Les dendrimères sont très prometteurs du fait de leur structure unique et de leur multivalence. Cependant, leur synthèse souffre de problèmes de défauts de structure et de présence de produits secondaires très similaires. Des approches synthétiques alternatives sont donc fortement désirées. L'objectif de ma thèse consiste à explorer la synthèse sur support solide et l’approche d'autoassemblage pour la préparation de dendrimères.La première partie de ma thèse se concentre sur la synthèse de dendrimères en phase solide. Nous avons tout d'abord développé une méthode de synthèse pour les dendrimères poly(amidoamines) basée sur la chimie des peptides. Nous avons ensuite construit une petite bibliothèque de dendrimères de type triazine en faisant varier la taille et la terminaison des dendrimères pour créer une variété de dendrimères. Nous avons aussi tenté de synthétiser des dendrimères poly(aminoesters) bien que nous n'ayons pu les obtenir du fait du caractère labile de ces dendrimères.La deuxième partie de ma thèse vise à appliquer l’approche d'autoassemblage pour la construction de dendrimères supramoléculaires comme théranostiques combinant l'imagerie et la thérapie. Nous avons synthétisé un petit dendrimère amphiphile portant DOTA pour chélater le Gd (III). Ce dendrimère est capable de s'autoassembler en supramolécule et d’encapsuler l’agent anticancéreux doxorubicine, pour construire des agents théranostiques à base de dendrimères multivalents.L’ensemble de ma thèse se consacre au développement de stratégies en phase solide et de l'autoassemblage pour construire des dendrimères pour les applications dans les domaines biomédicaux et des matériaux. / Dendrimers hold great promise for wide applications thanks to their unique structural architecture and multivalent cooperativity. However, dendrimer synthesis often suffers from structural defects caused by incomplete reactions and difficulties associated with purification. Consequently, alternative synthetic approaches to overcome the limitations of current dendrimer synthesis are in high demand.My first PhD project mainly focuses on establishing novel strategies and methodologies for solid-phase dendrimer synthesis with advantages of convenient complete synthesis and easy purification procedures. We first developed a new and concise solid-phase synthesis of PAMAM dendrimers based on the adoption of peptide synthesis chemistry. We then constructed a small library of triazine dendrimers varying in generations and surface groups with a view to rapidly synthesizing dendrimers with structural diversity. We also strived to synthesize poly(aminoester) dendrimers although we had difficult to get it thorough.My second PhD program aims to apply the self-assembly approach for constructing supramolecular dendrimer theranostics. A small DOTA-conjugated amphiphilic dendrimer with Gd(III)-chelation was synthesized and self-assembled into supramolecular nanomicelles to encapsulate the anticancer drug doxorubicin. The obtained system constitutes a multivalent nanotheranostic to combine imaging purpose with therapeutic utility.In summary, my PhD program mainly contributes to elaborating strategies for dendrimer synthesis using both solid-phase method and self-assembly approach in the view to realizing and broadening their applications in the arenas of biomedical and material sciences.

La cristallisation en continu de nanoparticules énergétiques est un défi de longue date. Le Spray Flash Evaporation (SFE) est une technique majeure développée et brevetée en interne, pour la production en continu de matériaux énergétiques submicroniques ou nanométriques ; la technologie se base sur la surchauffe d’un solvant pulvérisé dans le vide et s’évaporant de manière flash. Ce présent travail de recherche a pour but de comprendre et contrôler la cristallisation au sein du procédé SFE. Le RDX et le cocristal CL-20:HMX 2:1 sont étudiés. La sursaturation, concernant le SFE, est une fonction du temps et de l’espace liée aux tailles et vitesses de gouttes : elle fut variée par un anti-solvant et par l’amélioration du SFE avec un système double buse. Ensuite, PVP 40K et PEG 400 ont été utilisés afin de contrôler la nucléation et la croissance. Les particules ont pu être ajustées d’une taille de 160 nm à 5 µm, avec des morphologies facettées ou sphériques et avec des sensibilités moindres. / The continuous formation of nanosized energetic material is a long-standing challenge. Spray Flash Evaporation (SFE) is a major technique, internally developed and patented, for continuously producing energetic materials at submicron or nano scale; it relies on the superheating of a solvent sprayed into vacuum and thus flashing. This present research project aims to understand and control the crystallisation occurring in the SFE process. RDX and the cocrystal CL-20:HMX 2:1 was studied overcome the limited in situ characterizations also. The supersaturation is a function of time and space in SFE, linked to the size distribution and velocity of droplets. Supersaturation was raised with an anti-solvent and by the enhancement of the SFE with a dual nozzle system. Then PVP 40K and PEG 400 were successfully used to alter the nucleation and the growth. The particles were subsequently tuned from 160 nm spheres to 5 µm grains and were less sensitive, especially toward electrostatic discharge.

