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This work reports a novel biocompatible and biodegradable arborescent amphiphilic polypept(o)ides-based polymer poly(γ-benzyl L-glutamate)-co-poly(γ-tert-butyl L-glutamate)-g-polysarcosine (P(BG-co-Glu(OtBu))-g-PSar) as a smart dual-responsive targeting drug vehicle. The synthesis pathway in this work highlighted the grafting reaction improvement of the polypeptides core and using polysarcosine (PSar) corona as a coating agent. The responsiveness of the polymer is caused by the pH sensitivity of the polypeptides and the reducible linker introduced between the core and corona. While adding the tripeptides arginine, glycine, and aspartate (RGD) as a ligand on the unimolecular micelles’ surface increases the targeting ability of the polymer. During the building of the arborescent, the coupling sites were controlled by using γ-tert-butyl L-glutamate (Glu(OtBu)-NCA) as a second monomer besides γ-benzyl L-glutamate (BG-NCA) since the deprotection conditions are different for Bz and tBu groups. Knowing the coupling sites provides accuracy in calculating the molecular weight (MW) of graft polymers since it facilitates the determination of the grafting yield (Gy). The arborescent unimolecular micelles were formulated by coating the hydrophobic core with PSar hydrophilic corona. The distribution of the coupling sites on the substrates in the last generation yielded end-grafted and randomly-grafted unimolecular micelles. A comparison between those micelles by DLS, TEM, and AFM revealed that the end-grafted micelles showed more uniformity in terms of morphology and size distribution. Also, the surface modification achieved via RGD addition increased the shape uniformity and contributed to avoiding the particles’ aggregation. The sizes and shapes of end-grafted unimolecular micelles match the drug delivery systems (DDSs) requirements. Doxorubicin (DOX) was encapsulated physically into the unimolecular micelles to study the drug loading capacity (DLC) and drug loading efficiency (DLE). The maximum DLC and DLE were 14% and 28% w/w, respectively. The drug release profiles were investigated in healthy- and cancer-mimicking media. The results showed that in cancer-mimicking microenvironment (low pH and high glutathione (GSH) content), the drug diffused out the micelles faster. In addition, a slower drug release was noticed for RGD decorated unimolecular micelles. Finally, the biocompatibility, cytotoxicity, and cellular uptake of the unimolecular micelles were studied. The obtained results were promising as the arborescent unimolecular micelles showed excellent biocompatibility; meanwhile, the DOX-loaded unimolecular micelles have good cytotoxicity compared to free DOX. RGD targeting ligand contributes to increasing the cellular uptake and supports the sustained release.

Tesis por compendio / [EN] The development of new and more complex polymeric materials involves challenging problems to basic sciences. The relationship between structure and molecular dynamics assumes great importance for the future development of novel technologies based on such polymers. Thus, the understanding of how small changes in the chemical structure affect the properties of the material is essential to progress in the technological and scientific area. An in-depth analysis of the molecular mobility leads to establish the structure-properties relationships. On this basis, the main aim of the present work is to study the molecular mobility of two different families of polymeric materials. For this purpose, the experimental techniques mainly used were Differential Scanning Calorimetry (DSC) and Dielectric Relaxation Spectroscopy (DRS). The first family of polymers characterized was a series of chemically cross-linked copolymers composed by Vinylpyrrolidone (VP) and Butyl Acrylate (BA) monomers. In the first place, the influence of the monomer molar ratio (XVP/YBA) on the copolymer properties was studied. Thus, a Fourier Transform Infrared Spectroscopy (FTIR) analysis verified dipole-dipole interactions between amide groups. The influence of these interactions on several parameters related to the molecular mobility was evidenced by the DSC, DRS and Dynamic Mechanical Analysis (DMA) techniques. Secondly, the effect of the cross-link density on the molecular dynamics of 60VP/40BA copolymers was analyzed using DSC and DRS. One single glass transition was detected by DSC measurements. The DRS analysis showed that an increase of the cross-linking produced a typical effect on the alpha process dynamics. However, the beta process, which possessed typical features of pure JG relaxation, unexpectedly lost the intermolecular character for the highest cross-linker content. The fastest gamma process was relatively unaffected. The second family of polymeric materials studied was a series of segmented