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<p>Glavni cilj istraživanja ove doktorske disertacije je bio valorizacija sporednog proizvoda žalfije (Salvia officinalis L.) iz fabrike čaja za dobijanje visoko-vrednih ekstrakata željenih osobina koji bi imali primenu u gotovim proizvodima prehrambene, kozmetičke i farmaceutske industrije.<br />U cilju ekstrakcije polifenolnih jedinjenja su primenjene konvencionalne (maceracija) i savremene (ultrazvučna ekstrakcija, mikrotalasna ekstrakcija i ekstrakcija subkritičnom vodom) ekstrakcione tehnike. U postupaku maceracije je optimizovana koncentracija etanola u ekstragensu, dok je za optimizaciju savremenih ekstrakcionih tehnika primenjen eksperimentalni dizajn i metoda odzivne povr&scaron;ine. Prinos polifenola (ukupnih fenola i ukupnih flavonoida) i antioksidativna aktivnost određena različitim in vitro testovima su bili ispitivani odzivi. Za svaki od navedenih ekstrakcionih postupaka je ispitivan uticaj glavnih ekstrakcionih parametara: ultrazvučna ekstrakcija (temperatura, vreme ekstrakcije i snaga ultrazvuka), mikrotalasna ekstrakcija (koncentracija etanola, vreme ekstrakcije i odnos rastvarač-droga) i ekstrakcija subkritičnom vodom (temperatura, vreme ekstrakcije i koncentracija HCl u ekstragensu). Tečni ekstrakti dobijeni ultrazvučnom, mikrotalasnom i subkritičnom ekstrakcijom su pokazali izuzetno visoku antioksidativnu aktivnost određenu &bdquo;hvatanjem&ldquo; DPPH i O2∙- radikala i kapacitetom redukcije Fe3+ jona i imali su znatno veći sadržaj polifenola u odnosu na ekstrakte dobijene maceracijom.<br />U cilju ekstrakcije terpenoidnih jedinjenja su primenjeni postupci Soxhlet ekstrakcije, destilacije vodenom parom i ekstrakcije superkritičnim CO2. Postupak superkritične ekstrakcije je optimizovan metodom odzivne povr&scaron;ine i optimalni uslovi ekstrakcije su bili pritisak 290 bar, temperatura 55˚C i protok CO2 od 0,4 kg/h, dok su predviđene i eksperimentalne vrednosti prinosa ekstrakcije bile 8,90 i 8,84%. Hemijskom analizom lipofilnih ekstrakata i etarskog ulja je utvrđeno da su oksidovani monoterpeni (&alpha;-tujon i kamfor), oksidovani seskviterpeni (viridiflorol) i polifenolni diterpeni (epirosmanol) dominantna jedinjenja prisutna u ovim uzorcima.<br />Tečni ekstrakti žalfije dobijeni konvencionalnim i savremenim ekstrakcionim tehnikama su spray drying tehnikom osu&scaron;eni u cilju prevođenja u stabilniju formu suvog ekstrakta. Suvim ekstraktima su određene fizičko-hemijske osobine (hemijski sastav, sadržaj vlage, higroskopnost, moć rehidratacije, WAI i WSI) i biolo&scaron;ka aktivnost (antimikrobna i antioksidativna aktivnost) i procenjena je njihova mogućnost primene u prehrambenoj i farmaceutskoj industriji.</p> / <p>The main aim of this dissertation was valorization of sage (Salvia officinalis L.) by-product from filter-tea factory for recovery of high-value extracts with desirable properties for application in food, cosmetics and pharmaceutical products.<br />Conventional (maceration) and novel (ultrasound-assisted, microwave-assisted and subcritical water extraction) extraction techniques were applied for polyphenols recovery. Ethanol concentration was optimized in maceration process, while experimental design and response surface methodology were applied for optimization of novel extraction techniques. Polyphenols yield (total phenols and total flavonoids) and antioxidant activity, determined by various in vitro assays, were investigated responses. Influence of main process parameters was determined for each technique: ultrasound-assisted extraction (temperature, extraction time and ultrasonic power), microwave-assisted extraction (ethanol concentration, extraction time and sample-solvent ratio) and subcritical water extraction (temperature, extraction time and HCl concentration in solvent). Liquid extracts obtained by novel extraction technique exhibited higher antioxidant activity determined by scavenging of DPPH and O2∙- radicals and reduction of Fe3+ and also provided higher polyphenols yield comparing to extracts obtained by maceration. Soxhlet extraction, hydrodistillation and supercritical fluid extraction were applied for terpenoids recovery. Supercritical fluid extraction process was optimized by response surface methodology and optimal conditions were pressure of 290 bar, temperature of 55˚C and CO2 flow rate of 0.4 kg/h, while predicted and experimentally obtained values of total extraction yield at these conditions were 8.90 i 8.84%, respectively. According to chemical analysis, the most abundant compounds in lipid extracts and essential oil were oxygenated monoterpenes (&alpha;-thujone and camphor), oxygenated sesquiterpenes (viridiflorol) and diterpene polyphenols (epirosmanol).<br />Sage liquid extracts obtained by conventional and novel extraction techniques were spray dried in order to obtain dry extract form. Physico-chemical properties (chemical profile, moisture content, hygroscopicity, rehydratation time, WAI and WSI) and biological activity (antimicrobial and antioxidant activity) were determined in dry extracts and their potential application in food and pharmaceutical formulations was discussed.</p>