Les différents rejets aqueux de types industriel, artisanal et/ou hospitalier, contiennent différents contaminants organiques ou inorganiques qu’il convient d’éliminer. Selon le type de l’industrie et de l’utilisation, ces rejets auront besoin de subir un ou plusieurs traitements. Il existe de nombreuses méthodes de traitement des eaux adaptées à chaque pollution et à chaque usage. Dans le cadre de ce travail, nous nous sommes intéressés à l’utilisation d’une méthode peu onéreuse qui met en jeu les ions ferriques, ions ferreux, oxygène moléculaire et la lumière solaire (Fe(III)/Fe(II)/O2/hν) pour induire la transformation de composés organiques appartenant à deux familles de pesticides : les sulfonylurées et les organophosphorés. L’objectif majeur de l’étude consiste à la compréhension du rôle des ions de fer(II) dans le processus photocatalytique largement reporté dans la littérature ainsi que d’identifier les principaux produits formés au cours du processus. L’étude de la dégradation des sulfonylurées par excitation UV du peroxyde a démontré, sans aucune surprise, une réelle efficacité du processus. La réaction met en jeu les radicaux hydroxyles qui ont été clairement mis en évidence et quantifiés sous irradiation continue et par photolyse laser. Le processus dépend de la concentration initiale du substrat, du pH et de la concentration du photoinducteur (H2O2). La présence dans le milieu de la plupart des ions inorganiques conduit à une inhibition partielle de la dégradation. Dans le cas des ions étudiés, l’ordre de la réactivité est SO42- > Cl- > NO3- > CO32- . Cet aspect est très important à considérer lorsqu’il s’agit de traiter des eaux par le procédé UV/H2O2 . Lors de l’étude du comportement photochimique du complexe [Fe(H2O)5(OH)]2+ sous excitation à 365 nm et en simulateur solaire, la principale espèce réactive mise en jeu est le radical hydroxyle. En présence de composés organiques, une dégradation totale a pu être obtenue et ceci même pour de faibles concentrations en complexe de fer(III) (1,0x10-6 mol L-1). Il y a donc une régénération in situ et sous irradiation du fer(III). L’ensemble des expériences entreprises a permis de montrer que la régénération met en jeu non seulement le fer(II) mais également l’oxygène. La présence simultanée du fer(III) à l’état de trace et du fer(II) joue un rôle clé. En effet, l’excitation du fer(III) permet la production d’état excités qui transfèrent l’énergie aux ions de fer(II). Ces derniers états excités de fer(II) réagissent avec l’oxygène moléculaire par un processus de transfert d’électrons pour générer du fer(III) et l’anion superoxyde. La solution se trouve ainsi de plus en plus enrichie en fer(III) au fur et à mesure de l’excitation lumineuse. Sur le plan analytique, nous avons utilisé la technique LC/MS et LC/ESI/MS2 pour appréhender la structure chimique des photoproduits formés par l’étude précise des processus de fragmentation. Parmi toutes les réactions habituelles du radical hydroxyl (hydroxylation du noyau aromatique, scission du pont sulfonylurée et déméthylation), nous avons montré que certaines sulfonylurées conduisent, en milieu légèrement acide, à un processus de scission du squelette triazinique. Une telle réaction a également pu être confirmée par des études théoriques au niveau B3LYP/6-31G (d,p). La présence simultanée d’un groupement methoxy et d’une amine secondaire adjacente au cycle triazine est une condition essentielle pour une telle ouverture. L’ouverture du cycle est une étape importante pour atteindre l’objectif de l’étude qui est d’obtenir la minéralisation des solutions et ainsi le traitement des rejets aqueux de types industriel, artisanal et/ou hospitalier. / Waste waters resulting from industrial and artisanal activities as well as from hospital discharges contain numerous toxic organic and inorganic contaminants that require efficient treatment. In the present work, we employed various combinations of ferric and ferrous ions, oxygen, hydrogen peroxide and sunlight (Fe(III)/Fe(II)/O2/hν) to induce the transformation of two pesticide families: sulfonylureas and organophosphorus. The main objective of the study was devoted to the role of iron(II) species in the whole transformation process and also to the elucidation of the generated byproducts. In a first step, we used the system H2O2/ hν as a preliminary process for the degradation of the pollutant. This allowed a complete and fast removal of sulfonylureas. The reaction mainly involves hydroxyl radicals that were identified and quantified by nanosecond laser photolysis technique. The process highly depends on the initial substrate concentration, pH and the concentration of the photoinductor (H2O2). The presence of inorganic ions that could be present in waste waters was shown to inhibit the degradation, in the following decreasing order: SO42- > Cl- > NO3- > CO32- . In a second step, the study of the photochemical behavior of the iron(III) aquacomplex, [Fe(H2O)5(OH)]2+, upon light excitation at 365 nm as well as by using a solar simulator also showed the generation of hydroxyl radical together with iron(II) species. A complete elimination of studied pesticides was obtained even at low concentrations of iron(III) complex (1,0x10-6 mol L-1), indicating the high efficiency of the process. To gain insight into the degradation mechanism, the evolution of iron species upon irradiation was investigated in the absence and in the presence of molecular oxygen. The results suggested that a regeneration mechanism of iron(III) occurs through two consecutives steps. First, the excitation of iron(III) in trace concentrations, leads to the formation of iron(II) excited states through energy transfer process followed an electron transfer process that involves molecular oxygen and iron(II) excited state. As a conclusion, the solution becomes more and more enriched by iron(III) via the light excitation and in the presence of oxygen revealing the photocatalytic behavior of [Fe(H2O)5(OH)]2+. Within this work, a special attention was also devoted to the identification of products formed during the above photocatalytic process. This was performed by using liquid chromatography coupled to tandem mass spectrometry LC/ESI/MS2. The close investigation of the fragmentation processes of the generated products, permitted the establishment of precise chemical structures. In addition to the classical degradation of sulfonylureas by hydroxyl radicals (hydroxylation of the aromatic ring, the scission of sulfonylurea bridge and demethylation) a ring opening of the triazine skeleton was also obtained. This was observed under acidic conditions and was clearly confirmed by theoretical studies at the B3LYP / 6-31G (d, p) level. This triazine scission was only obtained with sulfonylures that contain a methoxy group and a secondary amine adjacent to the triazine moiety. Such ring opening constitutes an important and fundamental step when decontamination or/and mineralization of waste waters are concerned.

Les verres moléculaires sont passionnants puisqu'ils soulèvent plusieurs interrogations quant à la nature même de leur existence. Comment expliquer l'émergence de la phase vitreuse au sein de petites molécules organiques d'une cinquantaine d'atomes? Existe-t-il une explication moléculaire permettant de comprendre ce phénomène ou s'agit-il d'une propriété d'ordre supérieur régie par ses propres lois où une interprétation au niveau moléculaire ne suffit pas à expliquer la formation d'un matériau vitreux? Est-il possible d'obtenir un modèle permettant de bien représenter la phase solide amorphe des verres moléculaires et prédire ses différentes propriétés physico-chimiques et mécaniques? C'est ce que la recherche présentée dans ce mémoire tente de résoudre en apportant quelques éclaircissements. Dans un premier temps, le lecteur sera plongé dans l'importance du projet avec un contexte littéraire actuel, un bref état de l'art de la recherche sur les verres moléculaires, ainsi qu'une brève présentation du chemin de pensée qui a mené à la création de ce projet de recherche sur les verres moléculaires. Dans un deuxième temps, il se verra montrer les différents concepts théoriques des techniques utilisées, que sont la spectroscopie par résonance magnétique nucléaire dynamique et l'analyse de ses bandes, ainsi que la simulation par calculs quantiques et par dynamique moléculaire, pour répondre aux questions précédentes. Dans un troisième et dernier temps, le lecteur se verra expliquer les différents résultats et leurs conséquences quant à la résolution du mystère des verres moléculaires, ainsi que les travaux qui demeurent à effectuer sur le projet pour parvenir à obtenir un bon modèle de prédiction pour les propriétés désirées. Les résultats obtenus au fil des travaux de recherche effectués et présentés en détail dans ce mémoire sont d'une grande importance pour la compréhension du phénomène de la phase vitreuse qui existe au sein des verres moléculaires. Entre autres, la quantification des énergies d'activation a permis de comprendre qu'en milieu solvaté, il faut avoir une énergie d'activation minimale d'environ 20kJ/mol pour une rotation d'angle dièdre pour qu'une phase vitreuse soit observée dans le matériau. De plus, les mesures ont montré que le modèle de simulation qui était utilisé avant le début de ces travaux de recherche n'était pas idéal pour bien représenter les mouvements au sein des verres moléculaires. Les mouvements en question incluent les oscillations des longueurs de liaisons, les oscillations des angles de valence et les rotations d'un angle dièdre autour d'une liaison. De nouveaux paramètres ont été obtenus par calculs quantiques et ils ont confirmé que les paramètres du champ de forces qui était utilisé n'étaient pas bons pour la simulation de verres moléculaires. Entre autres, les valeurs d'équilibre d'oscillations des longueurs de liaisons et des angles de valence n'étaient pas du tout les mêmes que celles définies dans le champ de forces utilisé. Les concepts associés aux travaux réalisés ainsi que les résultats obtenus ont été présentés dans plusieurs congrès, entre autres, au « Canadian Society for Chemistry » en 2015 et en 2016, respectivement à Ottawa (ON, Canada) et à Halifax (NS, Canada), sous forme d'affiches. Ils ont aussi été présentés aux congrès du centre québécois sur les matériaux fonctionnels en 2015, sous forme d'affiche, et en 2016, en présentation à l'oral.