polycarbonatediol polyurethane (PUPH) modified with different amounts of expanded graphite (EG) conductive filler. Scanning Electron Microscopy (SEM), X-ray diffraction measurements and FTIR analysis demonstrated a homogeneous dispersion of the EG filler in the matrix. DRS was used to study the dielectric properties of the PUPH/EG composites. The dielectric permittivity of the composites showed an insulator to conductor percolation transition with the increase of the EG content (2030 wt%). The addition of expanded graphite to the matrix caused a dramatic increase in the electrical conductivity of ten orders of magnitude, which is an indication of percolative behavior. / [ES] El desarrollo de nuevos materiales poliméricos de mayor complejidad produce un desafío cada vez mayor en el área de las ciencias básicas. La relación entre la estructura y la dinámica molecular resulta de gran importancia para el desarrollo de nuevas tecnologías basadas en estos materiales poliméricos. Así, una mayor comprensión de cómo pequeños cambios en la estructura química afectan a las propiedades de los materiales resulta esencial para el progreso científico y tecnológico. Un análisis en profundidad de la movilidad molecular permite establecer las relaciones estructura-propiedades. Partiendo de esta base, el principal objetivo del presente trabajo es el estudio de la movilidad molecular de dos familias diferentes de materiales poliméricos. Para ello, las técnicas experimentales utilizadas fueron principalmente la Calorimetría Diferencial de Barrido (DSC) y la Espectroscopia de Relajación Dieléctrica (DRS). La primera familia de polímeros caracterizada fue una serie de copolímeros entrecruzados químicamente compuestos por los monómeros Vinilpirrolidona (VP) y Acrilato de Butilo (BA). En primer lugar, se estudió la influencia de la proporción molar de monómero (XVP/YBA) en las propiedades del copolímero. A través de un análisis por Espectroscopia de Infrarrojo por Transformada de Fourier (FTIR), se verificó la existencia de interacciones dipolo-dipolo entre los grupos amida. Mediante el análisis por DSC, DRS y Análisis Dinamomecánico (DMA), se evidenció la influencia de estas interacciones en diferentes parámetros relacionados con la movilidad molecular. En segundo lugar, se analizó el efecto de la densidad de entrecruzamiento en la dinámica molecular de los copolímeros 60VP/40BA usando DSC y DRS. A través de las medidas de DSC se observó una única transición vítrea para todos los entrecruzamientos. El análisis por DRS mostró como el incremento en entrecruzante produjo el típico efecto en la dinámica del proceso alpha, pero sin embargo, el proceso beta, que tenía las características típicas de una relajación JG, perdió de forma inesperada su carácter intermolecular para el mayor contenido en entrecruzante. El proceso gamma no se vio afectado. La segunda familia de materiales poliméricos estudiada fue una serie de poliuretanos segmentados (PUPH) modificados con diferentes cantidades de grafito expandido (EG), utilizado como relleno conductivo (desde 0 a 50% en peso). El análisis de los resultados obtenidos mediante Microscopía Electrónica de Barrido (SEM), Difracción de Rayos X y FTIR demostró la homogénea dispersión del relleno de EG en la matriz de PUPH. La técnica DRS se usó para estudiar las propiedades dieléctricas de los materiales compuestos PUPH/EG. La permitividad dieléctrica de los materiales mostró una transición de percolación desde aislante a conductor al incrementarse el contenido en EG (rango de 20-30% en peso). La adición de grafito expandido a la matriz de PUPH causó un incremento significativo en la conductividad dieléctrica de diez órdenes de magnitud, lo que indica el comportamiento de percolación. / [CA] El desenvolupament de nous materials polimèrics de major complexitat produeix un desafiament cada vegada major en l'àrea de les ciències bàsiques. La relació entre l'estructura i la dinàmica molecular resulta de gran importància per al desenrotllament de noves tecnologies basades en aquests materials polimèrics. Així, una major comprensió de com petits canvis en l'estructura química afecten a les propietats dels materials, resulta essencial per al progrés científic i tecnològic. Un anàlisis en profunditat de la mobilitat molecular permet establir les relacions estructura-propietats. Partint d'aquesta base, el principal objectiu del present treball és l'estudi de la mobilitat molecular de dues famílies diferents de materials polimèrics. Per a això, les tècniques experimentals utilitzades van ser principalment la Calorimetria Diferencial de Rastreig (DSC) i l'Espectroscòpia de Relaxació Dielèctrica (DRS). La primera família de polímers caracteritzada va ser una sèrie de copolímers entrecreuats químicament compostos pels monòmers Vinilpirrolidona (VP) i Acrilat de Butilo (BA) . En primer lloc, es va estudiar la influència