Afin de dépolluer et de réhabiliter les sols contaminés par des hydrocarbures aromatiques polycycliques (HAP), différentes techniques ont été développées durant les dernières décennies, mais leur impact sur les fonctions du sol est rarement pris en compte. L'objectif de ce travail était d'évaluer l'impact des traitements par oxydation chimique sur différents paramètres physico-chimiques et biologiques de terres contaminées aux HAP et de proposer des solutions pour restaurer le fonctionnement biologique des terres oxydées. Les différentes expérimentations de laboratoire et de terrain ont montré que l'efficacité des réactions d'oxydation chimique (réaction de Fenton et persulfate activé) sur la teneur en HAP dépendait de la disponibilité de la pollution et des propriétés physico-chimiques des terres. Par ailleurs, des processus d'acidification ont été observés sur des terres non carbonatées, altérant fortement et durablement les paramètres physico-chimiques et biologiques. Cette altération était plus forte après utilisation du persulfate activé, engendrant ainsi des pertes en éléments traces métalliques dans les eaux de percolations. L'apport de matériaux susceptibles d'augmenter le pH a permis la restauration des activités biologiques et la capacité des terres à supporter la végétation lorsque les terres ont fortement été acidifiées. L'association de traitements d'oxydation chimique et de refonctionnalisation pourrait présenter un moyen de réhabilitation efficace. Un indice, dont l'objectif était de représenter l'état du sol en fonction du poids accordé à différents paramètres, a été proposé et a permis d'évaluer les variations induites par les traitements d'oxydation et les procédés de refonctionnalisation / In order to clean up polycyclic aromatic hydrocarbon (PAH) contaminated soils, various techniques have been developed during the last decades, but their impact on soil functions was rarely considered. The objective of this study was to assess the impact of chemical oxidation treatments on different physico-chemical and biological parameters of PAH contaminated soil and to propose solutions to improve the biological functioning of oxidized soil. Various laboratory and field experiments have shown that the efficiency of chemical oxidation reactions (Fenton reaction and activated persulfate) on PAH concentrations depended on pollutant availability and soil physico-chemical properties. Besides, intense acidification processes have been observed on uncarbonated soil with a strong impact on soil physico-chemical and biological parameters. Moreover, this alteration was higher with activated persulfate treatment, leading to the loss of trace metals in water percolation. In the strongly acidified soil, the input of materials, suitable for pH increase, resulted in the restoration of biological activities and soil capacity to support vegetation. The association of chemical oxidation treatment and restoration techniques could present a good mean for soil rehabilitation. Finally, an index, which aimed to represent soil conditions based on the weight given to different parameters, was proposed and was used to evaluate changes induced by oxidation treatments and restoration techniques

Adamcová, M.: Study of biological activity of alkaloids isolated from Argemone grandiflora (Papaveraceae) I. Diploma thesis, Charles University in Prague, Faculty of Pharmacy in Hradec Králové, Department of Pharmaceutical Botany and Ecology, Hradec Králové 2015. The aim of this study was isolation of substances from total diethyl ether alkaloid extract of Argemone grandiflora Sweet, their identification and assessment of their inhibition activity towards acetylcholinesterase, butyrylcholinesterase and prolyl oligopeptidase. Using common chromatografic methods, four alkaloids were isolated, that was identified as (+)-laudanosine, protopine, (-)-argemonine a (-)-platycerine. These substances was tested for their inhibition activity IC50: (+)-laudanosine (IC50 AChE = 617,00 ± 46,55 μM, IC50 BuChE = 644,77 ± 55,52 μM, IC50 POP = not mesured yet); protopine (IC50 AChE = 229,98 ± 21,02 μM, IC50 BuChE = 208,87 ± 17,67 μM, IC50 POP ˃ 1000 μM); (-)-argemonine (IC50 AChE = 4677,75 ± 1241,08 μM, IC50 BuChE = 885,45 ± 119,50 μM, IC50 POP = 337 ± 83,1 μM); (-)-platycerine (IC50 AChE = 223,65 ± 19,61 μM, IC50 BuChE = 1651,25 ± 327,7 μM, IC50 POP = 687 ± 74 μM). In comparison with the standards galanthamine (IC50 AChE = 1,710 ± 0,065 μM, IC50 BuChE = 42,30 ± 1,30 μM) and huperzine A (IC50 AChE = 0,033 ± 0,001...