Vários estudos têm mostrado os benefícios da aplicação agronômica de lodo de esgoto sobre as propriedades físicas e químicas do solo. No entanto, poucos são aqueles que avaliam o impacto desta prática sobre o comportamento de pesticidas em solos tropicais. O principal objetivo deste estudo foi avaliar o efeito da adição de diferentes fontes de lodo (Ribeirão Preto, Franca e Jundiaí) na sorção / dessorção e lixiviação do herbicida ametrina em solos canavieiros do estado de São Paulo (Neossolo Quartzarênico Órtico Típico (RQ), Latossolo Vermelho Distrófico Típico (LVd), Argissolo Vermelho Eutroférrico Chernossólico (PV) e Latossolo Vermelho Distroférrico (LVdf). Cinco concentrações (de 4,4 a 79,8 mg i.a. L-1) do herbicida foram utilizadas para obter os valores dos coeficientes de sorção de Freündlich (Kf) e dos coeficientes aparentes de sorção médio e para a menor concentração (Kd ap médio e Kd ap [menor]), a qual corresponde à dose de campo recomendada. Para o teste de lixiviação, o método utilizado foi o de lixiviação em colunas de solo (diâmetro = 5 cm e comprimento = 30 cm), utilizando-se três repetições para cada tratamento, sobre as quais foi simulada chuva de 200 mm uniformemente distribuídas durante 48 h, após a aplicação da solução de 14Cametrina na dose de 3,0 kg i.a. ha-1. De forma geral, a sorção da ametrina variou de moderada à alta em todos os tratamentos (2,68 < Kd ap [menor] < 85,71 L kg-1). Solos argilosos com maior teor de matéria orgânica e argilas do tipo 2:1, como é o caso do PV, apresentaram muito maior potencial de sorção da ametrina; enquanto que solos arenosos com baixos teores de matéria orgânica, como foram os casos do LVd e RQ, apresentaram moderado potencial de sorção. A aplicação de lodos menos estabilizados, com biomassa e material orgânico menos recalcitrante e, portanto, com maiores valores de carbono orgânico total, carbono orgânico dissolvido e pH, como é o caso do lodo de Ribeirão Preto, tendeu a diminuir o potencial de sorção da ametrina. Já a adição de lodos mais recalcitrantes, como o de Jundiaí, tendeu a aumentar o potencial de sorção da ametrina, principalmente em solos arenosos devido a sua menor capacidade tampão. Nestes cenários, poderá ocorrer redução da eficácia agronômica ametrina, uma vez que haverá menos produto disponível na solução do solo. A ametrina apresentou baixo potencial de lixiviação (< 1% da quantidade aplicada) em todos os tratamentos, os quais não apresentaram diferenças entre si, sendo que a grande maioria do pesticida (> 95% da quantidade aplicada) ficou retida na camada de 0-10 cm de profundidade da coluna de solo. Isto implica dizer que a ametrina apresenta baixo potencial de contamina águas subterrâneas, mesmo em solos arenosos, como RQ (90% de areia) / Several studies have shown the benefits of applying sewage sludge on the physical and chemical properties of the soils. However, just a few of them evaluates the impact of this practice on the behavior of pesticides in tropical soils. The main goal of this research was to evaluate the effects of applying different sources of sewage sludge (Ribeirão Preto, Franca e Jundiaí) on the sorption / desorption and leaching of ametryne in soils from São Paulo state (Brazil) cultivated with sugarcane (Neossolo Quartzarênico Órtico Típico (RQ), Latossolo Vermelho Distrófico Típico (LVd), Argissolo Vermelho Eutroférrico Chernossólico (PV) e Latossolo Vermelho Distroférrico (LVdf). Five concentrations (4.4 to 79.8 mg a.i. ha-1) of the herbicide were applied to the soil samples to attain the Freündlich sorption coefficients (Kf) and the apparent sorption coefficient for the lower concentration (Kd ap [menor]), which corresponded to the field application rate. For the leaching test the adopted method was the soil leaching columns (diameter = 5 cm and depth = 30 cm), in triplicates, over which a 200 mm rainfall evenly distributed during 48 h was simulated just after ametryne application at the rate of 3.0 kg a.i. ha-1. In general, ametryne sorption ranged from moderate to high in all treatments (2.68 < Kd ap [menor] < 85.71 L kg-1). Clay soils with higher organic matter and 2:1 clay contents, such as the PV, showed much higher sorption potential, whereas sand soils with low organic matter content, such as LVd and RQ, showed moderate sorption potential. The application of less stabilized sewage sludges, with less recalcitrant biomass and organic material and, therefore, with higher organic matter and dissolved organic carbon contents and pH values, such as the Ribeirão Preto, tends to