Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-10-27T12:46:47Z No. of bitstreams: 0 / Made available in DSpace on 2017-10-27T12:46:47Z (GMT). No. of bitstreams: 0 / Leishmaniose é uma zoonose desenvolvida por protozoários do gênero Leishmania. A doença se manifesta sob a forma visceral e cutânea cujo tratamento apresenta diversas limitações como alto custo, elevada toxicidade dos fármacos e altos índices de recidiva. A leishmaniose cutânea abrange lesões destrutivas e ulceradas que podem evoluir para condições mais graves culminando em óbito dos hospedeiros acometidos. Tratamentos alternativos tem sido implementados com a finalidade de proporcionar acessibilidade financeira e menores efeitos colaterais aos pacientes. A terapia fotodinâmica se insere nesse contexto devido à praticidade, custo reduzido, mínima toxicidade e sem relatos de resistência descritos na literatura. O objetivo desse trabalho foi avaliar os efeitos da terapia fotodinâmica em leishmaniose cutânea induzida em camundongos BALB/c infectados com leishmaniose cutânea. A otimização da PDT também foi avaliada pela administração de doadores de óxido nítrico (S-nitroso-MSA) encapsulados em nanopartículas de quitosana (CSNPs), já que esse composto é altamente reativo e potencialmente tóxico para o parasito. Camundongos BALB/c foram infectados no membro posterior esquerdo com 1.106 promastigotas de Leishmania (L) amazonensis que expressam o gene da luciferase e acompanhados por 4 semanas até o surgimento da lesão. Após esse período, os animais foram distribuídos em 6 grupos (n=4): Controle (não tratado), PDT1 (submetidos à uma sessão de PDT), PDT2 (duas sessões ), PDT1NPNO e PDT2NPNO (uma sessão e duas sessões de PDT em associação com S-nitroso-MSACPNPS, respectivamente), e NPNO (somente S-nitroso-MSA-CP NPS). A segunda sessão foi realizada 24 h após a primeira. A PDT foi efetuada usando um diodo emissor de luz (LED, λ=660 ± 22 nm) e azul de metileno (100 μM), com densidade de energia de 150 J/cm2. O progresso da doença foi avaliado por meio do tamanho da lesão e escala de dor utilizando um paquímetro e filamentos von Frey, respectivamente. A carga parasitária foi quantificada por intermédio do bioimageamento nas primeiras 96 h após o tratamento e nas 4 semanas seguintes. Os resultados obtidos demonstraram redução na carga parasitária durante o período experimental, com exceção do grupo PDT1NPNO. Houve redução parasitária significante em 72 h e 96 h para os grupos PDT2, PDT2NPNO e NPNO. A maior redução da lesão foi observada para o grupo PDT2 bem como menor sensibilidade ao estímulo doloroso. Nossos resultados indicam efeitos benéficos da PDT em duas sessões, sugerindo que pode ter ocorrido modulação do processo inflamatório. Entretanto, o uso das nanopartículas nas condições utilizadas nesse experimento não foi capaz de otimizar a eficiência da PDT nos animais infectados com Leishmania (L) amazonensis. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Partículas e filmes híbridos de polímeros e compostos de amônio quaternário (CAQ) foram caracterizados quanto a propriedades físicas e atividade contra cepas de Pseudomonas aeruginosa ATCC 27853 e Staphylococcus aureus ATCC 25923. Partículas híbridas foram obtidas a partir de fragmentos de bicamada (BF) de brometo de dioctadecildimetilamônio (DODAB), adicionados consecutivamente de soluções de carboximetilcelulose (CMC) e cloreto de poli (dialildimetilamônio) (PDDA) e, a seguir, caracterizadas por espalhamento de luz dinâmico para determinação de distribuições de tamanho, diâmetro médio (Dz) e potencial-zeta (ζ). Filmes híbridos foram obtidos por revestimento rotacional de lamínulas de vidro a partir de uma solução clorofórmica de poli (metil metacrilato) (PMMA) e CAQ onde [PMMA] = 10 mg/mL e [CAQs] = 0,03 4 mM de DODAB, brometo de cetiltrimetilamônio (CTAB) ou brometo de tetrapropilamônio (TPAB). Molhabilidade dos filmes e difusibilidade dos CAQs nos filmes imersos em água foram avaliadas por determinação de ângulo de contato e de tensão superficial na interface ar-água, respectivamente. Atividade antimicrobiana foi avaliada por plaqueamento e contagem de viáveis, tanto para os filmes quanto para as partículas. Para os filmes, também foram determinados halos de inibição. Partículas de DODAB BF/ CMC/ PDDA exibiram Dz e ζ dependentes da concentração dos componentes. A 0,1 mM de DODAB, 0,1 mg/mL de CMC e 0,1 mg/mL de PDDA, foram