O ácido elágico é um composto fenólico presente em algumas frutas e sementes. As maiores fontes da dieta humana são as frutas conhecidas como berries, a romã e as nozes. Dentre as frutas nativas brasileira, a jabuticaba apresenta teores de ácido elágico comparáveis aos das berries. Além disso, a jabuticaba representa uma boa fonte de flavonoides e destaca-se pelo sabor apreciado e pelo grande número de frutos que oferece a cada floração. Dessa forma, os objetivos deste trabalho foram: caracterizar duas espécies de jabuticaba, Sabará e Paulista (Myrciaria jaboticaba (Vell.) Berg and Myrciaria cauliflora (Mart.) O. Berg), em diferentes estádios de maturação, assim como as frações polpa, casca e semente, quanto ao teor e perfil de flavonoides, ácido elágico livre e total, elagitaninos, proantocianidinas e capacidade antioxidante in vitro. Ainda, avaliar o efeito da administração de extrato bruto e/ou frações fenólicas da jabuticaba Sabará sobre o status antioxidante e perfil bioquímico de ratos Wistar diabéticos induzidos por estreptozotocina. As frações fenólicas de jabuticaba também foram testados em modelo de prevenção de obesidade e diabetes tipo 2 induzidas por dieta hiperlipídica em camundongos C57 Black 6. Também foi avaliado o efeito de extrato bruto e frações fenólicas da jabuticaba em culturas celulares de hepatócitos FAO, macrófagos J774.1 e músculo L6. A biodisponibilidade de derivados do ácido elágico também foi estudada, tanto em modelo in vitro de fermentação quanto in vivo em ratos Wistar. Os resultados demonstraram que existem diferenças nos teores de compostos bioativos entre as espécies, e entre os estádios de maturação. A variedade Sabará destacou-se em relação à capacidade antioxidante, teor de proantocianidinas e ácido elágico total, e por ser mais cultivada e consumida pela população, foi escolhida para continuar os estudos in vivo. Em culturas celulares, o tratamento com os extratos de jabuticaba foi capaz de inibir a produção de óxido nítrico em macrófagos e hepatócitos, e aumentou a captação de glicose em células musculares. Os animais diabéticos tratados com a jabuticaba apresentaram alterações do perfil lipídico plasmático, com reversão dos altos teores de colesterol total e triacilglicerídeos. Outros efeitos como a redução da peroxidação lipídica e aumento da capacidade antioxidante plasmática também foram observados. No modelo de prevenção de obesidade e diabetes tipo 2, o tratamento com os extratos fenólicos da jabuticaba melhorou a sensibilidade à insulina e a tolerância à glicose, mesmo diante do consumo de dieta hiperlipídica e incremento ponderal dos animais. O estudo da biodisponibilidade mostrou que os derivados do ácido elágico são metabolizados especialmente pela microbiota intestinal e seus derivados foram detectados no plasma, cólon, fígado, rins, músculo e cérebro dos animais. Estes resultados demonstraram que a jabuticaba pode ser considerada uma excelente fonte de compostos bioativos e o seu consumo pode ser associado à prevenção de alterações metabólicas causadas pelo diabetes e obesidade, como a dislipidemia e a resistência à insulina. / Ellagic acid is a phenolic compound present in several fruits and nuts. Walnuts and berries are some known sources. Among the Brazilian native fruits, jaboticaba shows ellagic acid content comparable to that of berries. In addition, jaboticaba is a good source of flavonoids and stands out due to its appreciated flavor and the large number of fruits produced in each flowering. In this way, this work aimed to characterize two species of jaboticaba, Sabará and Paulista (Myrciaria jaboticaba (Vell.) Berg and Myrciaria cauliflora (Mart.) O. Berg), in different ripening stages, as well as pulp, skin and seeds, in relation to the content and composition of flavonoids, free and total ellagic acid, ellagitannins, proanthocyanidins and in vitro antioxidant capacity. Besides, evaluate the effect of raw extract and solid-phase purified phenolic fractions from Sabará jaboticaba administration on antioxidante status and biochemical profile in streptozotocin-induced diabetic Wistar rats. The jaboticaba phenolic fractions were also tested on high-fat-diet-induced obesity and type 2 diabetes in C57BL/6 mice. The effect of phenolic fractions on glucose transport in L6 muscle cells and nitric oxide production in FAO hepatocytes and J774 macrophages were also assessed. The bioavailability of polyphenols from jaboticaba were studied using in vitro and in vivo methods. The results indicated that the phenolic compounds contents are different between the two species, and among the different ripening stages. Sabará species presented the highest amounts of proanthocyanidins and total ellagic acid, and the highest antioxidant capacity. For being the most cultivated and consumed, this species was chosen for the in vivo studies. In cell cultures, the jaboticaba extracts inhibited the nitric oxide production in macrophages and hepatocytes, and increased glucose uptake in L6 muscle cells. In streptozotocin induced diabetic animals, treatment with jaboticaba led to improvement in lipid profile, reducing the levels of total cholesterol and triacylglycerol. Reduction in lipid peroxidation and increase in antioxidant capacity were also observed. In high-fat-diet induced diabetic mice, the phenolic fractions improved insulin sensitivity and glucose tolerance, even when mice become obese. The bioavailability study revealed that the ellagic acid derivatives and other jaboticaba polyphenols were metabolized, especially by the colonic microbiota, and their metabolites were detected in plasma, colon, kidneys, liver, brain, muscle, and stomach. These results demonstrated that jaboticaba may be considered an excellent source of bioactive compounds, and its consumption can be related to reduced risk of metabolic disorders caused by diabetes and obesity, such as dyslipidemia and insulin resistance.

