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Submitted by Michele Mologni (mologni@unoeste.br) on 2018-08-02T14:10:57Z No. of bitstreams: 1 Valter Alves Pradela.pdf: 805718 bytes, checksum: a1e7be8282642614c408dd3af31ccf75 (MD5) / Made available in DSpace on 2018-08-02T14:10:57Z (GMT). No. of bitstreams: 1 Valter Alves Pradela.pdf: 805718 bytes, checksum: a1e7be8282642614c408dd3af31ccf75 (MD5) Previous issue date: 2016-11-09 / The objective of the project was to verify the use of synthetic hydro-seed polymers as soil conditioners together with the formation of pre-sprouted seedlings (MPB) of sugarcane. The research was conducted in the greenhouse of FATEC of Presidente Prudente - SP. The material studied was cultivar RB 86 7515. The substrate used was Bioplant®. The treatments consisted of eight doses (0; 1; 2; 3; 4; 8; 20; 40 g L-1) of a superabsorbent polymer (Hidrogel®), added to the substrate prior to filling the tubes. The sugarcane minirrebolos were heat treated and planted in trays, inside the greenhouse along with the substrate, being irrigated daily (15 mm per day). At 10 days, each pre-budded seedling was removed from the tray and placed in tubes (290 mL). At 31 days, the seedlings were transferred to full sun condition and submitted to three different daily irrigation slides (5, 10 and 15 mm), remaining in these conditions until the end of the experiment, totaling 60 days. It was considered the Factorial design, with eight treatments (dosages), three irrigation slides (5, 10, and 15 mm) and five replicates (seedlings in tubes), the means being compared by the Scott-Knott test (p <0, 05). Multiple regressions were performed using Microcal Origin software, with only those that presented significant "F" at 5%. Two types of analysis were carried out, one being destructive, where plants were sampled and conducted to the laboratory, and another one of non-destructive nature, in which the variables were obtained through surveys. It was found that the use of different doses of the polymer negatively affects the mass of the roots. The fresh mass of the aerial part was positively affected with the use of polymers, whereas the dry mass presented an inverse relation. The doses of 8 g L-1 and 20 g L-1 with irrigation of 15 mm presented better results for shoot production. The values of photosynthetic rate, CO2 concentration and stomatal conductance were affected by the treatments, and the dose of 4 g L-1, with the lowest irrigation level (5 mm), already presented differences. In relation to the water flow, it was observed that the irrigation slides and the polymer doses positively affected this parameter. The aerial parts and roots were positively affected by irrigation and negatively affected by the polymer. / O objetivo do projeto foi verificar a utilização de polímeros sintéticos hidroretentores como condicionadores de solo junto a formação de mudas pré-brotadas (MPB) de cana-de-açúcar. A pesquisa foi conduzida na casa de vegetação da FATEC de Presidente Prudente - SP. O material estudado foi o cultivar RB 86 7515. O substrato utilizado foi o Bioplant®. Os tratamentos consistiram de oito doses (0; 1; 2; 3; 4; 8; 20; 40 g L-1) de um polímero superabsorvente (Hidrogel®), adicionados ao substrato antes do enchimento dos tubetes. Os minirrebolos de cana-de-açúcar foram tratados termicamente e plantados em bandejas, dentro da casa de vegetação juntamente com o substrato, sendo irrigados diariamente (15mm por dia). Aos 10 dias, cada muda pré-brotada foi removida da bandeja e colocada em tubetes (290 mL). Aos 31 dias, as mudas foram transferidas para condição de pleno sol e submetidas a três diferentes lâminas de irrigação diária (5, 10 e 15 mm), permanecendo nessas condições até o final do experimento, totalizando 60 dias. Foi considerado o delineamento Fatorial, com oito tratamentos (dosagens), três lâminas de irrigação (5, 10, e 15 mm) e cinco repetições (mudas em tubetes), sendo as médias comparadas pelo teste de Scott-Knott (p<0,05). As regressões múltiplas foram realizadas utilizando software Microcal Origin, sendo utilizadas apenas as que apresentaram “F” significativo à 5%. Realizaram-se dois tipos de análise, sendo uma destrutiva, onde plantas foram amostradas e conduzidas ao laboratório, e outra de natureza não destrutiva, na qual as variáveis foram obtidas através de levantamentos. Constatou-se que a utilização de diferentes doses do polímero afeta negativamente a massa das raízes. A massa fresca da parte aérea foi positivamente afetada com a utilização de polímeros, já a massa seca apresentou uma relação inversa. As doses de 8 g L-1 e 20 g L-1 com irrigação de 15 mm apresentou melhores resultados para produção de parte aérea. Os valores de taxa fotossintética, concentração de CO2 e condutância estomática foram afetados pelos tratamentos, sendo a dose de 4 g L-1, com o menor nível de irrigação (5 mm), já apresentava diferenças. Com relação ao fluxo de água, tem-se que as lâminas de irrigação e as doses de polímero afetaram positivamente este parâmetro. As partes aéreas e raízes foram afetadas positivamente pela irrigação e negativamente pelo polímero.