Neste trabalho, estudamos as propriedade ópticas da tetrapiridilporfirina (TPyP), usando clorofórmio como sol vente. Para a caracterização óptica linear foram medidos os espectros de fluorescência e absorbância, tendo este último nos permitido determinar a seção de choque para o estado fundamental com radiação incidente em 532 nm. Usamos a técnica de varredura Z com trem de pulsos (VZTP) para medirmos a absorção não linear da TPyP, em 532 nm, e determinamos, através de um modelo fenomenológico de cinco níveis, vários parâmetros espectroscópicos tais como seções de choques e tempos de vida dos estados. Além disso, com a utilização da técnica de espalhamento hiperRayleigh (HRS) medimos a primeira hiperpolarizabilidade da TPyP, dissolvida em clorofórmio em 1064 nm usando, como material de referência, a p-nitroanilina (PN A), diluída em metanol. / This work reports on the optical properties of the tetrakis(pyridil)porphyrin (TPyP). In order to perform the linear optical characterization, fluorescence and absorbance spectra were obtained, where the latter allowed the determination of the cross-section for the ground state with incident radiation at À = 532 nm. We used the Zscan tecnique with pulse trains (ZSPT) to measure the nonlinear absorption of TPyP, at 532 nm, and we managed to determine, through a phenomenological five levels model, several spectroscopic parameters such as cross-sections and lifetime of the states. Moreover, we measured the first hyperpolarizability of TPyP dissolved in chloroform, at À = 1064 nm, using the Hyper-Rayleigh scattering (HRS) technique. The reference material used for HRS measurements was p-nitroaniline (PNA) dissolved in methanol.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Porphyrins are very attractive system to study self-assembly due to its basic structure, chemical and thermal stability, synthetic versatility and important technological applications. This work presents the development of self-assembled systems meso-porphyrin derived from cardanol, the major constituent of the LCC. We were developed Langmuir and Langmuir-Blodgett (LB) thin films and superparamagnetic nanosystems coated with meso-porphyrin. The Langmuir films showed molecular area mean of the 177 à 2 confirmed by compressibility modulus. The 700 nm band observed in the Langmuir films supports the coexistence of monomers and dimers similar to the spectra of the solution (CHCl3/CH3COOH). The Brewster angle microscopy measurements showed formation of bright block domains with different sizes and shapes for the monolayer that disappears after surface pressure starts to increase. The UVâvis spectra of the Langmuir films and FTIR reflection of the LangmuirâBlodgett films (LB) indicated that the molecules exhibit preferential orientation with the parallel planes to the water (Langmuir) and in the substrate (LB). The LB film of 5 layers showed better response as electrode and has been tested as a promethazine sensor. Magnetic Fe 3 O 4 nanoparticles with an average size of 11 nm were coated with oleic acid layer and a meso-porphyrin layer to producing a novel superparamagnetic fluorescent nanosystem. Also were obtained systems coated with meso-porphyrins metallated with Co2+, Ni2+, Cu2+ and Zn2+ ions. The systems were characterized by TEM, FT-IR, TGA, vibrating sample magnetometry, UV-Vis, fluorescence and confocal miscroscopy. The systems showed good thermal stability, excellent magnetization and nanosized dimensions. / Porfirinas sÃo sistemas muito atrativos para estudos de automontagem graÃas a suaestrutura ba se, estabilidadequÃmica e tÃrmica, versatilidade sintÃtica e importantes aplicaÃÃes tecnolÃgicas. Este trabalho tem por finalidade apresentar o desenvolvimento de sistemas automontados da meso-porfirina derivada do cardanol, constituinte majoritÃrio do LCC. Foram desenvolvidos filmes finos de Langmuir e Langmuir-Blodgett (LB) e aplicado como sensor eletroquÃmico para prometazina e nanossistemas superparamagnÃticos revestidos com a meso-porfirina. Os filmes de Langmuir apresentaram Ãrea molecular mÃdia de 177 à 2 , confirmado pelo mÃdulo de compressibilidade. A banda centrada em λ = 700 nm observados nos filmes suporta a coexistÃncia de monÃmeros e dÃmeros semelhantes aos espectros em soluÃÃo de CHCl3/CH3COOH. A microscopia do Ãngulo de Brewster mostrou domÃnios com blocos brilhantes de diferentes tamanhos e formas para a monocamada que desapareceram apÃs o aumento da pressÃo de superfÃcie. Os espectros de UV-vis dos filmes e FT-IR no modo reflexÃo dos filmes de Langmuir-Blodgett (LB) indicaram que as molÃculas apresentam orientaÃÃo preferencial com os planos paralelos à Ãgua (no Langmuir) e no substrato (LB). O filme LB de 5 camadas apresentou melhor resposta como eletrodo e foi testado como um sensor de prometazina. As nanopartÃculas magnÃticas de Fe 3 O 4 com tamanho mÃdio de 11 nm foram revestidos com uma camada de Ãcido oleico seguido da meso-porfirina produzindo um novo nanossistema superparamagnÃtico fluorescente. Foram obtidos tambÃm os sistemas revestidos com porfirinas metaladas com os Ãons Co2+, Ni2+, Cu2+ e Zn2+, os quais foram caracterizados por MET, FT-IR, anÃlise termogravimÃtrica, magnetometria de amostra vibrante, UV-Vis, emissÃo de fluorescÃncia e miscroscopia confocal. Os resultados mostraram que os sistemas apresentaram boa estabilidade tÃrmica, comportamento superparamagnÃtico e dimensÃes nanomÃtricas.