de la proporció molar de monòmer (XVP/YBA) en les propietats del copolímer. A través d'una anàlisi per Espectroscòpia d'Infraroig per Transformada de Fourier (FTIR), es va verificar l'existència d'interaccions dipol-dipol entre els grups amida. Mitjançant l'anàlisi per DSC, DRS i Anàlisi Dinamomecánico (DMA), es va evidenciar la influència d'aquestes interaccions en diferents paràmetres relacionats amb la mobilitat molecular. En segon lloc, es va analitzar l'efecte de la densitat d'entrecreuament en la dinàmica molecular dels copolímers 60VP/40BA mitjançant DSC i DRS. A través de les mesures de DSC es va observar una única transició vítria per a tots els continguts d'agent entrecreuant . L'anàlisi per DRS va mostrar com l'increment en agent entrecreuant va produir l'efecte esperat en la dinàmica del procés alfa. En canvi, el procés beta, que tenia les característiques típiques d'una relaxació JG, va perdre de forma inesperada el seu caràcter intermolecular per al major contingut en agent entrecreuant. El procés més ràpid gamma no es va veure afectat. La segona família de materials polimèrics estudiada va ser una sèrie de poliuretans segmentats (PUPH) modificats amb diferents quantitats de grafit expandit (EG) , utilitzat com a farcit conductiu (des de 0 a 50% en pes). L'anàlisi dels resultats obtinguts per mitjà de Microscòpia Electrònica de Rastreig (SEM), Difracció de Rajos X i FTIR va mostrar la dispersió homogènia del EG en la matriu de PUPH. La tècnica DRS es va utilitzar per a estudiar les propietats dielèctriques dels materials compostos PUPH/EG. La permitivitat dielèctrica dels materials va mostrar una transició de percolació des d'aïllant a conductor amb l'increment de contingut en EG (20-30% en pes). L'addició d'EG a la matriu de PUPH va causar un increment significatiu en la conductivitat dielèctrica, de deu ordes de magnitud. / Redondo Foj, MB. (2015). A contribution to the study of the molecular mobility in polymeric materials by Thermal and Dielectric Analysis [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/59457 / Compendio

Les copolymères à blocs amphiphiles sont des macromolécules composées d’au moins un bloc hydrophile lié chimiquement à un ou plusieurs blocs hydrophobes. En milieu aqueux, ils s’auto-associent pour former des micelles dont les cœurs constitués des blocs hydrophobes sont protégés de l’eau par une couronne constituée des blocs hydrophiles hydratés. La majorité des copolymères à blocs amphiphiles génèrent dans l’eau des micelles « gelées » ne présentant aucun échange de chaînes entre elles. Ceci vient du fait que l’énergie nécessaire pour extraire un bloc hydrophobe du cœur des objets est beaucoup trop importante. Par conséquent, les caractéristiques des micelles sont plus contrôlées cinétiquement que thermodynamiquement. Pour diminuer cette énergie nous avons incorporé des unités hydrophile acide acrylique (AA) dans le bloc hydrophobe de poly(acrylate de n-butyle) (PnBA). L’incorporation de 50% molaire d’unités AA dans le bloc hydrophobe conduit à la formation d’agrégats pH-sensibles dans le cas du dibloc PAA-b-P(AA0.5-stat-nBA0.5) comme montré dans une étude antérieure. Cette thèse a consisté en une analyse quantitative de la dynamique d’auto-association de copolymères dibloc et tribloc amphiphiles à base d’acrylate de n-butyle et d’acide acrylique dont les blocs hydrophobes contiennent 50% d’unités hydrophiles réparties de manière statistique. Les copolymères à blocs ont été synthétisés par polymérisation radicalaire contrôlée par ATRP. L’influence de la concentration, du pH, de la température et de la force ionique sur la structure et les propriétés mécaniques des systèmes auto-assemblés a été systématiquement étudiée. Par diffusion statique de la lumière nous avons montré la présence d’une concentration d’agrégation critique (CAC) au-dessus de laquelle, des micelles de type étoile (dibloc) ou fleur (tribloc) sont formées par auto-association des blocs hydrophobes. A plus fortes concentrations, des interactions répulsives de type volume exclu apparaissent entre les micelles étoiles. Pour les micelles fleurs, à l’inverse des interactions attractives conduisent au pontage des fleurs jusqu’à l’obtention de réseaux tri-dimensionnels au-dessus de la concentration de percolation. Une attraction trop importante entre les fleurs peut même conduire à une séparation de phase à forte force ionique et bas pH. En diffusion dynamique de la lumière, nous avons montré que la formation des réseaux s’accompagnait de l’apparition d’un mode lent dont l’origine a été expliquée par un mouvement balistique d’hétérogénéités relaxées dans les systèmes. La vitesse de relaxation de ces hétérogénéités s’avèrent être dépendantes des propriétés mécaniques des hydrogels. La formation des réseaux et la dynamique d’échange des chaînes ont été étudiées par rhéologie. La viscosité augmente