A aplicação da técnica de leito de jorro na secagem de pastas têm sido objeto de inúmeras investigações nos últimos anos, devido a possibilidade de obtenção de produtos de alta qualidade em uma operação de reduzido custo. No presente trabalho, avaliou-se a influência dessa técnica sobre as características e o desempenho de liberação de microcápsulas contendo diferentes fármacos modelo. Microcápsulas de caseína-pectina contendo indometacina e paracetamol foram preparadas por coacervação e posteriormente secas por leito de jorro e por spray drying. Após a secagem por leito de jorro, verificou-se uma redução na quantidade de indometacina recuperada a partir das microcápsulas. Não se observou segregação do fármaco durante a operação de secagem por leito de jorro, indicando que a reduzida recuperação do mesmo foi resultado do estabelecimento uma interação fármaco-polímero, a qual ocorre especificamente entre a caseína e a indometacina. A avaliação físico-química desses materiais indicou que a interação proposta possui natureza covalente e os estudos in vivo de atividade antiinflamatória das microcápsulas contendo indometacina mostraram a irreversibilidade dessa ligação em ambiente biológico. A metodologia de estímulo resposta foi avaliada e otimizada para a determinação do tempo de residência das microcápsulas em leito de jorro. Apesar de confiáveis, os valores de tempo de residência obtidos não puderam ser correlacionados à formação da interação fármaco-polímero, por se apresentarem estáveis quando da variação das condições operacionais do secador. Por outro lado, a vazão e a temperatura do ar de secagem mostraram influência significante sobre a formação da referida interação. Posteriormente à investigação da interação indometacina-caseína, foi avaliada a funcionalidade das microcápsulas obtidas por leito de jorro e por spray drying. Para tanto, foram realizados estudos de liberação in vitro, os quais mostraram a similaridade entre os perfis de dissolução da indometacina do paracetamol independentemente do método de secagem empregado. Uma exceção está na formulação não reticulada contendo indometacina, que apresentou um elevado nível de ruptura após a secagem por leito de jorro. Os dados obtidos na avaliação da funcionalidade dos sistemas juntamente com a constatação experimental do maior aproveitamento energético na secagem por leito de jorro, permitem considerar que a utilização dessa técnica na secagem de microcápsulas é promissora, visto que a interação fármaco-polímero discutida nesse trabalho é específica e dependente do tipo de fármaco encapsulado / The use of spouted bed technique in the drying of paste has been subject to many researches in the past years due to the possibility of obtaining high quality products at low cost. In present work the influence of this technique on microcapsule drug delivery systems performance was evaluated. Casein-pectin microcapsules with entrapped indomethacin and acetaminophen were prepared using the complex coacervation method. Thereafter the coacervates were dried using the spouted bed and spray drying techniques. After spouted bed drying an interaction between indomethacin and casein was observed, with reduction of drug recovery from microcapsules. The mass balance studies showed the absence of indomethacin segregation during spouted bed drying, which indicates drug-polymer interaction. This interaction was not observed for acetaminophen. The physico-chemical evaluation suggests that the indomethacin interaction had covalent nature and in vivo studies showed its stability under enzymatic biological conditions. The microcapsule residence time during spouted bed drying was determined using a validated and optimized stimulus response method. Despite the reliable results obtained it was not possible to determine the influence of residence times on drug-polymer interaction due to the stability of those values with operational conditions. On the other hand air temperature and air flow rate during spouted bed drying affected significantly the degree of drug polymer interaction. In order to evaluate the spouted bed and spray dried microcapsule?s performance a dissolution study was performed. The results showed very similar drug release, with exception for the non-crosslinked formulations dried in spouted bed. These microcapsules were ruptured by spouted bed mechanical stresses. The results obtained on the microcapsules performance evaluation and the characteristics of thermal efficiency and high evaporative capacity of spouted bed demonstrate the potential application of casein-pectin spouted bed drying