decrease ametryne sorption potential. Otherwise, the addition of more recalcitrant sludges, such as the Jundiaí, tends to enhance its sorption potential, mainly in sand soils due to its lower buffer capacity. In those cases, the agronomic efficacy of ametryne may be reduced since there is lower concentration of the compound available in the soil solution. The ametryne presented low leaching potential in all treatments (< 1% of the applied amount), which were not different among themselves, and that its majority (> 95% of the applied amount) was found at 0 -10 cm soil depth in the column. It implies that ametryne has low potential to contaminate groundwater even in sandy soils, such as the RQ (90% sand)

Nesse trabalho foi estudada uma técnica para a detecção de OHTC na água salina. Descobriu-se que certos complexos de rutênio em determinados valores de pH reagem com a molécula de OHTC e isto é detectável por espectrofotometria UV-Vis. Foram estudados os complexos fac-[RuCl2(S-DMSO)3(O-DMSO)] (complexo 1), {[(DMSO)2H][trans-RuCl4(DMSO)2]} (complexo 2) e cis-[RuCl2(bpy)2].2H2O (complexo 3). O complexo 1 possui um dos ligante (O-DMSO) que pode ser substituído pelo OHTC. Já o complexo 2 possui um dos ligantes (S-DMSO) na posição trans um ao outro, e o complexo 3 possui os 2 íons Cl- para tal finalidade. Determinou-se que o complexo 1 é viável, mesmo em presença de sais presentes na água do mar. Assim a reação foi realizada em função do tempo, variação do pH, temperatura e concentração de OHTC. Nos outros dois complexos os estudos foram realizados sem a variação da temperatura e concentração de OHTC. / p>In this work we studied a technique for detection of OHTC in water. It was discovered that complexes involving ruthenium, on determined pH values, react with the OHTC molecule and this is detectable by UV-VIS spectroscopy. The complexes fac-[RuCl2(S-dmso)3(O-dmso)] (complex 1), {[(DMSO)2H][trans-Ru(DMSO)2Cl4]} (complex 2), and cis-[RuCl2(bpy)2].2H2O (complex 3) were studied. The complex 1 present one position ( O - DMSO) which can be substituted by the OHTC. Additionally, the complex 2 present two ligands ( S- DMSO) trans between each other, and the complex 3 present two chloride ions for the same porpose of complex 1 respectively. It was determined that the complex 1 was able to react with OHTC even in presence of the salts present in sea water. Thereby, the reaction involving complex 1 and OHTC was monitored in function of the time, pH, temperature, and finally concentration of OHTC. On the other two complexes, the reaction was studied without variation of temperature and concentration of OHTC.

Nesse trabalho foi estudada uma técnica para a detecção de OHTC na água salina. Descobriu-se que certos complexos de rutênio em determinados valores de pH reagem com a molécula de OHTC e isto é detectável por espectrofotometria UV-Vis. Foram estudados os complexos fac-[RuCl2(S-DMSO)3(O-DMSO)] (complexo 1), {[(DMSO)2H][trans-RuCl4(DMSO)2]} (complexo 2) e cis-[RuCl2(bpy)2].2H2O (complexo 3). O complexo 1 possui um dos ligante (O-DMSO) que pode ser substituído pelo OHTC. Já o complexo 2 possui um dos ligantes (S-DMSO) na posição trans um ao outro, e o complexo 3 possui os 2 íons Cl- para tal finalidade. Determinou-se que o complexo 1 é viável, mesmo em presença de sais presentes na água do mar. Assim a reação foi realizada em função do tempo, variação do pH, temperatura e concentração de OHTC. Nos outros dois complexos os estudos foram realizados sem a variação da temperatura e concentração de OHTC. / p>In this work we studied a technique for detection of OHTC in water. It was discovered that complexes involving ruthenium, on determined pH values, react with the OHTC molecule and this is detectable by UV-VIS spectroscopy. The complexes fac-[RuCl2(S-dmso)3(O-dmso)] (complex 1), {[(DMSO)2H][trans-Ru(DMSO)2Cl4]} (complex 2), and cis-[RuCl2(bpy)2].2H2O (complex 3) were studied. The complex 1 present one position ( O - DMSO) which can be substituted by the OHTC. Additionally, the complex 2 present two ligands ( S- DMSO) trans between each other, and the complex 3 present two chloride ions for the same porpose of complex 1 respectively. It was determined that the complex 1 was able to react with OHTC even in presence of the salts present in sea water. Thereby, the reaction involving complex 1 and OHTC was monitored in function of the time, pH, temperature, and finally concentration of OHTC. On the other two complexes, the reaction was studied without variation of temperature and concentration of OHTC.