obtidas partículas pequenas (Dz = 100 nm; ζ = 30 mV). Com 0,5 mM de DODAB, 0,5 mg/mL de CMC e 0,5 mg/mL de PDDA foram obtidas partículas grandes (Dz = 470 nm; ζ = 50 mV). Contra 107 UFC/mL, 1 - 2 µg/mL de PDDA, sozinho em solução ou em forma de partículas, matou 99 % das células de P. aeruginosa. O mesmo ocorreu contra S. aureus (107 UFC/mL) em 10 µg/mL de PDDA. A ação antimicrobiana mostrou-se dependente da quantidade de cargas positivas nas partículas e independente do tamanho da partícula. Filmes de PMMA/ CAQ apresentaram maior molhabilidade do que aqueles de PMMA puro. Filmes de PMMA/ DODAB e PMMA/ TPAB submersos em água não causaram alterações de tensão superficial na interface ar-água, indicando baixa difusibilidade destes CAQs a partir dos filmes. Filmes de PMMA/ CTAB submersos em água reduziram a tensão superficial até aproximadamente 60 mN/m, mostrando a difusibilidade do CTAB no filme e sua organização na interface ar-água. O efeito antimicrobiano dos filmes PMMA/ DODAB e PMMA/ CTAB foi dependente da concentração do CAQ utilizada no preparo do filme. Viabilidade celular de 0% contra 107 UFC/mL de ambas as bactérias ocorreu com 4 mM de DODAB ou, com 2 ou 0,2 mM de CTAB contra P. aeruginosa ou S. aureus, respectivamente. Filmes de PMMA/ TPAB não apresentaram atividade antimicrobiana. Com a emergência de micro-organismos resistentes aos antibióticos, os novos nanomateriais antimicrobianos híbridos de polímeros e compostos de amônio quaternário podem representar uma alternativa de fácil obtenção e baixo custo. / Hybrid particles and films from polymers and quaternary ammonium compounds (QAC) were characterized regarding its physical properties and antimicrobial activity against strains of Pseudomonas aeruginosa ATCC 27853 or Staphylococcus aureus ATCC 25923. Hybrid particles were obtained from dioctadecyldimethylammonium bromide (DODAB) bilayer fragments (BF), consecutively added of carboximethylcellulose (CMC) and poly (diallyldimethylammonium) chloride (PDDA) solutions, and then, characterized by dynamic light-scattering for determination of size distributions, z-average diameter (Dz) and zeta-potential (ζ). Hybrid films were obtained by spin-coating of a chloroformic solution of poly (methylmethacrylate) (PMMA) and QAC on glass coverslips at [PMMA] = 10 mg/mL and [QACs] = 0.03 -4 mM where QACs were DODAB, cetyltrimethylammonium bromide (CTAB) or tetrapropylammonium bromide (TPAB). Films wettability and QACs diffusibility in the films immersed in water were evaluated by determinations of contact angle and surface tension at air-water interface, respectively. Antimicrobial activity was evaluated by plating and CFU counting both for particles and films. For the hybrid films, width of inhibition zone was also determined. DODAB BF/ CMC/ PDDA particles exhibited Dz and ζ dependent on the concentrations of the components. At 0.1 mM DODAB, 0.1 mg/mL CMC, and 0.1 mg/mL PDDA, small cationic particles were obtained (Dz = 100 nm; ζ = 30 mV). At 0.5 mM DODAB, 0.5 mg/mL CMC and 0.5 mg/mL PDDA, large cationic particles were obtained (Dz = 470 nm; ζ = 50 mV). At 107 CFU/mL, cell viability of 1 % for P. aeruginosa was obtained for PDDA in solution or covering particles at 1 or 2 µg/mL PDDA, respectively. Against S. aureus (107 CFU/mL) at 10 µg/mL PDDA, a similar result was obtained. The antimicrobial effect was dependent on the amount of positive charge on particles and independent on particle size. The hybrid films of PMMA/ QAC showed higher wettability than those of pure PMMA. PMMA/ DODAB and PMMA/ TPAB hybrid films, submerged in water, did not cause changes in surface tension at the air-water interface, indicating low diffusibility for both DODAB and TPAB in hybrid films. Films of PMMA/ CTAB, submerged in water, reduced the surface tension to about 60 mN/m, showing that CTAB could diffuse from the film to the air-water interface and change its surface tension. The antimicrobial effect of PMMA/ DODAB and PMMA/ CTAB hybrid films was clearly dependent on the QAC concentration used to prepare the films. Cell viability of 0% for P. aeruginosa and S. aureus (107 CFU/mL) occurred at 4 mM DODAB, or 2 and 0.2 mM CTAB, respectively. Films of PMMA/ TPAB showed no antimicrobial activity. With the emergence of microorganisms resistant to antibiotics, the novel hybrid antimicrobial nanomaterials may become important since they are inexpensive and easy to obtain.