régulièrement avec la concentration jusqu’à la concentration de percolation où une augmentation brusque de la viscosité se produit et un temps de relaxation apparaît. Le temps de vie des ponts a été finement contrôlé et modulé sur plusieurs décades par modification du pH, de la température et de la force ionique. La formation in-situ des hydrogels nous a permis de mettre en évidence un phénomène de vieillissement des réseaux après leur formation avant d’atteindre un état stationnaire. Ce phénomène s’est traduit par une augmentation du temps de relaxation au cours du temps avant d’atteindre une valeur plateau. Ceci nous a également permis de comprendre pourquoi il était possible de générer des réseaux homogènes, par vieillissement, possédant une dynamique extrêmement lente voir nulle. / Amphiphilic block copolymers are macromolecules composed of at least one hydrophilic block chemically linked to one or several hydrophobic blocks. In water, these macromolecules self-assemble to form micelles composed of a hydrophobic core surrounded by a hydrated hydrophilic corona. The majority of amphiphilic block copolymers form “frozen” micelles in aqueous solution. This means that there is no dynamic exchange of chains between micelles because the energy necessary to extract a hydrophobic block from the core of micelles is too high. Consequently, the characteristics of the micelles are controlled kinetically and not thermodynamically. In order to decrease this energy, we have incorporated acrylic acid units (AA) in the hydrophobic block of poly(n-butyl acrylate) (PnBA). It was previously shown that the incorporation of 50% molar of AA units in the hydrophobic block led to generation of pH-sensitive micelles in the case of PAA-b-P(AA0.5-stat-nBA0.5) diblocks. This thesis presents of a quantitative analysis of the dynamics of self-assembled amphiphilic diblock and triblock copolymer based on acrylic acid units and n-butyl acrylate units. The hydrophobic blocks contained 50% of acrylic acids units incorporated randomly. The block copolymers were synthesized by controlled radical polymerization (ATRP). The influence of the concentration, pH, temperature and the ionic strength on the structure and the mechanical properties of the self-assembled systems was systematically studied. At low concentrations, static light scattering measurements showed the formation of star-like micelles (diblock) or flower-like micelles (triblock) above a critical aggregation concentration (CAC). At higher concentrations, purely repulsive excluded volume interactions between micelles appeared in the case of diblock copolymers. In the case of triblock copolymers bridging of flower-like micelles induced in addition attractive interactions leading to network formation above the percolation concentration. At high ionic strength and low pH, we showed that the attraction between flower-like micelles became sufficiently stong to induce phase separation. Dynamic light scattering measurements showed besides a fast mode due to cooperative diffusion, a second slow relaxation mode that appeared at the percolation concentration. The origin of this mode was explained by a balistic motion induced by the relaxation of heterogeneities inside the system. The velocity of heterogeneities was determined by the mechanical relaxation of the hydrogels. The formation of the network and the exchange dynamic of chains were studied by rheology. The viscosity of solutions increased sharply at the percolation concentration. The terminal visco-elastic relaxation time of the network is related to the lifetime of bridges. It could be controlled and tuned over several decades by varing of pH, temperature and the ionic strength. The in-situ formation of networks revealed an aging of networks after their formation before they reached their stationary state. Aging caused a slow increase of the relaxation time before reaching its steady value. This explains why it is possible to generate homogeneous networks even if the network at steady is kinetically frozen.

Le poly (acide lactique) (PLA), est un polymère synthétisé à partir de ressources renouvelables, qui est l'objet de beaucoup d'études à l'heure actuelle mais qui souffre d'une faible résistance au choc. Le but de ce travail est de rechercher des pistes permettant la préparation d'un matériau à base de PLA avec une résistance au choc améliorée tout en minimisant la perte de résistance à la traction. Les travaux présentés ici ont étudié le rôle de nanoparticules élastomères de poly (acrylate de butyle) (PBA) chargées de laponite (LRD) (PBA-LRD) ainsi que de nanocomposites coeur-écorce (PBA-LRD)/poly(méthacrylate de méthyle) (PMMA) en tant qu'agents de renforcement d'une matrice de PLA. Ces nanoparticules ont été dispersées dans la matrice PLA à l'état fondu. La synthèse de ces nanoparticules a été effectuée par polymérisation