yield, quality and development degree of recovered embryos. Sixty eight Nelore cows with body condition score of 7.56 and body weight of 557.6 kg were divided in three different groups: control (C), urea before day 0 (UB; urea supply from day -5 to day 0) and urea after day 0 (UA; urea supply from day 0 to day 5). Animals were grazing in Brachiaria brizantha cv. Marandu pasture and received 3.0 kg/animal/day of concentrate during 16 days. Two concentrates were formulated and the total diets (concentrate + estimate forage intake) had 12.0% (control diet) and 14.6% of CP (NPN diet). The difference in CP between diets was the addition of 100g/cow/day of urea. Animals were synchronized, superovulated and inseminated. The embryos were collected seven days (day 7) after insemination (day 0) and quality and development degree were also evaluated. Blood samples were collected on day -5, 0 and 5 for measurement of PUN, glucose, insulin and progesterone. There was significant effect of treatments on average PUN concentration at day -5 (C = 16.18ab, UB = 17.72a and UA = 14.47b mg/dL; P = 0.0007), at day 0 (C = 18.95b, UB = 22.71a and UA = 21.15ab mg/dL; P = 0.0010) and at day 5 (C = 20.93a, UB = 19.08b and UA = 21.51a mg/dL; P = 0.0022). For glucose, insulin and progesterone there was no effect of treatments. It was observed neither effect of urea inclusion nor the moment of urea inclusion in diet on the total number of recovered structures, total number of fertilized structures and total number of viable embryos. However, it was observed effect of the moment of urea inclusion on the rate of fertilized structures in relation to the total number of recovered structures (UB = 75.3 vs. UA = 50.7%) and on the rate of viable embryos in relation to the total number of recovered structures (UB = 73.2 vs. UA = 39.4%). The UA treatment lead to lowest fertilizing oocyte capacity in relation to UB treatment with an approximate reduction of 32.7% on oocytes fertilized proportion over the total recovered structures in this treatment.

Este estudo teve como objetivo avaliar o efeito de níveis crescentes de uréia na dieta de vacas em lactação sobre a produtividade, características físico-químicas e de composição do leite, bem como composição da proteína do leite. Foram utilizadas nove vacas Holandesas em lactação, em delineamento experimental tipo quadrado latino 3X3, com 3 tratamentos, 3 períodos e 3 quadrados. O experimento teve duração total de 63 dias divididos em 3 períodos de 21 dias. Os tratamentos foram: tratamento A (controle) com dieta formulada para suprir 100% das exigências do NRC (2001) em termos de PB, proteína degradável no rúmen (PDR), proteína não degradável no rúmen (PNDR), utilizando farelo de soja como principal fonte protéica e cana-de-açúcar como volumoso; tratamento B, dieta com a inclusão de 0,75% de uréia, em substituição parcial ao farelo de soja, e tratamento C, dieta com inclusão de 1,5% de uréia, em substituição parcial ao farelo de soja. Todas as dietas foram isoenergéticas (1,53 Mcal/kg de energia líquida de lactação) e isoprotéicas (16% de proteína bruta). Não foram observadas diferenças entre os tratamentos, quando os resultados foram analisados por regressão polinomial simples, quanto a: consumo de matéria seca, produção de leite, produção de leite corrigida para 3,5%, produção de proteína, produção de gordura, produção de lactose e produção de sólidos totais e Log CCS. Também não houve influência dos tratamentos sobre pH, crioscopia, densidade e prova de resistência ao álcool. No entanto, a acidez, sofreu efeito linear decrescente (p = 0,017) em função dos níveis de uréia na dieta. Quanto à composição do leite, os teores de proteína, gordura, lactose, uréia, extrato seco total e extrato seco desengordurado não foram influenciados pelos tratamentos. A composição da proteína também não foi alterada pela inclusão de até 1,5% de uréia na dieta, não sendo observada diferença entre os tratamentos para a proteína bruta, proteína verdadeira, caseína, proteína do soro, nitrogênio não caseinoso, nitrogênio não protéico, uréia, bem como as relações proteína verdadeira: proteína bruta e caseína: proteína verdadeira. Estes resultados sugerem que o uso de até 1,5% de uréia na matéria seca da