O material Y2O3:Eu3+ vem sendo usado comercialmente como luminóforo vermelho desde da década de 1960, em uma grande variedade de aplicações devido ao seu elevado rendimento quântico (próximo de 100 %), elevada pureza de cor e boa estabilidade. Portanto, este trabalho propõe um novo método de síntese baseado nos complexos benzenotricarboxilatos (BTC) de terras raras trivalentes (RE3+) dopados com íons Eu3+. O objetivo principal é produzir materiais luminescente RE2O3:Eu3+ a temperatura mais baixa (500 °C) e em escala nanométrica. Os complexos precursores [RE(BTC):Eu3+] e [RE(TLA)·n(H2O):Eu3+], onde RE3+: Y, Gd e Lu; BTC: ácido trimésico (TMA) e ácido trimelítico (TLA) foram calcinados em diferentes temperaturas de 500 a 1000 °C, a fim de obter os materiais luminescentes RE2O3:Eu3+. Os complexos foram caracterizados por análise elementar de carbono e hidrogênio, analise térmica (TG), espectroscopia de absorção no infravermelho (FTIR), difração de raios-X - método do pó (XPD) e microscopia eletrônica de varredura (SEM). Todos os complexos são cristalinos e termo estáveis até 460 °C. Dados de fosforescência dos complexos de Y, Gd e Lu mostram que o nível T1 do aníon BTC3- tem energia acima do nível emissor 5D0 do íon Eu3+, indicando que os ligantes podem atuar como sensibilizadores de energia intramolecular. O estudo das propriedades fotoluminescentes dos complexos dopados foi baseado nos espectros de excitação e emissão e curvas de decaimento de luminescência. Ademais, foram determinados os parâmetros de intensidades experimentais (&#937;&#955;), tempos de vida (&#964;), taxas de decaimentos radiativo (Arad) e não-radiativo (Anrad). Os materiais luminescentes RE2O3:Eu3+ foram sintetizados de forma bem sucedida por meio do método benzenotricarboxilatos calcinados a 500, 600, 700, 800, 900 e 1000 °C, apresentando alta homogeneidade química e controle de tamanho de cristalito. Os nanomateriais foram caracterizados pelas técnicas de FTIR, XPD SEM e TEM revelando a obtenção dos materiais C-RE2O3:Eu3+ mesmo a 500 °C. Os dados de XPD dos materiais confirmaram um aumento do tamanho dos cristalitos de 5 até 52 nm (equação de Scherrer) de em função da temperatura de calcinação de 500 a 1000 °C, respectivamente, corroborados pelas técnicas de SEM e TEM. Os espectros de emissão de RE2O3:Eu3+ mostram uma banda larga atribuída a transição interconfiguracional de transferência de carga ligante-metal (LMCT) em 260 nm, i.e. O2-(2p)&#8594Eu3+(4f6). Além disso, foram observadas linhas finas de absorção devido as transições intraconfiguracionais 4f do íon európio (7F0,1&#85945LJ; J: 0, 1, 2, 3 e 4), como esperado. As propriedades fotoluminescentes dos luminóforos foram baseadas nos espectros (excitação e emissão) e curvas de decaimento luminescente. Os parâmetros de intensidade experimental, tempos de vida, assim como as taxas de decaimentos radiativos e não radiativos foram calculados. As propriedades fotônicas dos nanomateriais são consistentes com o sítio de baixa simetria C2 ocupado pelo íon Eu3+ no C-RE2O3:Eu3+, produzindo emissão vermelha dominada pela transição hipersensível 5D0&#85947F2 do íon Eu3+ no sitio C2, ao invés do sítio centrossimétrico S6. Além disso, os nanomateriais Y2O3:Eu3+ exibem características espectroscópicas semelhantes e elevados valores de eficiência quântica (&#951;~91 %), compatível com os luminóforos comerciais disponíveis no mercado. Este novo método pode ser utilizado para o desenvolvimento de novos nanomateriais contendo íons terras raras, assim como outros íons metálicos. / Y2O3:Eu3+ has been used as luminophore since the early 1960s, despite the large variety of potential substitute materials tested so far, this luminophore still be used as commercial red-emission luminescent material in large range of applications due excellent quantum efficiency (close to 100 %), high color purity and good stability. Consequently, This work propose a new benzenetricarboxylate (BTC) method, which use Eu3+ ion doped in the trivalent rare earths (RE3+) complexes to produce RE2O3:Eu3+ luminescent materials at lower temperature (500 °C) and nanoscale. The [RE(BTC):Eu3+] and [RE(TLA)·n(H2O):Eu3+] complexes where RE3+: Y, Gd and Lu; BTC: trimesic acid (TMA) and trimellitic acid (TLA) and annealed materials (500, 600, 700, 800, 900 and 1000 °C) can be obtained without the need of intricate experimental setup. The complexes were characterized by carbon and hydrogen elemental analysis, thermal analyses (TG), infrared absorption spectroscopy (FTIR), X-ray powder diffraction (XPD) and scanning electron microscopy (SEM). The complexes are crystalline and thermostable up to 460°C. Phosphorescence data of the complexes with Y, Gd and Lu show that the T1 state of the BTC3- anion has energy higher than the 5D0 emitting level of the Eu3+ ion, indicating that the ligands can act as an intramolecular energy sensitizer. The photoluminescence properties of the doped complexes were studied based on the excitation and emission spectra and luminescence decay curves. The experimental intensity parameters (&#937;&#955;), lifetimes (&#964;), radiative (Arad) and non-radiative (Anrad) decay rates were determined and discussed. In addition, the RE2O3:Eu3+ nanomaterials were successfully synthesized with this unprecedented