en émulsion ou miniémulsion. La laponite a été incorporée dans les nanoparticules afin de minimiser la perte de la rigidité tout en améliorant la résistance au choc de PLA. Trois types de tensioactifs et des modifications de surface de la laponite ont été testées pour améliorer l'adhérence entre les particules de PBA et la matrice de PLA. Enfin une écorce de PMMA a été utilisée pour assurer la bonne adhérence entre les particules de PBA et de matrice PLA. Nous avons montré que les particules coeur-écorce ont permis d'augmenter la résistance au choc au 3 fois du PLA tout en réduisant la diminution du module d'Young et la perte de résistance à la traction (~25%). Les propriétés de les particules synthétiques et les propriétés des mélange du PLA avec les particules PBA ou particules coeur-écorce ont été étudiées par diverses techniques de caractérisation (DLS, FTIR, ATG, MET, MEB, RMN 1H, DSC, DMTA...) / Poly (lactic acid) (PLA), come from renewable resources, one of the most important biopolymers, suffers from weak impact resistance. The aim of this work is to develop a process that will allow preparing a PLA with improved impact resistance while minimizing loss in tensile strength. The work presented here examined in detail the synthesis of poly(butyl acrylate) (PBA) nanoparticles charged with laponite (LRD) (PBA-LRD) and (PBA-LRD) / poly(methyl methacrylate) (PMMA) core-shell nanocomposites. They were dispersed phase in PLA matrix and were synthesized by emulsion or miniemulsion polymerization. The clay such as laponite was included in these nanoparticles to minimize the loss of rigidity while improving the impact resistance of PLA. Note that three types of surfactants and some modify agents for LRD have been tried to improve the adhesion between the PBA particles and matrix PLA, PMMA was finally used to ensure a good adhesion between the PBA particles and the matrix. To this end, we explored successively the PLA blend, using PBA nanocomposites and the PBA/PMMA core-shell nanoparticles as reinforcing agents, with improved impact resistance, showing that core-shell particles allowed increasing of 3 times of impact strength of the PLA with a minimum amount of loss (~25%) in Young?s modulus and tensile strength. The properties of the synthetic particles and the properties of PLA blends have been demonstrated by various characterization techniques (DLS, FTIR, TGA, TEM, SEM, 1H-NMR, DSC, DMTA ...)

A atividade catalítica de clusters trigonais de acetato de rutênio e porfirinas supramoleculares contendo quatro unidades de clusters periféricos ou complexos de bis(bipiridina)rutênio, na oxidação de substratos orgânicos por iodosil-benzeno ou terc-butil-hidroperóxido, é abordada nesta tese. Foram feitos estudos cinéticos para elucidar o mecanismo de catálise, com especial destaque para duas espécies supramoleculares isoméricas representadas por Mn(3-TRPyP) ou Mn(4-TRPyP), nos quais os complexos de bis(bipiridina)(cloro)rutênio se coordenam à tetrapiridilporfirina através das posições meta ou para da ponte piridínica, respectivamente. Além da maior seletividade proporcionada pelos catalisadores supramoleculares, a substituição do íon cloreto pela água nos complexos periféricos de rutênio, intensificou a atividade catalítica, gerando novos sítios ativos, do tipo Ru(IV)=O. Também foram estudados clusters trinucleares de rutênio, altamente reativos, no estado Ru(III)Ru(IV)Ru(IV)=O. Estes foram gerados eletroquimicamente em solução aquosa, apresentando pronunciada atividade catalítica na oxidação do alcool benzílico. Finalmente, uma espécie dimérica de cluster, ainda inédita, com ponte oxo, foi caracterizada e investigada do ponto de vista catalítico. / The catalytic activity of trinuclear ruthenium clusters and supramolecular tetrapyridylporphyrins containing four peripheral cluster units or bis(bipyridine)ruthenium complexes, in the oxidation of organic substrates by iodosylbenzene or tert-butil-hydroperoxide, is dealt with in this thesis. Kinetic studies were performed in order to elucidate the mechanisms of catalysis involving two isomeric species denoted Mn(3-TRPyP) or Mn(4-TRPyP), in which the bis(bipyridine)(chloro)ruthenium complexes are bound to the tetrapyridylporphyrin center, at the meta or para positions of the pyridine bridge, respectively. In addition to the improved selectivity by such supramolecular catalysts, the substitution of the chloride ion by water in the peripheral ruthenium complexes, greatly enhanced their catalytic activity by generating new Ru(IV)=O reactive sites. Highly reactive trinuclear ruthenium clusters of the type Ru(III)Ru(IV)Ru(IV)=O were also generated electrochemically in aqueous solution, exhibiting pronounced catalytic activity in the oxidation of benzyl alcohol. Finally, a novel dimeric oxo-bridged cluster species was characterized, and its role in catalysis investigated.