<p>Glavni cilj istraživanja ove doktorske disertacije je bio ispitivanje hemijskog sastava lista koprive (Urtica dioica L.), primena različitih ekstrakcionih tehnika radi izolovanja aktivnih jedinjenja iz lista, ispitivanje njihovog hemijskog sastava, kao i formulacija prehrambenog proizvoda dodavanjem ekstrakta lista.<br />U cilju ispitivanja sastava lista primenjene su različite analitičke tehnike kao &scaron;to su GC/MS, GC/FID, UHPLC-DAD/MS/MS, ICP-OES, živin analizator, AAS i spektrofotometrija. Pri tome je dokazano prisustvo različitih klasa hemijskih jedinjenja među kojima su pigmenti (hlorofil i karotenoidi), terpenoidi, fenolni i polifenolna jedinjenja, vitamini (vitamin C i vitamini B grupe) i masne kiseline.<br />Za izdvajanje biolo&scaron;ki aktivnih jedinjenja primenjene su različite tehnike ekstrakcije, kao &scaron;to<br />su: maceracija, Soxhlet ekstrakcija, ultrazvučna (UAE), mikrotalasna (MAE) i superkritična<br />ekstrakcija (SFE). Preliminarne UAE ekstrakcije su pokazale da je voda bila najpogodnija kao rastvarač, odnosno da su vodeni ekstrakti pokazali najveću antioksidativnu aktivnost, kao i najveći sadržaj ukupnih fenola (TPC) i flavonoida (TFC). Pripremljeni vodeni ekstrakti su dalje ispitivani u pogledu sastava, antioksidativne, citotoksične i antimikrobne aktivnosti, gde su rezultati međusobno poređeni kako bi se odabrala najpogodnija ekstrakciona tehnika. Kod SFE je ispitan uticaj uslova ekstrakcije, odnosno pritiska i temperature na<br />sastav dobijenih ekstrakata i njihovu biolo&scaron;ku aktivnost (antioksidativna i citotoksična). Iscrpljeni list korpive je nakon SFE bio ekstrahovan primenom UAE i MAE tehnika, gde su dobijenim ekstraktima utvrđeni sastav i biolo&scaron;ka aktivnost. Nakon svih ispitivanja, MAE ekstrakt i suvi list koprive su dalje primenjeni u formulaciji prehrambenog proizvoda (hleba), gde je variran njihov sadržaj, dok su analizirani sastav, tehnolo&scaron;ki kvalitet hleba, kao i biolo&scaron;ka aktivnost (antioksidativna i citotoksična).</p> / <p>The main goals of this PhD thesis were investigation<br />of chemical composition of stinging nettle leaves<br />(Urtica dioica L.), application of different extraction<br />techniques for isolation of biologically active<br />compounds from leaves, investigation of their<br />chemical composition and formulation of food<br />product with addition of dried leaves and/or its extract.<br />For those purposes, different analytical techniques<br />were applied, i.e. GC/MS, GC/FID, UHPLCDAD/<br />MS/MS, ICP-OES, direct mercury analyzer,<br />AAS and spectrophotometry. Different classes of<br />chemical compounds were detected and identified,<br />such as: pigments (chlorophylls and carotenoids),<br />terpenoids, phenolic and polyphenolic compounds,<br />vitamins (vitamin C and B group) and fatty acids.<br />For the purpose of isolation of biologically active<br />compounds, different extraction techniques were<br />applied: maceration, Soxhlet extraction, ultrasound<br />(UAE), microwave (MAE) and supercritical (SFE)<br />extraction. Preliminary conducted extraction, as well<br />as total phenolics (TPC) and flavonoids (TFC)<br />contents, showed that water was the most suitable<br />solvent for further course of investigation. Water<br />extracts were further analyzed regarding their<br />chemical composition, antioxidant, cytotoxic and antimicrobial activities. Obtained result were<br />compared in order to select the most efficient<br />extraction technique. In the case of SFE, influence of<br />pressure and temperature on extraction yield,<br />composition and biological activity of prepared<br />extracts were monitored. Exhausted plant material<br />after SFE was used for further MAE extraction, while<br />obtained extracts were analyzed to investigate<br />chemical composition and biological activity.<br />After conducted experiments and analysis, MAE<br />extract was used for formulation of food product<br />(bread) where it was added in different amounts in<br />combination of without dried leaves. Obtained<br />products were analyzed regarding their chemical<br />composition, technological requirements and<br />biological activity.</p>

Made available in DSpace on 2017-07-25T19:30:54Z (GMT). No. of bitstreams: 1 Thiago Massao Inagaki.pdf: 2612126 bytes, checksum: d3942c0b1697752935db49380ed68c84 (MD5) Previous issue date: 2016-02-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Although recognized, the effects of lime and gypsum applications over soil organic matter dynamics is still scarcely studied. This research was developed based in the hypothesis the lime and gypsum applications create a favorable environment for biological activity, leading to increase of carbon sequestration and crop productivity. In this way, the objectives of this study were: a) to evaluate the impact of lime and gypsum applications in the soil biological quality, soil