method using the benzenetricarboxylate precursor complexes annealed at 500, 600, 700, 800, 900 and 1000 °C, with controllable particle size and high chemical homogeneity, crystallite size from 6 to 52 nm (Scherrer\'s equation), confirmed by SEM and TEM images. The nanomaterials characterized by the FTIR, XPD, SEM and TEM techniques revealed that the C-RE2O3:Eu3+ materials were obtained even at 500 °C. The RE2O3:Eu3+ excitation spectra show a broad absorption band assigned to interconfigurational ligand-to-metal charge-transfer (LMCT) band at 260 nm, i.e. O2-(2p)&#8594;Eu3+(4f6). Besides, it is observed the narrow absorption lines arising from the 4f intraconfigurational transitions of the Eu3+ ion (7F0,1&#8594;5LJ; J : 0, 1, 2, 3 and 4), as expected. The characterization of the photoluminescence properties of the luminophores was also based on the analysis of the emission spectra and luminescence decay curves. The experimental intensity parameters (&#937;&#955;), lifetimes (&#964;), as well as radiative (Arad) and non-radiative (Anrad) decay rates were calculated and discussed. The photonic properties of the luminophores are consistent with the low C2 symmetry site occupied by the Eu3+ ion in the cubic C-type RE2O3:Eu3+, yielding the red emission color, which is dominated by the hypersensitive 5D0&#8594;7F2 transition of the Eu3+ ion in the C2 instead of the centrosymmetric S6 sites. Furthermore, the Y2<O3:Eu3+ nanomaterials prepared by this new method exhibit similar emissions spectral features and high values of emission quantum efficiency (&#951;~91 %), compatible with the commercial phosphors currently available in the market. This novel synthetic method can be used to produce large range of rare earth nanophotonic materials, as well as other metal ions.

O presente estudo teve por objetivo desenvolver metodologias para imobilização de sondas moleculares fluorescentes em matrizes de sílica de tamanho controlado, bem como estudar a interação das sondas livres e imobilizadas com oxigênio e ferro. A classe de fluoróforos escolhida foi a das porfirinas, que apresentam baixa solubilidade em água e têm seu uso limitado, apesar de apresentarem pelo menos duas propriedades interessantes: (i) interagem com oxigênio formando oxigênio singlete, sendo candidatas a drogas para terapia fotodinâmica, e (ii) têm sua fluorescência suprimida ao complexarem metais, podendo atuar como sondas fluorescentes. A imobilização de porfirinas em esferas de sílica de tamanho inferior a 100 nm foi realizada através de um processo sol-gel ou pelo uso de microemulsões. O método sol-gel exigiu a modificação prévia da molécula da porfirina com reagente organosilano e resultou em esferas na faixa de 70 nm. O método da microemulsão dispensou a modificação da porfirina e resultou em esferas na faixa de 30 nm, muito estáveis em água. Os fluoróforos imobilizados preservaram suas propriedades óticas e a sua capacidade de gerar oxigênio singlete. Os estudos envolvendo a detecção de oxigênio singlete foram realizados pelo método físico direto, a partir do registro da fosforescência característica no infravermelho-próximo, e pelo método químico indireto usando a sonda 1,3difenilisobenzofurano. O tempo de vida do oxigênio singlete obtido quando uma suspensão, em acetonitrila, de esferas de sílica carregadas com porfirinas foi excitada em 532 nm foi de 52 &#181;s e está de acordo com o valor determinado para uma solução padrão contendo azul de metileno sob as mesmas condições. As porfirinas imobilizadas em sílica apresentaram eficiência de geração de oxigênio singlete similar ou até superior ao rendimento quântico das porfirinas livres. Após estudos concluiu-se que a elevada geração de oxigênio singlete pode ser atribuída a mudanças no equilíbrio monômero-dímero após a imobilização das porfirinas na matriz de sílica. O emprego das porfirinas imobilizadas em esferas de sílica como sondas fluorescentes para detecção de ferro também foi investigado. Estudos da interação da hematoporfirina IX livre e imobilizada com ferro apresentaram sítios de forte e fraca interação de acordo com a faixa de concentração de ferro utilizada. A supressão da fluorescência da Hp IX livre e imobilizada em sílica obedece a um comportamento linear na faixa de concentração de ferro de 0 a 60 &#181;M. Portanto, a imobilização de porfirinas em nanoesferas de sílica permitiu a dispersão de porfirinas insolúveis em água e manteve as moléculas acessíveis ao oxigênio molecular e aos íons ferro, preservando suas propriedades e ampliando a possibilidade de aplicações. / The present study is focused on developing methodologies for the immobilization of fluorescent molecular probes in size controlled silica matrixes, and studying the interactions of free and entrapped molecules with molecular oxygen and iron. This study was based on porphyrins, a class of compounds with low solubility in water and limited use, but with at least two very interesting properties: (i) interaction with molecular oxygen to yield singlet oxygen, potential drug for use in photodynamic therapy; and (ii) fluorescence quenching by metal ions, potential fluorescent probe. The immobilization of porphyrins in silica spheres of size < 100 nm was achieved by the sol-gel or microemulsion approach. The