Neste trabalho, foram estudadas a oxidação do cicloexano e a epoxidação do (Z)- cicloocteno com iodosilbenzeno (PhIO) e H2O2 como oxidantes, comparando as FeIIIclorinas pentafluorossubstituídas com as FeIIIporfirinas, [Fe(TFPCMG)]Cl, [Fe(TFPCMGCH3)]Cl2, [Fe(TFPP)]Cl e [Fe(TF4TMAPP)](CF3SO3)5 como catalisadores em meio homogêneo e suportadas via ligação iônica e/ou covalente em matrizes de sílica quimicamente modificada. No caso do substrato (Z)-cicloocteno, os metalocomplexos utilizados levaram a rendimentos elevados para formação do ciclooctenóxido, tanto em meio homogêneo quanto heterogêneo, quando PhIO foi utilizado como oxidante. A atividade catalítica foi mantida mesmo após três reciclagens sucessivas. Com o H2O2 como oxidante, os rendimentos foram menores exceto com o metanol, quando se observa um aumento nos rendimentos de epoxidação, porque favorece a formação do intermediário ativo FeIIIhidroperóxido. Já os sistemas heterogeneizados apresentam desempenho bastante inferior quando comparado aos catalisadores em solução. Os melhores rendimentos foram observados com DCE um solvente mais viscoso que aumenta o tempo de vida da gaiola do solvente favorecendo o processo biomimético. Os catalisadores imobilizados foram caracterizados por espectroscopias UV-Vis e de RPE. Estas técnicas deram informações do estado de oxidação e de spin do metal, bem como a geometria do macrociclo na superfície da matriz sólida. Os resultados catalíticos puderam ser explicados pela natureza dos grupos funcionais que ligam o metalocomplexo à sílica, bem como, pelas informações fornecidas pela técnica de RPE quanto ao estado de oxidação do ferro e à geometria dos metalocomplexos imobilizados, dando consistência aos mecanismos propostos nos processos de oxidação. / In this work, the cyclohexane oxidation and the (Z)-cyclooctene epoxidation with iodosylbenzene (PhIO) e H2O2 as oxidants were studied. A comparison between fluorinated FeIIIchlorins and FeIIIporphyrins, [Fe(TFPCMG)]Cl, [Fe(TFPCMGCH3)]Cl2, [Fe(TFPP)]Cl, [Fe(TF4TMAPP)](CF3SO3)5 as catalysts was made either in solution or supported in silica matrices via eletrostatic interaction and/or covalent bonds. In the case of (Z)-cyclooctene epoxidation by PhIO, all the studied metallocomplexes achieved high yields for the epoxide production in both homogeneous and heterogeneous systems. The catalytic activity was maintained even after three successive recyclings. On the other hand, when H2O2 was used as oxidant the yields were lower. Differently, raised yields of epoxidation were observed when using methanol as solvent due to favored formation of the active intermediate FeIIIhydroperoxide. The performance of the heterogeneous systems was significantly lower than that of the catalysts in solution. The best yields were observed with DCE, a viscous solvent that probably raises the shelf life of the solvent cage favoring the biomimetic process. The supported systems were characterized by EPR and UV-Vis spectroscopies. These techniques gave information about the oxidation state and the metal spin, as well as the macrocycle geometry on the solid matrix surface. The catalytic results were explained by the nature of the functional groups that bound the metallocomplex to the silica matrix. In addition, the information obtained by the EPR technique regarding the state of oxidation of iron and the geometry of the supported metallocomplexes gave consistence to the proposed mechanisms in the oxidation processes.