Urea is the main nitrogen (N) fertilizer used worldwide, but N losses in the form of ammonia (NH3) is a major problem when this fertilizer is topdressed over crop residues. The treatment of urea with N-(n-butyl) thiophosphoric triamide (NBPT) decreases the activity of urease enzyme and volatilization losses in many crops. However, the amount of straw over the soil in green cane trash blanketing (GCTB) systems affect the effectiveness of NBPT-treated urea in reducing NH3 losses. The hypothesis of this study is that an increase of NBPT concentration in NBPT-treated urea above the commercial concentration adopted nowadays (530 mg kg-1) is necessary to reduce volatilization losses and improve the efficiency of this fertilizer in GCTB systems. The aim of this study was to evaluate, under field conditions, NH3 losses from urea amended with four NBPT concentrations and applied over sugarcane straw. Six field trials were carried out across the State of São Paulo, the main sugarcane-cropped area in Brazil. It was adopted the randomized block experimental design with four replications. The treatments consisted of urea amended with the NBPT concentrations 0, 530, 850, 1500 and 2000 mg kg-1, ammonium nitrate and a control treatment (without N fertilizer). The NH3 volatilization was measured through an enclosure semi-static collector system containing two polyethylene foam discs treated with orthophosphoric acid and glycerol. The foam discs were collected and replaced at 2, 4, 6, 8, 10, 12, 16, 20, 25 and 30 days after the fertilizer application (DAF). The N trapped into the foams was extracted using deionized water and the N concentration determined by Flow Injection Analysis (FIA). Boltzmann sigmoidal models were fitted to cumulative losses of NH3 along the days. Cumulative losses between locals were compared by Tukey HSD and the effect of NBPT concentrations were tested by regression analyses (P<0.05). There was a significant effect of local and environmental conditions on amount of NH3 losses. NBPT was less effective in reducing NH3 losses under high temperatures and thick straw layer, probably because of the high urease activity and the early inhibitor degradation. The increase on NBPT concentration on urea above 530 mg kg-1 not only delayed the time of maximum rate of loss (Tmax), but also reduced cumulative NH3 losses. The two higher NBPT concentrations promoted an average delay of six days from untreated urea Tmax. Linear reduction of NH3 emissions occurred up to the NBPT concentration of 1000 mg kg-1 that reduced 43% of NH3 losses as compared to urea. Any increment in NBPT concentration above this range did not reflect in substantial reduction of NH3 losses. Increase NBPT concentration showed potential in reducing NH3 volatilization losses under GCTB sugarcane, however, further research is necessary to evaluate the impact of NH3 savings on sugarcane yield and the economic feasibility of this technology. / A ureia é o principal fertilizante nitrogenado utilizado em todo o mundo, porém, perdas de nitrogênio (N) na forma de amônia (NH3) são um importante problema associado ao uso desse fertilizante. O tratamento da ureia com N-(n-butil) tiofosfórico triamida (NBPT) reduz a atividade da enzima urease e a volatilização de NH3 em muitos cultivos. Entretanto, a quantidade de palha sobre o solo em sistemas de cultivo da cana-de-açúcar colhida sem queima (CCSQ) afeta a eficiência do tratamento da ureia com NBPT em reduzir as perdas de NH3. A hipótese deste estudo é que é necessário aumentar a concentração de NBPT na ureia acima da atual concentração comercial (530 mg kg-1) para reduzir as perdas por volatilização, de modo a viabilizar o uso de ureia tratada com NBPT em sistemas de CCSQ. O objetivo desse estudo foi avaliar, em condições de campo, as perdas de NH3 de ureia tratada com quatro concentrações de NBPT e aplicada sobre a palhada de cana-de-açúcar. Seis experimentos de campo foram conduzidos no Estado de São Paulo, principal área cultivada com cana-de-açúcar no Brasil. Foi utilizado delineamento aleatorizado em blocos com quatro repetições. Os tratamentos consistiram em ureia tratada com NBPT nas concentrações 0, 530, 850, 1500 e 2000 mg kg-1, nitrato de amônio e um tratamento controle (sem adubação nitrogenada). A volatilização e NH3 foi mensurada através de sistema coletor semiestático fechado, contendo dois discos de espuma de polietileno embebidos com solução de ácido ortofosfórico e glicerina. Os discos de espuma foram coletados e substituídos aos 2, 4, 6, 8, 10, 12, 16, 20, 25 e 30 dias após a aplicação dos fertilizantes (DAF). O N retido nas espumas foi extraído usando água deionizada e a concentração de N determinada por Análise por Injeção em Fluxo (FIA). Modelos sigmoides de Boltzmann foram ajustados para as perdas cumulativas de NH3 ao longo dos dias. As médias das perdas acumuladas entre locais foram comparadas usando teste de Tukey e o efeito das concentrações de NBPT foi testado por análise de regressão (P<0,05). Houve forte influência do local e das condições ambientais nas perdas de NH3. O NBPT foi menos eficiente reduzir as perdas de NH3 em condições de alta temperatura e grossa camada de palha, provavelmente devido à alta atividade de urease e à degradação prematura do inibidor. O aumento na concentração de NBPT na ureia acima de 530 mg kg-1 não apenas retardou o pico de máxima taxa de perda diária (Tmax), mas também reduziu as perdas acumuladas de NH3. As duas maiores concentrações de NBPT promoveram um retardamento médio de seis dias em relação ao Tmax da ureia. Uma redução linear nas emissões de NH3 foi verificada até a dose de 1000 mg kg-1 de NBPT, que levou a uma redução de 43% nas perdas em comparação à ureia não tratada. Incrementos na concentração de NBPT acima desse valor não se refletiram em redução substancial das perdas de NH3. Aumentar a concentração de NBPT na ureia demonstrou potencial em reduzir as perdas e NH3 por volatilização em sistemas de CCSQ, entretanto são necessárias mais pesquisas avaliando o impacto do N preservado no sistema sobre a produtividade da cana-de-açúcar e a viabilidade econômica dessa tecnologia.