sol-gel method required the modification of porphyrin molecules with an organosilane reagent and resulted in spheres of about 70 nm. The microemulsion method did not require the modification of porphyrin molecules and resulted in spheres of about 30 nm, very stable in aqueous solution. The immobilized porphyrins preserved their optical properties and the capacity to generate singlet oxygen. Singlet oxygen was detected by a direct method from its characteristic phosphorescence decay curve at near-infrared and by a chemical method using 1,3-diphenylisobenzofuran to trap singlet oxygen. The lifetime of singlet oxygen, when a suspension of porphyrin-loaded silica spheres in acetonitrile was excited at 532 nm, was determined as 52 &#181;s, which is in good agreement with the value determined for a standard methylene blue solution under the same conditions. The porphyrin-loaded silica spheres have an efficiency of singlet oxygen generation similar or even higher than the quantum yield of free porphyrins. This high efficiency of singlet oxygen generation was attributed to changes on the monomer-dimer equilibrium after photosentisizer immobilization in the silica matrix. The use of the immobilized porphyrins as fluorescent probes for iron sensing was also investigated. The interaction of free and silica immobilized hematoporphyrin IX with iron resulted in sites of strong and weak interaction according to the concentration range. The fluorescence quenching of Hp IX, free and immobilized in silica spheres follows a linear correlation with the iron concentration from 0 to 60&#181;M. In conclusion, the immobilization of porphyrins in silica nanoespheres allowed the dispersion of insoluble porphyrins in water, while preserving the accessibility to molecular oxygen and metal ions and broadening the scope of applications.

L'activation de la liaison Csp3-H peu réactive et sa fonctionnalisation en liaison carbone-hétéroatome constituent un défi pour les chimistes de synthèse. Un exemple d'intérêt industriel est la réaction d'oxydation du cyclohexane, dont les produits finaux (cétone et alcool) sont des intermédiaire clés pour la production de polyamides tels que les Nylon-6 et 6,6. Parmi les possibilités d'activation, la catalyse représente une méthode de choix. Dans le cadre de cette thèse des suspensions aqueuses à base de nanoparticules ont été évaluées en termes de stabilité et de performances catalytiques. Dans un premier temps, des colloïdes de ruthénium ont été synthétisés à partir de RuCl3,3H2O et caractérisés par des analyses physico-chimiques (MET, SPX, SAXS, UV-visible, etc.). Des espèces actives de Ru+3 dont la structure est de type Ru(OH)3-xClx ont été obtenues. Après optimisation des conditions de réaction, des conversions élevées, associées à des sélectivités pertinentes vis-à-vis de la cétone (jusqu'à 98%), ont été obtenues. Des études cinétiques et mécanistiques ont montré que la voie radicalaire est prépondérante. De plus, ces colloïdes de Ru aisément recyclables ont également été testés avec succès en oxydation d'autres hydrocarbures saturés et insaturés. Dans un second temps, un catalyseur à base de dioxyde de manganèse, métal moins coûteux et abondant, a été synthétisé par un procédé redox original, à partir de KMnO4 et en présence d'un ammonium quaternaire à tête polaire hydroxylée (HEA16Cl), qui joue simultanément le rôle de réducteur et d'agent stabilisant. Ce système s'est révélé être une alternative pertinente aux procédés à base de métaux nobles. Les nanobâtonnets de MnO2 se sont ainsi montrés actifs en oxydation du cyclooctane avec une sélectivité totale en cétone. / The activation of the Csp3-H bond and its transformation into a carbon-heteroatom bond remains a great challenge for the organic chemistry. An example of industrial application is the oxidation reaction of cyclohexane, leading to the production of the corresponding ketone and alcohol, key intermediates of Nylon-6 and Nylon-6,6 polyamides. Among the strategies to activate this unreactive bond, catalysis affords a relevant and sustainable tool. In this work, aqueous suspensions of metal nanoparticles were evaluated in terms of their stability and catalytic performances. Firstly, ruthenium colloids were synthesized from RuCl3.3H2O and fully characterized by various physico-chemical analyses (TEM, XPS, SAXS, UV-visible, etc.). Ru+3 active species were obtained, with a Ru(OH)3-xClx structure. After optimization of the reaction conditions, high conversions, combined with pertinent selectivities towards the ketone (up to 98%), were achieved. The presence of radical species was proved through kinetic and mechanistic studies. Furthermore, these easily recyclable Ru colloids were also evaluated in the oxidation of several saturated and unsaturated hydrocarbons. Secondly, a catalyst based on manganese dioxide, a cheap and abundant metal, was synthesized by an original redox process, starting from KMnO4 and in the presence of a hydroxylated quaternary ammonium (HEA16Cl), which plays the role of a reducing and stabilizing agent. This system proved to be a relevant alternative to methodologies based on noble metals. The MnO2 nanorods showed a good activity in the cyclooctane oxidation with a 100% selectivity towards the ketone.