dieta não altera a capacidade de produção, as características físico-químicas e de composição do leite, bem como a composição da proteína do leite. / The aim of this study was to evaluate the effects of three different dietary levels of urea on milk yield and composition, and milk protein composition. Nine lactating Holstein cows were used in a 3X3 latin square arrangement, with 3 treatments, 3 periods of 21 days each and 3 squares. The treatments were: A) NRC-based (NRC, 2001) diet to provide 100% of crude protein (CP), as well as, rumen undegradable protein (RUP) and rumen degradable protein (RDP) requirements, by using soybean meal and sugar cane; B) 0,75% urea inclusion; partially substituting soya meal from diet C) 1,5% urea inclusion, partially substituting soya meal from diet. Energy and protein levels of treatment diets comply with NRC (2001), and were isoenergetic and isoproteic. No statistical differences were observed among treatments, when results were analyzed by simple polynomial regression in relation to dry-matter intake, milk yield, 3,5% FCM, protein and fat yield, and somatic cell count (Log SCC). Cryoscopy, pH, milk density and alcohol stability, fat, lactose, urea, total solids and solids with no fat were not influenced by treatments. The protein composition, crude protein, true protein, casein, whey protein, non-casein nitrogen, milk urea nitrogen, as well as, true protein:crude protein and casein:true protein ratios were not influenced by the substitution of soybean meal by urea in ration. Results indicate that the use of urea up to 1,5% in DM does not alter milk yield and its composition.

Justificativa: Doses inadequadas de diálise estão associadas a maior morbidade e mortalidade em pacientes com uremia terminal em tratamento hemodialítico. Atualmente os métodos mais utilizados para medir a adequação da hemodiálise baseiam-se no cálculo da depuração fracional de uréia (Kt/V) e da taxa de redução da uréia (URR). Nesse estudo avaliou-se a reprodutibilidade do Kt/V e da URR e analisou-se o número aceitável de medidas mensais destes parâmetros para determinar de forma fidedigna a adequação da hemodiálise. Métodos: Avaliamos 43 pacientes clinicamente estáveis, em cinco sessões de hemodiálise (sessões 1 a 5), durante três semanas. Três diálises consecutivas na primeira semana (sessões 1, 2, 3) e duas sessões de meio de semana, nas duas semanas subseqüentes (sessões 4 e 5). Resultados: Não houve diferença entre a média dos Kt/Vs obtidos em diálises seqüenciais (1, 2 e 3) comparada a média dos Kt/Vs obtidos em diálises no meio da semana (2, 4 e 5). O mesmo aconteceu com a URR e com os coeficientes de variação do Kt/V e da URR. Também não encontramos diferença entre uma medida mensal (Kt/V 2) e três medidas mensais (média dos Kt/Vs 2, 4 e 5). O mesmo ocorreu com a URR. A diferença entre o Kt/V 2 e a média dos Kt/Vs 2, 4 e 5 foi de – 0,02 unidades e entre a URR 2 em relação a média das URRs 2, 4 e 5 foi de – 0,5%. Além disso, se fizermos apenas uma medida mensal (Kt/V 2) 80% dos pacientes estarão a uma distância de no máximo 0,16 unidades abaixo da média dos Kt/Vs 2, 4 e 5 e no máximo 0,12 unidades acima. Em relação a URR 80% dos pacientes estarão a uma distância de no máximo 4,37% abaixo da média das URRs 2, 4 e 5 e no máximo 3,37% acima. O grau de concordância entre o Kt/V 2 e a média dos Kt/Vs 2, 4 e 5 é bom para pontos de corte do Kt/V igual ou superior a 1,3. No caso da URR a concordância é boa para pontos de corte acima de 65%. Conclusão: Concluímos que nesta população de pacientes clinicamente estáveis os parâmetros de adequação da hemodiálise mostraram-se reprodutíveis não havendo necessidade de aumentar o número de medidas mensais da quantidade de diálise ofertada. / Background: Inadequate doses of dialysis are associated with higher morbidity and mortality rates for end-stage renal disease (ESRD) patients undergoing hemodialysis treatment. Most methods aimed at measuring dialysis adequacy use the calculation of fractional clearance of urea (Kt/V) and urea reduction ratio (URR). This study evaluates the reproducibility of Kt/V and URR and analyzes the acceptable number of monthly measurements of these parameters to determine hemodialysis adequacy. Methods: We