Devido à sua intensa absorção de luz na região visível do espectro, as porfirinas e seus derivados (clorinas e bacterioclorinas) são de grande importância na terapia fotodinâmica (TFD) para o tratamento de doenças neoplásicas. Neste trabalho foram sintetizadas as novas vinil-porfirinas estrategicamente funcionalizadas (47 e 48), seguida de uma sistemática de reações de Diels-Alder com dieófilos ativados, com o propósito de obter clorinas e/ou bacterioclorinas para potenciais aplicações em TFD. / Due to their strong absorption in the visible region, porphyrins and related derivatives (chlorins and bacteriochlorins) are very important in photodynamic therapy (PDT) for the treatment of neoplasic diseases. In this work were synthesized the novel and strategically functionalizated vinyl-porphyrins 47 and 48, followed by systematic Diels-Alder reactions with activated dienophiles to obtain chlorins and/or bacteriochlorins, potentially useful on PDT.

Processos que envolvem sensibilização são extremamente importantes para diversas áreas do conhecimento, incluindo a biologia, a química e a medicina. A aplicação de sensibilização em medicina tem se destacado, especialmente, em face de uma modalidade alternativa de tratamento de câncer denominada terapia fotodinâmica (TFD). Uma das linhas de pesquisas fundamentais para a evolução da terapia fotodinâmica é o desenvolvimento de novos fotossensibilizadores (Fs) com composição definida, que absorvam na janela terapêutica (600- 800nm) e que apresentem maior eficiência na indução de apoptose. Os Fs que apresentam cargas positivas e que são relativamente lipofílicos, permeiam membranas e são atraídos pelo potencial negativo das mitocôndrias, que tem papel central no controle da vida e da morte celular. Neste trabalho foi realizado um estudo da influência dos grupos funcionais na atividade dos Fs, através da funcionalização da protoporfirina IX (Pp IX). Foram estudadas três diferentes rotas sintéticas. Na rota I (esquema 14), utilizou-se como composto de partida a Hematoporfina IX (Hp IX), a qual foi funcionalizada com grupos aminas e amidas, respectivamente, nas hidroxilas e nas carboxilas. Esta rota forneceu baixo rendimento global (20%), e compostos de difícil purificação, no entanto obteve-se 1 composto puro. Na rota II (esquema 15), utilizou-se como composto de partida a Pp IX, a qual foi funcionalizada nos grupos vinílicos com grupos aminas. Obteve-se 4 compostos, com rendimento global de reação superior a 50%, mas observou-se que ocorre uma reação de eliminação que impede a quartenarização das aminas localizadas nas posições α ao anel porfirínico. Na rota III (esquema 16), os grupos carboxílicos de Pp IX foram transformados em cloreto de ácido, que foram substituídos por compostos bifuncionais, amina primária e um segundo grupo. Esta rota possibilitou a obtenção de 7 compostos, inclusive compostos quaternários com rendimento global de reação superior a 70%. Dois derivados da clorofilina, que apresentam a banda QIV com um ε elevado em 650nm, foram também sintetizados. Todos os compostos, foram caracterizados estruturalmente de forma inequívoca através do espectro eletrônico (UV-vis e fluorescência), vibracional no infravermelho, RMN de 1H e 13C (1D e 2D) e espectrometria de massa. A série de compostos obtidos permitiu um estudo da relação entre a estrutura química do Fs com a sua fotoatividade. As propriedades fotofísicas foram caracterizadas por espectro de absorção e de emissão, fotólise de relâmpago a laser, eficiência quântica de fluorescência e de geração de oxigênio singlete. Estas determinações indicaram que as propriedades fotofísicas dos Fs não foram consideravelmente alteradas no processo sintético. Foi determinada a formação de agregados em solução aquosa e o equilíbrio monômero agregado foi deslocado no sentido da formação do monômero na presença de micelas de CTAB e SDS e de soro fetal. Observou-se, que a contribuição para desagregação é mais eficiente quando a carga da micela é oposta à do Fs. Foi determinado o coeficiente de partição octanol/água (logPo/a) em função do pH e constatou-se que os compostos que têm carga líquida apresentam valores de logPo/a entre -1 e 1 na faixa de pH entre 3 e 10. A incorporação destes compostos em lipossomos, seguiu perfil esperado considerando a carga, o logPo/a e a característica anfifílica dos compostos sintetizadas. Genericamente a eficiência de morte celular fotoinduzida