organic carbon (SOC) stocks and crop productivity in a long-term no-till system; and b) to evaluate through a laboratory incubation experiment the effects of lime and gypsum in the SOC stocks, Ca and Mg content and soil basal respiration. The field experiment was stablished in 1998 on clay Oxisol (Typic Hapludox), in Ponta Grossa – PR Brazil in a split-plot completely randomized block design. The main plots were comprised in three liming treatments: a) Control, with no lime applications, b) Incorporated lime (IL) at the rate of 4,5 Mg ha-1 and c) Surface-applied lime (SL) at the rate of 4.5 Mg ha-1 divided in three annual applications of 1,5 Mg ha-1 from the experiment establishment. The subplots were comprised by gypsum applied on soil surface at four rates: 0, 3, 6 and 9 Mg ha-1. The soil samples were collected in 2013, fifteen years after the experiment establishment. A laboratory incubation experiment was also carried out to evaluate the effects of both practices. We collected undisturbed samples in 5x5 cm steel rings, which were maintained under 28ºC in 50% of water maximum retention. The experiment design was completely randomized plots with 2x4 factorial design. The treatments assessed were: a) application or not of 4.5 Mg ha-1 of lime; and b) gypsum rates of 0, 3, 6, and 9 Mg ha-1. Over the ring surface, we added corn and soybean residues in order to simulate no-till conditions. In the field experiment, liming provided increase of soil biological activity, SOC stocks, crop productivity, biomass-C input and soil fertility. The C-biomass input and Ca content contributed significantly for increases in SOC stocks. The soil biological activity (measured by enzyme activities) was positively influenced mainly by the labile SOC fractions. Gypsum application positively contributed to increases in SOC labile fractions and arylsulfatase activity. In the incubation experiment, the lime application significantly increased the soil basal respiration, labile SOC stocks and Ca and Mg contents. The gypsum applications significantly increased the labile SOC stocks and Ca content. We observed significant contributions of soil basal respiration and Ca content in the SOC stocks increase. We conclude the lime and gypsum consist in important strategies to promote increases in SOC stocks, governed mainly by the role of Ca as a SOC biding agent and the C-biomass input; and that the use of undisturbed samples were an efficient strategy to assess the effects of lime and gypsum in no-till system. / Apesar de reconhecidos, os efeitos da calagem e gessagem sobre a dinâmica da matéria orgânica ainda são pouco estudados. Este trabalho foi desenvolvido baseando-se na hipótese de que as aplicações de calcário e gesso criam condições favoráveis para o aumento da atividade biológica do solo conduzindo a um incremento do sequestro de carbono e produtividade das culturas. Dessa forma, o objetivo desse trabalho foi: a) avaliar o impacto da calagem e gessagem na atividade biológica do solo, estoques de C e produtividade agronômica em uma área de plantio direto de 15 anos; e b) Avaliar através de um estudo de incubação em laboratório utilizando amostras indeformadas de solo simulando condições de plantio direto, os efeitos da adição de calcário e gesso no solo sobre os estoques de C, conteúdo de Ca e Mg e respiração basal do solo. O experimento a campo foi implantado em 1998 em um Latossolo vermelho argiloso em Ponta Grossa – PR. O delineamento experimental foi em blocos inteiros aleatorizados com parcela subdividida. Os tratamentos implementados nas parcelas foram: a) controle, sem calcário; b) calcário aplicado de forma incorporada (C-inc) na dose de 4,5 Mg ha-1; e c) calcário aplicado em superfície (C-sup) na dose de 4,5 Mg ha-1, dividido em três aplicações anuais de 1.5 Mg ha-1 a partir da instalação do experimento. Os tratamentos que compuseram as subparcelas foram quatro doses de gesso: 0, 3, 6 e 9 Mg ha-1. As amostras de solo foram coletadas em 2013, quinze anos após a implantação do experimento. Um experimento realizado em laboratório com amostras incubadas também foi realizado para estudar os efeitos das práticas. Foram coletadas amostras indeformadas em anéis cilíndricos 5 x 5 cm, mantidas a 28ºC a 50% da capacidade máxima de retenção de água. O delineamento experimental foi inteiramente aleatorizado com fatorial 2 x 4. Os tratamentos foram: a) aplicação ou não de 4,5 Mg ha-1 de calcário em superfície; e b) aplicações superficiais de gesso nas doses de 0, 3, 6 e 9 Mg ha-1. Na superfície do anel foi adicionado resíduos de palha de milho e de soja em períodos distintos para simular uma condição de plantio direto. No experimento a campo, a calagem proporcionou aumento da atividade biológica do solo, estoques