evaluated 43 clinically stable patients in five hemodialysis sessions (1 to 5) along three weeks. Three consecutive sessions were carried out in the first week (1, 2, 3), while the two other studied sessions were carried out in the middle of the week at weekly intervals (4, 5). Results: There was no difference between mean Kt/V in sessions 1, 2, and 3 and in sessions 2, 4, and 5. The same was observed for URR and the coefficients of variation for Kt/V and URR. Either differences were found between one monthly measurement (2) or three monthly measurements (mean of 2, 4, and 5) for Kt/V and URR. The difference between Kt/V 2 and the arithmetic mean of Kt/Vs 2, 4, and 5 was – 0.02 units, and between URR 2 and the mean of URRs 2, 4, and 5 was – 0.5%. When only one monthly measurement (Kt/V 2) was considered, 80% of the patients presented ≤0.16 unit below or ≤0.12 above the mean of Kt/Vs 2, 4, and 5. For URR, 80% of patients presented ≤4.73% below or ≤3.37% above the arithmetic mean of URRs 2, 4, and 5. The degree of agreement between Kt/V 2 and the mean of Kt/Vs 2, 4 and 5 is good for Kt/Vs of 1.3 or higher. URR agreements are good for URR of 65% or higher. Conclusion: In this population, hemodialysis adequacy parameters were reproducible, and an increase in the number of monthly measurements seems not to be necessary.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A utilização de novos materiais aplicados aos processos de separação por membranas tem sido objeto de constante pesquisa acadêmica e tecnológica. Na permeação de gases petroquímicos, a modificação de estruturas poliméricas e o uso de membranas de transporte facilitado por adição de sais contendo metais ou nanopartículas destacam-se dentre as opções disponíveis. Os objetivos deste trabalho foram avaliar alterações químicas, estruturais e térmicas na matriz polimérica de poli(uretano-ureia) (PUU) provocadas pela adição de nanopartículas de prata (AgNps) e obter dados de pemeabilidade de gases petroquímicos (C2H4, C2H6, CO2 e N2) para avaliar a influência das AgNps no transporte desses gases através do filme polimérico. Alterações nos espectros de FTIR nas bandas de estiramento das ligações C-O-C e C=O (uretânica e ureica), e deslocamentos nos picos de difração, demonstram que houve interação entre as AgNps e o oxigênio éter do PUU. A interação com as AgNps diminuiu a estabilidade térmica dos domínios flexíveis do polímero, região onde são encontrados os grupos éteres. As imagens de TEM mostraram que houve baixa dispersão das Nps na matriz polimérica. A interação das AgNps com o grupo éter diminuiu a permeabilidade de todos os gases, porém a redução da permeabilidade do CO2 e do C2H4 foi muito mais significativa, mostrando a interferência das AgNps na sorção desses dois gases. O transporte facilitado de olefinas através dos filmes poliméricos não foi observado, em parte, causado pela baixa dispersão das AgNps na matriz polimérica. Apesar da interação, não foi possível responder se a superfície das Nps estava ativada para o transporte facilitado. Contudo, através dos resultados do trabalho foi possível propor um mecanismo de interação entre as AgNps e o PUU, e verificar como a presença das Nps pode alterar a interação da matriz polimérica com gases petroquímicos / The use of new materials applied to processes of membrane separation has been the target of constant academic and technological researches. In permeation of petrochemical gases, the modification of polymeric structure to form facilitated transport membranes are one of the worthy available options. In this sense, the goal of this work is, not only evaluate the influence of the addition of silver nanoparticles (AgNps) in the chemical, morphological and thermal properties of poly(urethane urea) (PUU) films, but also obtain permeability data for some petrochemical gases (C2H4, C2H6, CO2 e N2). FTIR spectra exhibited changes in the C-O-C and C=O stretching bands profile of (from urethane and urea groups) and XRD analyses exhibited shifts in peaks. These results demonstrate the AgNps interacted with the ether oxygen of PUU. The interaction with AgNps reduced the thermal stability of polymer soft segments, where the ether linkages are located. TEM images showed a lower dispersion