Vários estudos têm mostrado os benefícios da aplicação agronômica de lodo de esgoto sobre as propriedades físicas e químicas do solo. No entanto, poucos são aqueles que avaliam o impacto desta prática sobre o comportamento de pesticidas em solos tropicais. O principal objetivo deste estudo foi avaliar o efeito da adição de diferentes fontes de lodo (Ribeirão Preto, Franca e Jundiaí) na sorção / dessorção e lixiviação do herbicida ametrina em solos canavieiros do estado de São Paulo (Neossolo Quartzarênico Órtico Típico (RQ), Latossolo Vermelho Distrófico Típico (LVd), Argissolo Vermelho Eutroférrico Chernossólico (PV) e Latossolo Vermelho Distroférrico (LVdf). Cinco concentrações (de 4,4 a 79,8 mg i.a. L-1) do herbicida foram utilizadas para obter os valores dos coeficientes de sorção de Freündlich (Kf) e dos coeficientes aparentes de sorção médio e para a menor concentração (Kd ap médio e Kd ap [menor]), a qual corresponde à dose de campo recomendada. Para o teste de lixiviação, o método utilizado foi o de lixiviação em colunas de solo (diâmetro = 5 cm e comprimento = 30 cm), utilizando-se três repetições para cada tratamento, sobre as quais foi simulada chuva de 200 mm uniformemente distribuídas durante 48 h, após a aplicação da solução de 14Cametrina na dose de 3,0 kg i.a. ha-1. De forma geral, a sorção da ametrina variou de moderada à alta em todos os tratamentos (2,68 < Kd ap [menor] < 85,71 L kg-1). Solos argilosos com maior teor de matéria orgânica e argilas do tipo 2:1, como é o caso do PV, apresentaram muito maior potencial de sorção da ametrina; enquanto que solos arenosos com baixos teores de matéria orgânica, como foram os casos do LVd e RQ, apresentaram moderado potencial de sorção. A aplicação de lodos menos estabilizados, com biomassa e material orgânico menos recalcitrante e, portanto, com maiores valores de carbono orgânico total, carbono orgânico dissolvido e pH, como é o caso do lodo de Ribeirão Preto, tendeu a diminuir o potencial de sorção da ametrina. Já a adição de lodos mais recalcitrantes, como o de Jundiaí, tendeu a aumentar o potencial de sorção da ametrina, principalmente em solos arenosos devido a sua menor capacidade tampão. Nestes cenários, poderá ocorrer redução da eficácia agronômica ametrina, uma vez que haverá menos produto disponível na solução do solo. A ametrina apresentou baixo potencial de lixiviação (< 1% da quantidade aplicada) em todos os tratamentos, os quais não apresentaram diferenças entre si, sendo que a grande maioria do pesticida (> 95% da quantidade aplicada) ficou retida na camada de 0-10 cm de profundidade da coluna de solo. Isto implica dizer que a ametrina apresenta baixo potencial de contamina águas subterrâneas, mesmo em solos arenosos, como RQ (90% de areia) / Several studies have shown the benefits of applying sewage sludge on the physical and chemical properties of the soils. However, just a few of them evaluates the impact of this practice on the behavior of pesticides in tropical soils. The main goal of this research was to evaluate the effects of applying different sources of sewage sludge (Ribeirão Preto, Franca e Jundiaí) on the sorption / desorption and leaching of ametryne in soils from São Paulo state (Brazil) cultivated with sugarcane (Neossolo Quartzarênico Órtico Típico (RQ), Latossolo Vermelho Distrófico Típico (LVd), Argissolo Vermelho Eutroférrico Chernossólico (PV) e Latossolo Vermelho Distroférrico (LVdf). Five concentrations (4.4 to 79.8 mg a.i. ha-1) of the herbicide were applied to the soil samples to attain the Freündlich sorption coefficients (Kf) and the apparent sorption coefficient for the lower concentration (Kd ap [menor]), which corresponded to the field application rate. For the leaching test the adopted method was the soil leaching columns (diameter = 5 cm and depth = 30 cm), in triplicates, over which a 200 mm rainfall evenly distributed during 48 h was simulated just after ametryne application at the rate of 3.0 kg a.i. ha-1. In general, ametryne sorption ranged from moderate to high in all treatments (2.68 < Kd ap [menor] < 85.71 L kg-1). Clay soils with higher organic matter and 2:1 clay contents, such as the PV, showed much higher sorption potential, whereas sand soils with low organic matter content, such as LVd and RQ, showed moderate sorption potential. The application of less stabilized sewage sludges, with less recalcitrant biomass and organic material and, therefore, with higher organic matter and dissolved organic carbon contents