A atividade catalítica de clusters trigonais de acetato de rutênio e porfirinas supramoleculares contendo quatro unidades de clusters periféricos ou complexos de bis(bipiridina)rutênio, na oxidação de substratos orgânicos por iodosil-benzeno ou terc-butil-hidroperóxido, é abordada nesta tese. Foram feitos estudos cinéticos para elucidar o mecanismo de catálise, com especial destaque para duas espécies supramoleculares isoméricas representadas por Mn(3-TRPyP) ou Mn(4-TRPyP), nos quais os complexos de bis(bipiridina)(cloro)rutênio se coordenam à tetrapiridilporfirina através das posições meta ou para da ponte piridínica, respectivamente. Além da maior seletividade proporcionada pelos catalisadores supramoleculares, a substituição do íon cloreto pela água nos complexos periféricos de rutênio, intensificou a atividade catalítica, gerando novos sítios ativos, do tipo Ru(IV)=O. Também foram estudados clusters trinucleares de rutênio, altamente reativos, no estado Ru(III)Ru(IV)Ru(IV)=O. Estes foram gerados eletroquimicamente em solução aquosa, apresentando pronunciada atividade catalítica na oxidação do alcool benzílico. Finalmente, uma espécie dimérica de cluster, ainda inédita, com ponte oxo, foi caracterizada e investigada do ponto de vista catalítico. / The catalytic activity of trinuclear ruthenium clusters and supramolecular tetrapyridylporphyrins containing four peripheral cluster units or bis(bipyridine)ruthenium complexes, in the oxidation of organic substrates by iodosylbenzene or tert-butil-hydroperoxide, is dealt with in this thesis. Kinetic studies were performed in order to elucidate the mechanisms of catalysis involving two isomeric species denoted Mn(3-TRPyP) or Mn(4-TRPyP), in which the bis(bipyridine)(chloro)ruthenium complexes are bound to the tetrapyridylporphyrin center, at the meta or para positions of the pyridine bridge, respectively. In addition to the improved selectivity by such supramolecular catalysts, the substitution of the chloride ion by water in the peripheral ruthenium complexes, greatly enhanced their catalytic activity by generating new Ru(IV)=O reactive sites. Highly reactive trinuclear ruthenium clusters of the type Ru(III)Ru(IV)Ru(IV)=O were also generated electrochemically in aqueous solution, exhibiting pronounced catalytic activity in the oxidation of benzyl alcohol. Finally, a novel dimeric oxo-bridged cluster species was characterized, and its role in catalysis investigated.