of Np in the polymer matrix. The interaction between AgNps and ether groups also decreased the permeability of all gases. Reduction of CO2 and C2H4 permeability were clear, demonstrating the hindrance of AgNps in the sorption of both gases. The olefin transport facilitated through the polymeric films was not verified. . This is partially caused by the lower dispersion of AgNps in the polymer matrix. Although an interaction between the AgNps and ether oxygen was observed, it was not possible to confirm if the Nps surface was really activated to facilitated transport. However, considering the results obtained it was possible to propose the interaction mechanism between AgNps and PUU; and also to indicate how the presence of Nps can change the interaction between the polymeric matrix and the petrochemical gases

Justificativa: Doses inadequadas de diálise estão associadas a maior morbidade e mortalidade em pacientes com uremia terminal em tratamento hemodialítico. Atualmente os métodos mais utilizados para medir a adequação da hemodiálise baseiam-se no cálculo da depuração fracional de uréia (Kt/V) e da taxa de redução da uréia (URR). Nesse estudo avaliou-se a reprodutibilidade do Kt/V e da URR e analisou-se o número aceitável de medidas mensais destes parâmetros para determinar de forma fidedigna a adequação da hemodiálise. Métodos: Avaliamos 43 pacientes clinicamente estáveis, em cinco sessões de hemodiálise (sessões 1 a 5), durante três semanas. Três diálises consecutivas na primeira semana (sessões 1, 2, 3) e duas sessões de meio de semana, nas duas semanas subseqüentes (sessões 4 e 5). Resultados: Não houve diferença entre a média dos Kt/Vs obtidos em diálises seqüenciais (1, 2 e 3) comparada a média dos Kt/Vs obtidos em diálises no meio da semana (2, 4 e 5). O mesmo aconteceu com a URR e com os coeficientes de variação do Kt/V e da URR. Também não encontramos diferença entre uma medida mensal (Kt/V 2) e três medidas mensais (média dos Kt/Vs 2, 4 e 5). O mesmo ocorreu com a URR. A diferença entre o Kt/V 2 e a média dos Kt/Vs 2, 4 e 5 foi de – 0,02 unidades e entre a URR 2 em relação a média das URRs 2, 4 e 5 foi de – 0,5%. Além disso, se fizermos apenas uma medida mensal (Kt/V 2) 80% dos pacientes estarão a uma distância de no máximo 0,16 unidades abaixo da média dos Kt/Vs 2, 4 e 5 e no máximo 0,12 unidades acima. Em relação a URR 80% dos pacientes estarão a uma distância de no máximo 4,37% abaixo da média das URRs 2, 4 e 5 e no máximo 3,37% acima. O grau de concordância entre o Kt/V 2 e a média dos Kt/Vs 2, 4 e 5 é bom para pontos de corte do Kt/V igual ou superior a 1,3. No caso da URR a concordância é boa para pontos de corte acima de 65%. Conclusão: Concluímos que nesta população de pacientes clinicamente estáveis os parâmetros de adequação da hemodiálise mostraram-se reprodutíveis não havendo necessidade de aumentar o número de medidas mensais da quantidade de diálise ofertada. / Background: Inadequate doses of dialysis are associated with higher morbidity and mortality rates for end-stage renal disease (ESRD) patients undergoing hemodialysis treatment. Most methods aimed at measuring dialysis adequacy use the calculation of fractional clearance of urea (Kt/V) and urea reduction ratio (URR). This study evaluates the reproducibility of Kt/V and URR and analyzes the acceptable number of monthly measurements of these parameters to determine hemodialysis adequacy. Methods: We evaluated 43 clinically stable patients in five hemodialysis sessions (1 to 5) along three weeks. Three consecutive sessions were carried out in the first week (1, 2, 3), while the two other studied sessions were carried out in the middle of the week at weekly intervals (4, 5). Results: There was no difference between mean Kt/V in sessions 1, 2, and 3 and in sessions 2, 4, and 5. The same was observed for URR and the coefficients of variation for Kt/V and URR. Either differences were found between one monthly measurement (2) or three monthly measurements (mean of 2, 4, and 5) for Kt/V and URR. The difference between Kt/V 2 and the arithmetic mean of Kt/Vs 2, 4, and 5 was – 0.02 units, and between URR 2 and the mean of URRs 2, 4, and 5 was – 0.5%. When only one monthly measurement (Kt/V 2) was considered, 80% of the patients presented ≤0.16 unit below or ≤0.12 above the mean of Kt/Vs 2, 4, and 5. For URR, 80% of patients presented ≤4.73% below or ≤3.37% above the arithmetic mean of URRs 2, 4, and 5. The degree of agreement between Kt/V 2 and the mean of Kt/Vs 2, 4 and 5 is good for Kt/Vs of 1.3 or higher. URR agreements are good for URR of 65% or higher. Conclusion: In this population, hemodialysis adequacy parameters were reproducible, and an increase in the number of monthly measurements seems not to be necessary.