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18824号 / 理博第4082号 / 新制||理||1587(附属図書館) / 31775 / 京都大学大学院理学研究科化学専攻 / (主査)教授 杉山 弘, 教授 三木 邦夫, 教授 秋山 芳展 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Construction sites are frequently cited as major sources of pollution that degrade the quality of surface water. The highly erodible topsoil is transported off site by stormwater runoff causing negative effects downstream. Research has shown that the small particles, which are the most susceptible to erosive forces, have more pollutants associated with them than larger soil particles. Currently, in the state of Florida, it is not permissible to discharge water to a receiving water body if the turbidity is more than 29 Nephelometric Turbidity Units (NTUs) above background or higher than background for an outstanding Florida water body. The removal of fine suspended sediment from water can be achieved by filtration, settling, and the use of chemical coagulants. Polyacrylamide (PAM), a coagulant, has been shown to be effective in removing fine suspended particles from water via coagulation and flocculation. The Stormwater Management Academy at the University of Central Florida has researched the use of PAM and collection mats in a treatment channel to meet state discharge requirements. In this study, turbid water using sediment from typical Florida soils was simulated and passed through a channel. The channel contained polymer blocks in a configuration previously determined to be the most effective. An important component of the treatment system is the floc collection. This research examined three types of collection mats, namely jute, coconut fiber and polypropylene mix to collect the flocs. This thesis presents the results of this investigation. The results for the sandy soil tests showed an average removal efficiency prior to the collection mat starting at 71% and decreasing to 44% at the end of the tests. The 20-foot coconut mat maintained an average removal efficiency of 90%. The turbidity due to silty-sandy soil was decreased with an average removal efficiency prior to the collection mat ranging from 50% to 65%. The average removal efficiency for the 20-foot coconut mat started at 85%and decreased to 60% during the tests. The turbidity due to crushed limestone showed an average removal efficiency prior to the collection mat ranging from 81% down to 69% over time. The average results from the 20-foot coconut mat ranged from 65% to 80%. Turbidity was tested on the samples under two conditions, a 30 second settling time and completely mixed. Statistical results show a significant decrease (?=0.05) in turbidity between the mixed and settled samples. Statistical analyses were performed on the collected data, which concluded that the capability of the mat to reduce turbidity can be repeated with a 95% confidence interval. The 20-foot length coconut mat had the highest turbidity removal efficiency for every soil type examined. Further statistical analysis showed that the achieved turbidity reduction was significantly different (?=0.05) for the various materials. It was observed that generally, each type of mat clogged during testing indicating that longer collection mats be used, possibly lining the entire channel. Recommendations from this study are to provide a settling area after the collection mats and line the entire length of the channel with the collection mat selected.

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The objectives of this study were to (1) determine an intermittent aeration strategy that could be used to conserve nitrogen (N) via nitrification in dairy manure, (2) determine the effect of recycled flush water on the bio-availability of N during nitrification, and (3) determine effective and economical dosages of chemicals to remove phosphorus (P) from liquid dairy manure. Intermittent aeration strategies, defined in terms of time the aerator is on and off (ON h:OFF h), could be used to conserve N in dairy manure. Testing of four treatments (continuous aeration [100%], 1h:0.33h [75%], 1h:0.67h [60%], and 1h:1h [50%]) showed that only treatments using air provided for 100% and 75% of the time could support nitrification. The 100% and 75% aeration treatments conserved an average of 38% and 25% of influent total ammonia nitrogen (TAN) as nitrite-N+nitrate-N, respectively. Less than 2% of influent TAN was conserved using 60% and 50% treatments. The effect of manure handling technique on N bioavailability and nitrification was tested using flushed and scraped dairy manure. Nitrification was inhibited in scraped manure. Four aluminum- and iron-based salts and five cationic polyacrylamide polymers were evaluated for P removal using jar tests. Ferric chloride (FeCl3·6H2O), aluminum sulfate (Al2[SO4]3·13H2O, alum), and Superfloc 4512 were selected for further study. Polymer addition enhanced floc size and improved P removal. Treatment of manure (0.89% total solids) from Tank 2 at Virginia Tech's dairy using either FeCl3 or alum in combination with polymer resulted in more than 90% P removal. Chemical treatment and transport of P-rich sludge from a 2,270 cubic meter storage tank would result in an estimated 40% cost savings over transport of the entire manure volume offsite for land application elsewhere. The manure treatment strategies tested provide some solutions to dairy farmers regarding adjustment of N:P ratios so that manure can be applied to meet nutrient needs of crops while adhering to regulations set forth by nutrient management plans. / Master of Science

Les particules LDL et HDL petites et denses sont liees a un risque cardiovasculaire augmente. Malgre les fortes correlations negatives entre les taux de TG et la taille des particules LDL et HDL, les valeurs predictives de differents ratios et parametres de lipides et d'apolipoproteines sont partiellement caracterisees. Les objectifs du memoire sont d'identifier les determinants de la taille des particules LDL et HDL et d'evaluer les potentiels predictifs de differents ratios et parametres. Les tailles des particules LDL de 1956 sujets ont ete mesurees par electrophorese sur gradient de gel de polyacrylamide (PAGGE). Les particules LDL des hommes sont plus petites que celle des femmes. Le CLDL/ apoBLDL a la plus importante contribution a la variance de la taille des LDL. Tous les autres ratios etudies sont de mauvais predicteurs. Les meilleurs moyens de mesurer les tailles des particules LDL afin de predire le risque cardiovasculaire demeurent les mesures sur PAGGE