Urea is the main nitrogen (N) fertilizer used worldwide, but N losses in the form of ammonia (NH3) is a major problem when this fertilizer is topdressed over crop residues. The treatment of urea with N-(n-butyl) thiophosphoric triamide (NBPT) decreases the activity of urease enzyme and volatilization losses in many crops. However, the amount of straw over the soil in green cane trash blanketing (GCTB) systems affect the effectiveness of NBPT-treated urea in reducing NH3 losses. The hypothesis of this study is that an increase of NBPT concentration in NBPT-treated urea above the commercial concentration adopted nowadays (530 mg kg-1) is necessary to reduce volatilization losses and improve the efficiency of this fertilizer in GCTB systems. The aim of this study was to evaluate, under field conditions, NH3 losses from urea amended with four NBPT concentrations and applied over sugarcane straw. Six field trials were carried out across the State of São Paulo, the main sugarcane-cropped area in Brazil. It was adopted the randomized block experimental design with four replications. The treatments consisted of urea amended with the NBPT concentrations 0, 530, 850, 1500 and 2000 mg kg-1, ammonium nitrate and a control treatment (without N fertilizer). The NH3 volatilization was measured through an enclosure semi-static collector system containing two polyethylene foam discs treated with orthophosphoric acid and glycerol. The foam discs were collected and replaced at 2, 4, 6, 8, 10, 12, 16, 20, 25 and 30 days after the fertilizer application (DAF). The N trapped into the foams was extracted using deionized water and the N concentration determined by Flow Injection Analysis (FIA). Boltzmann sigmoidal models were fitted to cumulative losses of NH3 along the days. Cumulative losses between locals were compared by Tukey HSD and the effect of NBPT concentrations were tested by regression analyses (P<0.05). There was a significant effect of local and environmental conditions on amount of NH3 losses. NBPT was less effective in reducing NH3 losses under high temperatures and thick straw layer, probably because of the high urease activity and the early inhibitor degradation. The increase on NBPT concentration on urea above 530 mg kg-1 not only delayed the time of maximum rate of loss (Tmax), but also reduced cumulative NH3 losses. The two higher NBPT concentrations promoted an average delay of six days from untreated urea Tmax. Linear reduction of NH3 emissions occurred up to the NBPT concentration of 1000 mg kg-1 that reduced 43% of NH3 losses as compared to urea. Any increment in NBPT concentration above this range did not reflect in substantial reduction of NH3 losses. Increase NBPT concentration showed potential in reducing NH3 volatilization losses under GCTB sugarcane, however, further research is necessary to evaluate the impact of NH3 savings on sugarcane yield and the economic feasibility of this technology. / A ureia é o principal fertilizante nitrogenado utilizado em todo o mundo, porém, perdas de nitrogênio (N) na forma de amônia (NH3) são um importante problema associado ao uso desse fertilizante. O tratamento da ureia com N-(n-butil) tiofosfórico triamida (NBPT) reduz a atividade da enzima urease e a volatilização de NH3 em muitos cultivos. Entretanto, a quantidade de palha sobre o solo em sistemas de cultivo da cana-de-açúcar colhida sem queima (CCSQ) afeta a eficiência do tratamento da ureia com NBPT em reduzir as perdas de NH3. A hipótese deste estudo é que é necessário aumentar a concentração de NBPT na ureia acima da atual concentração comercial (530 mg kg-1) para reduzir as perdas por volatilização, de modo a viabilizar o uso de ureia tratada com NBPT em sistemas de CCSQ. O objetivo desse estudo foi avaliar, em condições de campo, as perdas de NH3 de ureia tratada com quatro concentrações de NBPT e aplicada sobre a palhada de cana-de-açúcar. Seis experimentos de campo foram conduzidos no Estado de São Paulo, principal área cultivada com cana-de-açúcar no Brasil. Foi utilizado delineamento aleatorizado em blocos com quatro repetições. Os tratamentos consistiram em ureia tratada com NBPT nas concentrações 0, 530, 850, 1500 e 2000 mg kg-1, nitrato de amônio e um tratamento controle (sem adubação nitrogenada). A volatilização e NH3 foi mensurada através de sistema coletor semiestático fechado, contendo dois discos de espuma de polietileno embebidos com solução de ácido ortofosfórico e glicerina. Os discos de espuma foram coletados e substituídos aos 2, 4, 6, 8, 10, 12, 16, 20, 25 e 30 dias após a aplicação dos fertilizantes (DAF). O N retido nas espumas foi extraído usando água deionizada e a concentração de N determinada por Análise por Injeção em Fluxo (FIA). Modelos sigmoides de Boltzmann foram ajustados para as perdas cumulativas de NH3 ao longo dos dias. As médias das perdas acumuladas entre locais foram comparadas usando teste de Tukey e o efeito das concentrações de NBPT foi testado por análise de regressão (P<0,05). Houve forte influência do local e das condições ambientais nas perdas de NH3. O NBPT foi menos eficiente reduzir as perdas de NH3 em condições de alta temperatura e grossa camada de palha, provavelmente devido à alta atividade de urease e à degradação prematura do inibidor. O aumento na concentração de NBPT na ureia acima de 530 mg kg-1 não apenas retardou o pico de máxima taxa de perda diária (Tmax), mas também reduziu as perdas acumuladas de NH3. As duas maiores concentrações de NBPT promoveram um retardamento médio de seis dias em relação ao Tmax da ureia. Uma redução linear nas emissões de NH3 foi verificada até a dose de 1000 mg kg-1 de NBPT, que levou a uma redução de 43% nas perdas em comparação à ureia não tratada. Incrementos na concentração de NBPT acima desse valor não se refletiram em redução substancial das perdas de NH3. Aumentar a concentração de NBPT na ureia demonstrou potencial em reduzir as perdas e NH3 por volatilização em sistemas de CCSQ, entretanto são necessárias mais pesquisas avaliando o impacto do N preservado no sistema sobre a produtividade da cana-de-açúcar e a viabilidade econômica dessa tecnologia.