seguiu o perfil de incorporação das drogas em células HeLa. Os estudos comparativos da citolocalização foram realizados por co-encubação das porfirinas sintetizadas com rodamina 123 (Rd), que se concentra em mitocôndrias. A localização em organelas citoplasmáticas foi determinada através de imagens obtidas por microscopia de fluorescência confocal. A sobreposição da emissão da Rd foi de 80% e 31% com o composto catiônico PpNpNI e aniônico PpNetPO3, respectivamente, comprovando a localização mitocondrial do composto positivo. / Processes that involve sensitization are extremely important for several areas of knowledge, including biology, chemistry and medicine. The application of sensitization in medicine is especially important, in face of an alternative modality of cancer treatment called Photodynamic Therapy (PDT). One of the lines of basic research important for the evolution of PDT is the development of new photosensitizers (PS) with defined composition, that absorb in the therapeutical window (600-800nm) and that present greater efficiency in the induction of apoptosis. Positively charged PS with the proper lipophilic/hidrophilic balance permeate membranes and are attracted by the negative potential of mitochondria, which is an organelle that has central roles in the control of cell life and death. In this work the influence of the functional groups in the activity of PS was carried out, through the functionalization of protoporphyrin IX (Pp IX). Three different synthetic routes were used. In route I (scheme 14), Hematoporphyrin IX (Hp IX), was used as departure compound and it was modified with amino and amide groups in hydroxyls and carboxyls, respectively. We found low yield in the synthetic (20%) and purification steps. However 1 pure PS was obtained. In route II (scheme 15), Pp IX was used as departure compound, which was modified in the vinilic groups with amino groups. We obtained 4 compounds, with global yield superior than 50%, but it was observed that an elimination reaction occurs that hinders the quarternization of the amino groups located in position α to the porphyrin ring. Into route III (scheme 16), the carboxilic groups of Pp IX had been transformed into chloride acid, which was substituted by bi- functional groups, primary amine in one side and another group in the other. This route made it possible to obtain 7 compounds, including quaternary ammonium compounds with global yield superior than 70%. Two derivatives of chlorophyllin, that present QIV band with large extinction coefficient in 650nm, also were synthesized. All compounds were characterized structurally through the electronic and vibrational spectra (UV-vis and fluorescence, IR), RMN of 1H and 13C (1D and 2D) and mass spectrometry. This series of compounds allowed us to study the relation between the chemical structure of the Fs with its photoactivity. The photophysical properties were characterized by emission and absorption spectra, laser flash photolysis, fluorescence emission in the visible and NIR regions (generation of singlet oxygen). These determinations indicated that the photophysical properties of the PS were not modified in the synthetic process. The formation of aggregates were characterized in aqueous solution and the balance between aggregate and monomer species was dislocated in the direction of the formation of monomers in the presence of CTAB, SDS micelles and fetal serum. It was observed, that the disaggregating efficient is larger with micelles that have the opposite charges to that of the PS. The Octanol water partition coefficient (logPo/a), was determined as a function of pH. logPo/a values between -1 and 1 were observed for charged PS in the pH range of 3-10. The incorporation of these compounds in liposomes, followed the expected profile considering the charge, logPo/a and the amphifilic nature. Generically, the photoinduced cell death efficiency followed the profile of incorporation of the PS in HeLa cells. Comparative studies of cytolocalization were carried out by co-incubation of the cells with porphyrins and Rhodamine 123 (Rd), which localizes in mitochondria. The localization in cytoplasmic organelles was determined through fluorescence confocal microscopy images. The overlapping emission of the Rd was of 80% and 31% with the cationic PpNpNI and the anionic PpNetPO3 compounds, respectively, proving the mitochondrial localization of the positive PS.