Mass spectrometry coupled with liquid chromatography and gel electrophoresis enables separation and detection of components in a complex mixture. During the last two decades, its applications were dramatically extended and remarkable progress has been made in many fields, in particular, environmental and biological analyses. This dissertation focuses on identification and characterization of biologically active compounds and comparative analysis of protein expression changes. The first two projects (Chapters 2 and 3) focus on the application of LC/MS approach to profile the bioactivated intermediates of 4, 4'-methylenedianiline (DAPM) from rat vascular smooth muscle cells (VSMCs) and bile. In our study, several DAPM metabolites were detected and characterized in detail by liquid chromatography-electrospray tandem mass spectrometry. The structural assignments of these metabolites from VSMCs and rat bile significantly improve our understanding of DAPM biotransformations and toxicity. The third project described in Chapter 4 focuses on using electrospray tandem mass spectrometry (ES-MS/MS) and theoretical calculation (GAUSSIAN 03 program) to investigate the unusual methyl radical loss and consecutive fragment ions that dominate the low-energy collision induced dissociation (CID) mass spectra of prodiginine compounds. Structures of the fragment ions are proposed and explanations are given to rationalize the observed competition between the formation of even-electron ions and radical ions. Our study shows that the lower apparent threshold associated with methyl radical loss points to a lower kinetic barrier. In Chapter 5, hypoxia-induced changes of zebrafish skeletal muscle were studied using two-dimensional difference in-gel electrophoresis (2D-DIGE) in vivo after 48 h in hypoxia vs. normoxia. The results showed that proteins involved in mitochondrial oxidative metabolism are down-regulated, whereas glycolytic enzymes are up-regulated to compensate for the loss of ATP synthesis in aerobic metabolism. The up-regulation of two spots identified as hemoglobin variants was also observed. These protein expression changes are consistent with a hypoxic response that enhances anaerobic metabolism or O2 transport to tissues.

Polímeros e copolímeros hidrossolúveis a base de acrilamida e seus derivados são sintetizados e aplicados principalmente como floculantes, auxiliando na remoção de sólidos finos presentes em águas residuais e industriais. As poliacrilamidas, como são assim chamadas, podem se apresentar em sua forma neutra ou contendo diferentes cargas iônicas (positivas ou negativas) em sua composição em função do tipo de aplicação específica. As poliacrilamidas são sintetizadas, em sua grande maioria, através de emulsões inversas via polimerização radicalar, visando à elevada massa molar do polímero formado. A formulação da poliacrilamida catiônica com fração molar de 0,6 do comonômero iônico foi otimizada através de planejamento fatorial experimental, variando-se os principais fatores de processo: concentração do pacote de surfactante para formação da emulsão inversa, tempo de micronização, concentração de VISCOPLEX® e concentração de ácido graxo. Com base nos resultados obtidos a partir do primeiro planejamento, foram estudadas as seguintes variáveis: HLB do sistema de surfactantes e a troca dos surfactantes monoméricos por surfactantes poliméricos. A otimização da formulação levou em conta principalmente o custo-benefício para produção e comercialização em escala industrial. O fator micronização foi elevado em seu máximo e os fatores VISCOPLEX® e ácido graxo foram excluídos da formulação, após conclusão dos estudos. A troca dos surfactantes monoméricos por poliméricos foi vantajosa devido ao ganho de qualidade do produto final, mesmo com maior custo de implementação. Para minimizar os custos de formulação o fator HLB foi utilizado em seu máximo, onde houve incremento do ALKONAT® L 50 para formação da emulsão inversa. / Acrylamide based hydrosoluble polymers and copolymers and their derivatives are synthesized and mainly applied as flocculants, assisting removal of fine solids present in wastewater and industrial wastewater. Polyacrylamides may be present in their neutral form or with different ionic charges (positive or negative) in their composition depending on the type of specific application. Polyacrylamides are synthesized, mostly by inverse emulsions using radical polymerization, aiming polymers with high molecular weight. Cationic polyacrylamide formulation with 0.6 mole fraction of the ionic comonomer was optimized through design of experiments (DOE), varying the major process factors: surfactant package concentration to form inverse emulsion, micronization time, VISCOPLEX® concentration and fatty acid concentration. Based on the responses from the first DOE, a second DOE was performed, where the variables surfactant system HLB and the exchange of monomeric surfactant by polymeric surfactants were investigated. The formulation optimization considered mainly cost-effective production and industrial scale. The micronization factor was set at its maximum and VISCOPLEX® and fatty acid factors were excluded from the formulation, after conclusion of studies. Exchanging monomeric surfactants by polymeric surfactants led to a final product with higher quality, even considering a higher implementation cost. In order to minimize formulation costs HLB factor was used at its maximum, increasing the content of ALKONAT® L50 to form the inverse emulsion.