de C, produtividade agronômica, aporte de C via resíduos culturais e fertilidade do solo. O aporte de C via resíduos culturais e o conteúdo de Ca+2 do solo contribuíram positivamente para o aumento dos estoques de C. A atividade biológica (medida através da atividade enzimática) foi positivamente influenciada principalmente pela atuação das frações mais lábeis do C. O gesso contribuiu positivamente para o aumento das frações mais lábeis do C e também para a atividade de arilsufatase. No experimento de incubação, a aplicação de calcário aumentou significativamente a respiração basal do solo, estoques de C e concentrações de Ca e Mg. A gessagem aumentou significativamente as frações mais lábeis do C e o conteúdo de Ca. Foram observadas influências significativas do conteúdo de Ca e da respiração basal no aumento dos estoques de C do solo. Conclui-se que a calagem e a gessagem consistem em importantes estratégias para proporcionar aumento dos estoques de C do solo governado principalmente pela atuação do Ca como ligante da matéria orgânica e pelo aporte de C via resíduos culturais e que a utilização de amostras indeformadas com aporte de resíduos em superfície consiste em uma eficiente estratégia para avaliar o efeito da aplicação de calcário e gesso em plantio direto.

Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2017-05-12T14:19:07Z No. of bitstreams: 1 2010 - Henriqueta Talita Guimar?es Barboza.pdf: 10302674 bytes, checksum: 6daf4f88308c3c733615f0772d6db594 (MD5) / Made available in DSpace on 2017-05-12T14:19:07Z (GMT). No. of bitstreams: 1 2010 - Henriqueta Talita Guimar?es Barboza.pdf: 10302674 bytes, checksum: 6daf4f88308c3c733615f0772d6db594 (MD5) Previous issue date: 2010-03-04 / Twelve heterocyclic dialkylphosphorylhydrazones compounds were synthesized in this work. Dialkylphosphorylhydrazones were obtained through 3 steps of reaction. The first step consists on the synthesis of different dialkylphosphonates obtained by reaction of triethyl phosphate (PCl3) with 3 mols of the corresponding alcohol. The second step occurs by the reaction with dialkylphosphonates synthesized and hydrazine, producing dialkylphosphorylhydrazines. The third and last step is the condensation reaction of these dialkylphosphorylhydrazines with different heterocycle substituted aromatic aldehydes. The analysis of the 1H NMR spectra allowed to observe the stereoisomers E and Z, with the formation of E diastereisomer preferencially. All the compounds were characterized by 1H, 13C and 31P NMR, IR and mass spectroscopy. Tests in vitro with, Alternaria sp., Colletotrichum sp., Fusarium sp. e Fusarium solani, known as patogenic in papaya (Carica papaya L.) were performed in order to confirm if the compounds showed fungicide activity. The substance 6 B was the one with the best performance in the inhibition of all fungal growths. Finally, tests with acetylcholinesterase enzyme indicated that all substances did not inhibit this enzyme. Figure 2 - General structures of dialkylphosphoryhidrazones synthesized. R ? Ethyl; propyl; isopropyl e isobuthyl. X = O, Y, Z e W = CH; X = S, Y, Z e W = CH; X = NH, Y, Z e W = CH; X = NH, Y= CH, Z=CH e W = N; X = CH, Y= N, Z=CH e W = N; / Neste trabalho foram sintetizadas doze (12) novas dialquilfosforilidrazonas heteroc?clicas. Esses compostos foram obtidos utilizando-se tr?s etapas de rea??o. A primeira etapa consiste na s?ntese de diferentes fosfonatos de dialquila, obtidos por meio da rea??o do tricloreto de f?sforo (PCl3) com tr?s mols do ?lcool correspondente. A segunda etapa ocorre por meio da rea??o dos fosfonatos de dialquila sintetizados com a hidrazina, formando as dialquilfosforilidrazinas. A terceira e ?ltima etapa ? a condensa??o destas dialquilfosforilidrazinas com diferentes alde?dos heteroc?clicos. A an?lise dos espectros de RMN-1H indica a forma??o de diastereois?meros, E e Z, com predomin?ncia do diastereis?meros E. Todos os compostos obtidos foram caracterizados por RMN de H1 e C13 e P31, IV, an?lises de massas. Em seguida foram realizados testes in vitro para verificar se os mesmos possuem atividade fungicida sobre os fungos Alternaria sp., Colletotrichum sp., Fusarium sp. e Fusarium solani, conhecidos por serem pat?genos da cultura de mam?o (Carica papaya L.). O composto 6 B foi o que apresentou o melhor efeito fungicida sobre o crescimento de todos os fungos. Finalmente foram realizados testes com a enzima acetilcolinesterase a fim de observar a toxicidade dos compostos sintetizados frente a esta enzima. Figura 1- Estrututa gen?rica das dialquilfosforilidrazonas heteroc?clicas sintetizadas. R ? Etil; propil; isopropil e isobutil. X = O, Y, Z e W = CH; X = S, Y, Z e W = CH; X = NH, Y, Z e W = CH; X = NH, Y= CH, Z=CH e W = N; X = CH, Y= N, Z=CH e W = N.