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A utilização de novos materiais aplicados aos processos de separação por membranas tem sido objeto de constante pesquisa acadêmica e tecnológica. Na permeação de gases petroquímicos, a modificação de estruturas poliméricas e o uso de membranas de transporte facilitado por adição de sais contendo metais ou nanopartículas destacam-se dentre as opções disponíveis. Os objetivos deste trabalho foram avaliar alterações químicas, estruturais e térmicas na matriz polimérica de poli(uretano-ureia) (PUU) provocadas pela adição de nanopartículas de prata (AgNps) e obter dados de pemeabilidade de gases petroquímicos (C2H4, C2H6, CO2 e N2) para avaliar a influência das AgNps no transporte desses gases através do filme polimérico. Alterações nos espectros de FTIR nas bandas de estiramento das ligações C-O-C e C=O (uretânica e ureica), e deslocamentos nos picos de difração, demonstram que houve interação entre as AgNps e o oxigênio éter do PUU. A interação com as AgNps diminuiu a estabilidade térmica dos domínios flexíveis do polímero, região onde são encontrados os grupos éteres. As imagens de TEM mostraram que houve baixa dispersão das Nps na matriz polimérica. A interação das AgNps com o grupo éter diminuiu a permeabilidade de todos os gases, porém a redução da permeabilidade do CO2 e do C2H4 foi muito mais significativa, mostrando a interferência das AgNps na sorção desses dois gases. O transporte facilitado de olefinas através dos filmes poliméricos não foi observado, em parte, causado pela baixa dispersão das AgNps na matriz polimérica. Apesar da interação, não foi possível responder se a superfície das Nps estava ativada para o transporte facilitado. Contudo, através dos resultados do trabalho foi possível propor um mecanismo de interação entre as AgNps e o PUU, e verificar como a presença das Nps pode alterar a interação da matriz polimérica com gases petroquímicos / The use of new materials applied to processes of membrane separation has been the target of constant academic and technological researches. In permeation of petrochemical gases, the modification of polymeric structure to form facilitated transport membranes are one of the worthy available options. In this sense, the goal of this work is, not only evaluate the influence of the addition of silver nanoparticles (AgNps) in the chemical, morphological and thermal properties of poly(urethane urea) (PUU) films, but also obtain permeability data for some petrochemical gases (C2H4, C2H6, CO2 e N2). FTIR spectra exhibited changes in the C-O-C and C=O stretching bands profile of (from urethane and urea groups) and XRD analyses exhibited shifts in peaks. These results demonstrate the AgNps interacted with the ether oxygen of PUU. The interaction with AgNps reduced the thermal stability of polymer soft segments, where the ether linkages are located. TEM images showed a lower dispersion of Np in the polymer matrix. The interaction between AgNps and ether groups also decreased the permeability of all gases. Reduction of CO2 and C2H4 permeability were clear, demonstrating the hindrance of AgNps in the sorption of both gases. The olefin transport facilitated through the polymeric films was not verified. . This is partially caused by the lower dispersion of AgNps in the polymer matrix. Although an interaction between the AgNps and ether oxygen was observed, it was not possible to confirm if the Nps surface was really activated to facilitated transport. However, considering the results obtained it was possible to propose the interaction mechanism between AgNps and PUU; and also to indicate how the presence of Nps can change the interaction between the polymeric matrix and the petrochemical gases