Este trabalho visa estudar a viabilidade do emprego de processos oxidativos avancados na degradacao de solucoes aquosas de polimeros que sao comumente utilizados em aplicacoes industriais e estao presentes em seus efluentes. Para maior entendimento das reacoes envolvidas no processo oxidativo utilizou-se modelagem molecular nos calculos de constantes cineticas. Na parte experimental estudou-se a degradacao de polietilenoglicol (PEG), polivinilpirrolidona (PVP) e poliacrilamida (PAM) pelos processos foto-Fenton e UV/H2O2. Realizaram-se analises de carbono organico dissolvido (COD), cromatografia liquida de alto desempenho (HPLC) e cromatografia de permeacao em gel (GPC). Observou-se separacao de fases para PVP e PAM, o que contribuiu para uma remocao final de COD de ate 85%. Nas analises de HPLC foram detectados como intermediarios da reacao os acidos: oxalico, formico, malonico e acetico. Os resultados de GPC indicaram comportamentos distintos das distribuicoes de pesos moleculares em funcao do tempo de reacao para os processos UV/H2O2 e foto- Fenton. No conjunto, os resultados comprovam a viabilidade dos processos estudados na degradacao destes polimeros, embora a analise de intermediarios para PAM nao tenha sido conclusiva quanto a formacao de acrilamida. A modelagem molecular confirma que a reacao de abstracao de hidrogenio de uma cadeia polimerica pelos radicais alquilperoxila e de fato a etapa mais lenta do processo oxidativo para PEG e PAM. Para PAM os resultados da modelagem mostram que o ataque dos radicais hidroxila acontece preferencialmente no hidrogenio ligado ao carbono terciario e que a abstracao de hidrogenio do grupo lateral amida parece pouco viavel, ou acontece por um mecanismo diferente do modelado. A reacao de formacao da acrilamida de acordo com o mecanismo proposto tambem apresentou uma constante cinetica muito baixa, o que esta de acordo com os resultados experimentais, ja que nao foi detectada acrilamida como produto da degradacao de poliacrilamida pelos processos foto-Fenton e UV/H2O2, com limite de deteccao de 50 ppb. / The aim of this work is to apply advanced oxidative processes to study the degradation of industrial wastewater containing water-soluble polymers. Kinetic constants of reactions involved in the oxidation processes were calculated by molecular modeling. In the experimental part the degradation of polyvinylpirrolidone (PVP), polyacrylamide (PAM) and polyethyleneglycol (PEG) was studied by photo-Fenton and UV/H2O2 processes. Intermediates of the degradation processes were identified by HPLC and the molecular weight distribution was monitored by GPC. In the experiments with PAM and PVP phase separation was observed, and more than 85% of the DOC was removed. The following intermediate acids were identified: acetic, malonic, formic and oxalic. The molecular weight distribution curves measured by GPC indicate that distinct reaction paths exist for each process studied, although the analysis of intermediates formed during the degradation of PAM was not conclusive with respect to acrylamide formation. The kinetic constants for the reactions involving hydrogen abstraction from PEG chain by hydroxyl and alkylperoxy radicals were calculated. The molecular modeling results confirm that hydrogen abstraction from polymeric chain by alkylperoxy radicals is the determinant step in the oxidation process for PEG and PAM. Polyacrylamide possesses three sites for attack by hydroxyl radicals and the favored path is the abstraction of tertiary hydrogen atom, followed by secondary hydrogen. The abstraction of the amide hydrogen was more difficult. The mechanism proposed for acrylamide formation was not the preferential reaction path. This was expected since acrylamide was not detected in the experiments with a limit detection of 50 ppb.