The experimental data presented in this thesis demonstrates the preparation and characterization of TiO₂ polymorphs (anatase and TiO₂-(B)) in the form of nanomaterials. The reduced dimension of the nanomaterials amplifies the properties compared to the bulk TiO₂; however, this is often at the cost of the tapped density. The anatase nanomaterials with pseudo-spherical nanoparticles of 5 to 70 nm in size were synthesized and their volumetric capacities compared. Both the gravimetric and volumetric capacity is higher for nanoparticles of less than 10 nm in diameter. The volumetric capacity is also dependent on the agglomerate size. For example at the very lowest rate of 50 mA/g, the agglomerate larger than 50 μm leads to the highest volumetric capacity; while at a rate higher than 600 mA/g the smaller agglomerates are preferred. Following this, we reported the synthesis of mesoporous TiO₂-(B) with the particle size along the [010] direction ranged from 3 to 300 nm, and the pore size increasing from 2.5 to more than 20 nm. By comparing the volumetric capacity of these TiO₂-(B) mesoporous materials, the optimal morphology for an improved volumetric capacity was identified. TiO₂-(B) with a novel microstructure was synthesized via a hydrothermal reaction. The primary particles are brick-like in shape with the shorter dimensions (4 - 10 nm) in parallel to the [100] and [010] directions, facilitating the Li⁺ ion diffusion in the particle. This TiO₂-(B) offers a superior rate capability compared to many other titanate anodes reported in the literature. In addition, it exhibits a great cycleability due to its exceptional structural stability and minimal SEI layer. Surface treatments could reduce its first cycle irreversible capacity to ~10%.

Nos travaux concernent la synthèse et la caractérisation d'oxydes dopés par la méthode d'électrodéposition sous champ magnétique.L'enjeu d'une telle recherche est double puisqu'il associe une étude de synthèses électrochimiques et l'obtention de matériaux associant des propriétés semi-conductrices et magnétiques.Les oxydes étudiés sont l'oxyde de cuivre (I) dopé par le manganèse ou par le cobalt, et l'oxyde de zinc dopé par le cuivre.Notre objectif est l'élaboration sous champ magnétique d'oxydes de type DMS (semi-conducteurs magnétiques dilués), et leurs caractérisations physiques et chimiques.En effet, l'addition du dopage et celui du champ magnétique appliqué pendant l'électrodéposition génèrent des effets sur les matériaux électrodéposés.Nous avons ainsi mis en évidence des modifications au niveau de la morphologie, de la texture, de la composition, et des propriétés optiques ou magnétiques des matériaux obtenus. / Our work focuses on the synthesis and characterization of doped oxides by electrodeposition method under magnetic field superimposition.The goal of this research presents two challenges, because it combines a study of electrochemical synthesis and obtaining materials with optical and magnetic properties. The materials which have been studied are manganese or cobalt doped copper (I) oxide on the one hand, and the copper doped zinc oxide in the other hand.Our goal is the elaboration of diluted magnetic oxides, and the study of their physical and chemical characterizations.Indeed, the effects of doping and of the magnetic field applied during the electrodeposition can provide interesting changes in morphology, texture, composition and optical and magnetic properties of the obtained materials.