<p style="text-align: justify;">Glavni cilj ove disertacije koji obuhvata dobijanje i hemijsku karakterizaciju ekstrakata i etarskih ulja rtanjskog čaja (Satureja montana L.), bosiljka (Ocimum basilicum L.) i korijandera (Coriandrum sativum L.), kao i njihove sme&scaron;e, je određivanje biolo&scaron;ke aktivnosti dobijenih ekstrakata u in vitro uslovima pradenjem sposobnosti neutralizacije slobodnih radikala i antiproliferativne aktivnosti.<br />Prvo je izvr&scaron;ena karakterizacija biljnih sirovina (rtanjski čaj, bosiljak i korijander), kao i njihove sme&scaron;e jednakih masenih udela (CBS) u pogledu sadržaja vlage, srednjeg prečnika čestica i sadržaja etarskog ulja. U cilju dobijanja etarskih ulja i ekstrakata iz ispitivanih sirovina su primenjeni hidrodestilacija (konvencionalni postupak) i superkritična ekstrakcija (savremena tehnika). GC-MS analizom je određen kvalitativni sastav i relativni udeo pojedinačnih monoterpenskih ugljovodonika, oksidovanih monoterpena, seskviterpena i ostalih jedinjenja. Dalje je GC-FID analizom kvantitativno određen sadržaj i prinos pojedinačnih terpena (&alpha;-pinen, &beta;-pinen, d-limonen, &gamma;-terpinen, eukaliptol, linalool, kamfor, &alpha;-terpineol, geraniol, metil-havikol, karvakrol i eugenol) i izvr&scaron;eno je poređenje uzoraka dobijenih tradicionalnim i savremenim postupcima.<br />Etarskim uljima i lipofilnim ekstraktima je određena biolo&scaron;ka aktivnost ispitivanjem antioksidativne i antiproliferativne aktivnosti. In vitro anti-oksidativna aktivnost superkritičnih ekstrakata i etarskih ulja je određena DPPH testom, dok je antiproliferativna aktivnost određena u in vitro uslovima na tri linije tumorskih delija (HeLa, MDA-MB-453, K562) i na normalne humane fibroblaste (MRC-5).<br />U cilju boljeg određivanja sličnosti između etarskih ulja i lipofilnih ekstrakata rtanjskog čaja, bosiljka, korijandera i njihove sme&scaron;e (CBS) su primenjene hemometrijska tehnike: analiza glavnih komponenata (Principal component analysis) i hijerarhijska klaster analiza (Hierarchical cluster analysis).</p> / <p>The main aim of this dissertation was recovery and chemical characterization of extracts and essential oils of winter savory (Satureja montana L.), basil (Ocimum basilicum L.) and coriander (Coriandrum sativum L.), as well as their mixture, and determination biological activity of extracts in in vitro conditions by capacity towards neutralization of free radicals and antiproliferative activity.<br />Plant materials (winter savory, basil and coriander) and their mixture (CBS) were characterized in terms of moisture content, mean particle size and essential oil content. In order to obtain essential oil and extracts from investigated plants, hydrodistillation (conventional procedure) and supercritical fluid extraction (novel technique) were applied. GC-MS analysis was used for determination of qualitative content and relative abundance of monoterpene hydrocarbons, oxygenated monoterpenes, sesquiterpenes and other volatile compounds. Furthermore, GC-FID analysis was used for quantitative determination of content and yield of terpene compounds (&alpha;-pinene, &beta;-pinene, d-limonene, &gamma;-terpinene, eucalyptol, linalool, camphor, &alpha;-terpineol, geraniol, methyl-chavicol, carvacrol i eugenol) and samples obtained by traditional and novel techniques were compared. Biological potential of essential oil and lipophilic extracts was determined by antioxidant and antiproliferative activity. In vitro antioxidant activity of supercritical extracts and essential oils was determined by DPPH assay, while antiproliferative activity was determined in in vitro conditions on three cancer cell lines (HeLa, MDA-MB-453, K562) and on normal human fibroblasts (MRC-5).<br />Chemometric techniques such as principal component analysis (PCA) i hierarchical cluster analysis (HCA) were applied for better understanding of similarities between essential oils and lipid extracts.</p>