and pH values, such as the Ribeirão Preto, tends to decrease ametryne sorption potential. Otherwise, the addition of more recalcitrant sludges, such as the Jundiaí, tends to enhance its sorption potential, mainly in sand soils due to its lower buffer capacity. In those cases, the agronomic efficacy of ametryne may be reduced since there is lower concentration of the compound available in the soil solution. The ametryne presented low leaching potential in all treatments (< 1% of the applied amount), which were not different among themselves, and that its majority (> 95% of the applied amount) was found at 0 -10 cm soil depth in the column. It implies that ametryne has low potential to contaminate groundwater even in sandy soils, such as the RQ (90% sand)

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2014-08-01T11:50:31Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao Daniela Cristina Vinhal.pdf: 4105984 bytes, checksum: f00413027a2eaed20e59defa2239af07 (MD5) / Made available in DSpace on 2014-08-01T11:50:31Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao Daniela Cristina Vinhal.pdf: 4105984 bytes, checksum: f00413027a2eaed20e59defa2239af07 (MD5) Previous issue date: 2012 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In Brazil, the estimates for the year 2012 point to approximately 134,000 new cases of skin cancer, being mostly related to exposure to ultraviolet radiation. According to current consensus, such damage can be minimized by prophylactic use of sunscreens, which aims to protect human skin against harmful effects of UV radiation. This way, this study proposed to plan, synthesize, characterize and evaluate a new compound to be a sunscreen (17). The structural planning is made from photoprotective triazona ethylhexyl prototypes (12) and cinnamate (4) having the compound 15 which was produced from vanillin, a natural abundant and low cost product. In addition, 17 compound has molecular weight above 800 Daltons, which is in accordance with the photoprotective recently launched on the market, because it minimizes or even prevents its absorption through the skin. The synthetic route proposal consisted of two stages, which after optimized lead to obtain the 17 compound in 78.6% overall yield. It is noteworthy that the 15 compound was obtained in quantitative yield and the 17 compound was purified by Soxhlet extractor, using amyl alcohol as solvent. These facts make its synthesis a bit laborious and inexpensive, fundamental characteristics of a technological product, from the financial point of view. All the synthesized compounds were characterized by spectrometric techniques of nuclear magnetic resonance of hydrogen-dimensional and two-dimensional, infrared, mass and ultraviolet, in equal ways. From the spectrophotometric absorption technique it was identified that 17 compound had two peaks of maximum absorption (λmax.) in the UV, and 306 nm in the region of UVB and 344 nm for UVA. It is also possible to calculate the parameters of the molar absorptivity (ε) and specific extinction coefficient (E), whose values were above 104 -1 cm-1 for ε and 5,843 4,337 for E. Moreover, the 15 and 17 compounds were also M evaluated on their redox profile using the technique of cyclic voltammetry which showed that the 17 compound keeps stable considering the applied potential. The thermogravimetric thermal analysis the 17 compound showed a weight loss of 47.88% in the range of 330 °C under an atmosphere of synthetic air, characterized as a stable compound at high temperatures. From the in vitro evaluation by the spectrophotometric method described by Mansur it presented SPF equal to 4.58, while under the same conditions the methoxycinnamato of octyl (4), sunscreen sold worldwide, presented SPF equal to 2.79. At the end of this work it is possible to observe that the proposed synthetic route to obtain the 17 compound was effective, given the obtained high yields, laborious and low cost steps. Finally, we conclude that the structural planning employee was ratified, since the described physical-chemicals organic evaluated had great similarities with the prototype sunscreen (12) and (4) used in its planning. / No Brasil, as estimativas para o ano de 2012 apontam para a ocorrência de, aproximadamente, 134 mil casos novos de câncer de pele, sendo em sua maioria relacionados com exposição à radiação ultravioleta. Segundo consenso atual, tais danos podem ser minimizados através do uso profilático de protetores solares, cujo