This is the first study comparing morphologies of CNT films on Kanthal wire, with their field emission properties, and as such offers ways to design better cylindrical emitter devices. A low turn-on field was achieved (0.35 V/µm), the field emission results have been explained using a simple model, and a fluorescent lamp was fabricated. Whilst previous work has been done on the link between “as grown” CNT films and their respective field emission properties on flat substrates, very little work has been done on linking morphology to emission performance on wire substrates, where the morphology can be very different. Microscopic structures such as towers, ridges and clumps consisting of many aligned or entangled CNTs were grown using an aerosol chemical vapour deposition (a-CVD) technique. Hydrogen added to the carrier gas resulted in a decrease in defect density in the growth of undoped CNTs, and an increase in defect density in the growth of nitrogen doped CNTs (N-CNTs) and boron doped CNTs (BCNTs). In-situ transmission electron microscopy (TEM) studies show that damage to CNT tips results in a significantly higher turn-on field compared to undamaged tips. This can be recovered by making the CNT emit current for several minutes which makes the tip recrystallize due to heat caused by the Nottingham effect. The field emission properties of the “as grown” CNT films are dominated by protruding CNTs found at the edges of ridge and tower microscopic structures. The field emission properties are also related to the dimensions of these structures with the longest ridges (hence those with the longest protruding CNTs) resulting in the lowest turn-on electric field. The ridge and tower structures act to accommodate protruding CNTs at their edges and their physical dimensions (mainly width) act to separate these emitters so that screening is minimised. This work shows that efficient emitters can be fabricated effectively from simple a-CVD techniques and microscopic structures act to improve, not degrade, field emission properties.

Electronic Excitation Energy Transfer is an important intermolecular photophysical process that can affect the excited state lifetime of a chromophore. A molecule in an electronically excited state can return to the ground state by radiative as well as non-radiative processes. During the excited state lifetime, if the chromophore (energy donor) finds a suitable species (energy acceptor) nearby with resonant energy levels, it can transfer the excitation energy to that species and return to the ground state. This process is called Electronic Excitation Energy Transfer. When the energy donor is fluorescent, the process is called Fluorescence Resonance Energy Transfer (FRET) [1]. FRET is a non-radiative process that affects the fluorescence intensity as well as the excited state lifetime of the donor. It occurs due to the electrostatic coulombic interaction between the transition charge densities of the donor and the acceptor. The rate of energy transfer can be evaluated using the Fermi golden rule of quantum mechanics [2]. When the donor and the acceptor are separated by distances that are much larger in comparison with the sizes of the donor and the acceptor, the interaction between them can be thought of as that between their transition dipoles. In such a case, the interaction between the donor and the acceptor is dipolar and the rate of energy transfer has an R−6 dependence, where R is the distance between the donor and the acceptor [3]. This dependence has first been suggested theoretically by Forster in 1947 [4] followed by the experimental verification by Stryer and Haugland [5]. Since then the process has been used as a spectroscopic ruler to study the conformational dynamics of biopolymers like DNA, RNA, proteins etc [6]. A variety of dye molecules have been explored for donors and acceptors in FRET and the range of distances that can be measured using FRET involving dyes is in the range 1 − 10 nm. When the distances between the donor and the acceptor are not much larger in comparison with their sizes, the dipolar approximation to the interaction is not a very good approximation, thereby leading to deviations from the traditional R-6 dependence. Such non-R-6dependencies are found for polymers, quantum wells, quantum wires etc [7–9]. The interest in such dependencies is due to the need for developing nanoscopic rulers that can measure distances well beyond 10 nm. The objective of our work has been to study energy transfer from fluorophores to various kinds of acceptors that have extended charge densities and understand the distance dependence of the rate of energy transfer [10]. We use the Fermi golden rule as the starting point and develop analytical models for evaluating the rate as a function of the distance between the donor and the acceptor. We study the process of energy transfer from fluorescent dye molecules that serve as energy donors to a variety of energy acceptors namely, graphene, doped graphene, single-walled carbon nanotubes and metal nanoparticles. We also study transfer from fluorophores to a semiconducting sheet and a semiconducting tube of electronic charge density. There have been experimental studies in the literature of the fluorescence quenching of dyes near single-walled carbon nanotubes [11–13]. But, there are no studies of the distance dependence of rate. Single-walled carbon nanotubes can be thought of as rolled up sheets of graphene. However, interestingly, there were no reports of fluorescence quenching by graphene at the time when we thought of this possibility. Therefore, we first study the process of energy transfer from a fluorophore, which is kept at a distance z above a layer of graphene to the electronic energy levels of graphene. We find that the long range behavior of the rate has an z -4 dependence on the distance [14, 15]. From our study of transfer from pyrene to graphene, we find that fluorescence quenching can be experimentally observed up to a distance of ~ 30 nm, which is quite large in comparison with the traditional FRET limit (10 