objetivo é proteger a pele humana contra efeitos nocivos da radiação UV. Neste sentido, o presente trabalho se propôs planejar, sintetizar, caracterizar e avaliar um novo composto candidato a fotoprotetor (17). O planejamento estrutural se deu a partir dos protótipos fotoprotetores etilhexil triazona (12) e cinamato (4), tendo como partida o composto 15 que foi produzido a partir da vanilina, um produto natural abundante e de baixo custo. Ademais, o composto 17 apresenta peso molecular acima de 800 Daltons, o que está de acordo com os fotoprotetores lançados no mercado recentemente, pois minimiza ou mesmo impede sua absorção através da pele. A rota sintética proposta constituiu-se por duas etapas, que após otimizadas levaram a obtenção do composto 17 em rendimento global de 78,6%. Vale salientar que o composto 15 foi obtido em rendimento quantitativo e o composto 17 foi purificado através do extrator de Soxhlet, empregando álcool amílico como solvente. Tais fatos tornam sua síntese pouco laboriosa e pouco onerosa, características fundamentais a um produto tecnológico, sob o ponto de vista financeiro. Todos os compostos sintetizados foram caracterizados através das técnicas espectrométricas de ressonância magnética nuclear de 1H unidimensional e 1H-13C bidimensional, infravermelho, massas e ultravioleta, de forma inambígua. A partir da técnica de absorção espectrofotométrica, indentificou-se para o composto 17 dois picos de absorção máxima (λmáx.) no UV, sendo 306 nm na região da UVB e 344 nm na UVA. Também pode-se calcular os parâmetros de absortividade molar (ε) e coeficiente de extinção específico (E), cujos valores foram acima de 104 para ε e 5.843 e 4.337 para E. Por conseguinte, os compostos 15 e 17 também foram avaliados quanto ao seu perfil redox através da técnica de voltametria cíclica, a qual ilustrou que o composto 17 mantém-se estável frente aos potenciais aplicados. Quanto a análise térmica termogravimétrica, o composto 17 apresentou uma perda de massa de 47,88% na faixa de 330 °C sob atmosfera de ar sintético, caracterizando-o como composto estável sob temperaturas elevadas, visto que seu ponto de fusão ocorre em 186 oC. A partir da avaliação in vitro pelo método espectrofotométrico descrito por Mansur o mesmo apresentou FPS igual a 4,58 ao passo que sob as mesmas condições o para-metoxicinamato de octila (4), filtro solar comercializado mundialmente, apresentou FPS de 2,79. Ao término deste trabalho podemos observar que a rota sintética proposta para a obtenção do composto 17 se mostrou eficaz, face aos altos rendimentos obtidos, etapas pouco laboriosas e de baixo custo. Por fim, podemos concluir que o planejamento estrutural empregado foi ratificado, uma vez que os descritos físico- químicos orgânicos avaliados apresentaram grandes similaridades com os protótipos fotoprotetores (12) e (4) empregados no seu planejamento.

Parmi tous les neurotransmetteurs identifiés à ce jour, la sérotonine (5-hydroxytryptamine, 5-HT) est impliquée dans le système le plus complexe de récepteurs. Parmi eux, les récepteurs 5-HT7 qui sont les derniers découverts (1993) semblent avoir des implications multiples tant au niveau central que périphérique. Le potentiel thérapeutique représenté par la découverte de ligands 5-HT7 sélectifs vis-à-vis d'autres RCPGs a motivé notre projet de recherche. Nos études sont orientées vers la conception de trois classes distinctes de ligands. Une première famille à été conçue sur une charpente benzimidazolone. Diverses pharmacomodulations ont permis un changement du profil d'activité de 5-HT1A vers 5-HT7. Une deuxième famille de composés à structure furo- ou pyrano[2,3-b] pyridinique constitue des analogues azotés d'un des plus intéressants agonistes sélectifs 5-HT7 actuels. La synthèse de ces dérivés a été conduite via la mise en oeuvre d'une étape clé de cycloaddition intramoléculaire de Diels-Alder à partir de 1,2,4-triazines judicieusement fonctionnalisées en 3 par une chaine aminoalkynol. Cette méthodologie nous a permis de faire varier les substituants alkyle de l'amine, la nature et la position du motif aryle sur le noyau pyridinique, ainsi que la taille du cycle non-aromatique. La synthèse d'une dernière famille de dérivés bisaryliques a enrichi les études de relation structure-activité, connues dans la littérature, associées à ce type de ligands 5-HT7. La variation du cycle aromatique central (phényle, 1,3-diazine et 1,2,4- triazine) a révélé d'importantes conséquences sur l'affinité des molécules.