nm). Recent experiments that have been performed after our theory was reported have in fact observed the fluorescence quenching of dyes near graphene. Further, the process has been found to be very useful in fabricating devices based on graphene [16], in eliminating fluorescence signals in resonance Raman spectroscopy [17] and in visualizing graphene based sheets using fluorescence quenching microscopy [18]. The process has also been found to be useful in quantitative DNA analysis [19, 20]. We study the transfer of an amount of energy hΩ from a dye molecule to doped graphene [21]. We consider the shift of the Fermi level from the K-point into the conduction band of graphene as a result of doping and evaluate the rate of transfer. We find a crossover of the distance dependence of the rate from z -4 to exponential as the Fermi level is increasingly shifted into the conduction band, with the crossover occurring at a shift of the Fermi level by an amount hΩ/2. We study the process of transfer of excitation energy from a fluorophore kept at a distance d away from the surface of a carbon nanotube to the electronic energy levels of the nanotube. We find both exponential and d−5 behavior of the rate [22]. For the case of metallic nanotubes, when the emission energy of the fluorophore is less than a threshold, the dependence is exponential. Otherwise, it is d−5 . For the case of semiconducting nanotubes, we find that the rate follows an exponential dependence if the amount of energy that is transferred can cause only the excitonic transition of the tube. However, if any other band gap transition is allowed, the rate follows a d−5 dependence. For the case of transfer from pyrene to a (6, 4) nanotube, we find that energy transfer is appreciable up to a distance of ~ 17 nm. We then study the process of energy transfer from a fluorophore to a semiconducting sheet of electronic charge density [10]. We find that the rate has an z-4 dependence. For the case of transfer to a semiconducting tube, we find that the rate has a d -5dependence. The dependencies are in agreement with those obtained for graphene and carbon nanotubes respectively. This shows that the asymptotic distance dependencies are a consequence of the dimensionality of the transition charge densities and are robust. Strouse et al. [23, 24] have studied the process of energy transfer from the dye fluorescein to a 1.4 nm diameter gold nanoparticle. Double-stranded DNA molecules of various lengths were used to fix the distances between the donor and the acceptor. The rate was found to have a d-4distance dependence. They refer to this process as Nanoparticle Surface Energy Transfer (NSET) and the range of distances that can be measured using NSET is more than double that of the traditional FRET experiments. However, theoretical studies that consider the transfer to the plasmonic modes of the nanoparticle find a predominant R-6 dependence [25]. We study the process of energy transfer from the dye fluorescein to a 1.4 nm diameter gold nanoparticle considering the excitation of plasmons as well as electron-hole pairs of the nanoparticle [26]. We find that the rate follows the usual Forster type R−6 distance dependence at large distances. But, at short distances, there are contributions of the form R−-n with n > 6. This is due to the quadrupolar and octupolar modes of excitation of the nanoparticle, the rates corresponding to which have R-8 and R−-10 dependencies respectively. Recent calculations using DFT also find similar deviations at short distances [27].

De nouveaux matériaux π-conjugués fonctionnels ont été élaborés selon deux approches. La première a consisté à préparer des molécules π-conjuguées fonctionnelles – basées sur un segment central de type 1,4-bis(phénylène-éthynyl)benzène – permettant de développer des nano-objets et des nanomatériaux hybrides associant les segments conjugués organiques à d'autres composantes : des nanotubes de carbone et de la silice sous la forme de nanoparticules ou de nanomatériaux. Le segment conjugué de base a été fonctionnalisé soit directement, soit par le biais de ses chaînes solubilisantes. La seconde approche a permis de développer une nouvelle famille d'oligomères conjugués organiques et solubles – basés sur des motifs de type thiénopyrazine – de faible gap énergétique entre les orbitales HOMO et LUMO. Les propriétés électro-optiques de ces composés exclusivement organiques ont été confrontées à des calculs prédictifs obtenus par des méthodes de la chimie théorique (DFT, TDFFT). Ces matériaux hybrides fonctionnels ont pu être valorisés. La fonctionnalisation des chaînes solubilisantes par des groupements ioniques imidazolium ont permis la conception de nouveaux matériaux polyélectrolytes pour accéder à des ionogels. La fonctionnalisation du segment conjugué en lui-même a pu être mis à profit pour la fonctionnalisation covalente de nanotubes de carbone ou de nanoparticules de silice. / New π-conjugated functional materials were elaborated in two ways. The first one consisted in the preparation of π-conjugated functional molecules – based on a 1,4-bis(phenylene-ethynyl)benzene central segment – in order to develop hybrid nano-objects and nanomaterials which combine organic conjugated segments with other components : carbon nanotubes or silica (nanoparticules, nanomaterials). The central conjugated unit is functionalized either on this π-conjugated system or at the end of the side chains. The second approach allows the development of a new family of organic soluble conjugated oligomers – based on thienopyrazine units – characterized by a low band gap between HOMO and LUMO orbitals. The electronic and optic properties of these organic compounds were compared to theoretical calculations (DFT, TDFFT). The functionalization of the side chains by ionic imidazolium units could permit the conception of new polyelectrolyte materials and open the access to new ionogel materials. The functionalization of the conjugated segment was used with advantage for the covalent functionalization of carbon nanotubes or silica nanoparticules.