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No. of bitstreams: 1 leonardoaparecidodesouza.pdf: 3898214 bytes, checksum: c399d46a865d8df8a5d46b3a56175bfc (MD5) Previous issue date: 2011-03-22 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, métodos da mecânica quântica foram aplicados na investigação das propriedades estruturais e ópticas não-lineares (ONL) de moléculas de porfirina (P) e tetrafenilporfirina (TFP), além dos sistemas híbridos formados por diferentes derivados porfirínicos (ZnP, H2P, ZnP-pp e H2P-pp) adsorvidos sobre a superfície de um nanotubo de carbono de parede simples (SWNT) a(5,5). Todas as geometrias moleculares foram calculadas usando a Teoria do Funcional da Densidade (DFT) e a primeira hiperpolarizabilidade β foi calculada no nível Hartree-Fock (HF). Primeiramente, foram avaliados os aspectos estruturais de sessenta e quatro moléculas de porfirinas e tetrafenilporfirinas complexadas com Zn(II) (ZnP e ZnTFP) ou na forma protonada (H2P e H2TFP), modificadas por substituintes ligados diretamente ao anel macrociclotetrapirrólico. Menores distorções dos anéis de porfirinas e tetrafenilporfirinas foram encontradas quando havia o radical espaçador etinil (et) entre os grupos doador-receptor de elétrons, NH2 e NO2, respectivamente. A primeira hiperpolarizabilidade média para as moléculas foi calculada e valores de β mais intensificados foram encontrados para as porfirinas e tetrafenilporfirinas contendo ligantes do tipo push-pull, destacando-se aquelas que contêm em suas estruturas o grupo espaçador etinil. A segunda parte deste trabalho envolveu o estudo da estrutura, estabilidade e propriedade ONL de uma série de complexos porfirina-nanotubo (ZnPSWNT, H2P-SWNT, ZnP-pp-SWNT e H2P-pp-SWNT). Os resultados indicaram que a estabilidade dos complexos está diretamente relacionada com a presença do metal Zn(II), além disso, os grupos push-pull também contribuem para a estabilidade. A partir dos valores médios da energia de estabilização da série de isômeros, foi estabelecida a seguinte ordem de estabilidade: ZnP-pp-SWNT > ZnP-SWNT ~ H2P-pp-SWNT > H2PSWNT. A funcionalização dos nanotubos de carbono com porfirinas intensificam a propriedade ONL calculada. O valor de β aumenta significativamente quando o SWNT é funcionalizado com as moléculas de H2P-pp e ZnP-pp se comparado com as porfirinas livres. Os resultados obtidos nesta dissertação indicam que nanocompostos híbridos, tais como os representados por H2P-pp-SWNT e ZnP-pp-SWNT, podem representar uma importante alternativa na proposição de novos materiais de interesse que apresentam respostas ONL. / In this work, quantum mechanical methods were applied to investigate the structural and nonlinear optical (NLO) properties of porphyrin (P) and tetraphenylporphyrin (TFP) molecules, as well as hybrid systems formed by different porphyrin derivatives (ZnP, H2P, ZnP-pp and H2P-pp) adsorbed on the surface of a single-walled carbon nanotube (SWNT) a(5,5). The molecular geometries were calculated using Density Functional Theory (DFT) and the first hyperpolarizability was calculated at the Hartree-Fock (HF) level. Firstly, the structural aspects of sixty four porphyrin and tetraphenylporphyrin molecules complexed with Zn (II) (ZnP and ZnTFP) or in the protonated form (H2P and H2TFP), modified by substituents bound directly to the macrociclotetrapirrólico ring were evaluated. The smallest distortions of the porphyrin and tetraphenylporphyrin ring were found when the bridge group was the ethynyl radical (et) conecting the electron donor and acceptor groups, NH2 and NO2, respectively. The average first hyperpolarizability for these molecules was calculated and β values were larger for porphyrins and tetraphenylporphyrin containing push-pull ligands type, especially those that contain in their structures the ethynyl linker. The second part of this work involved the study of structure, stability and NLO property of a series of porphyrin-nanotube complex (ZnP-SWNT, H2P-SWNT, ZnP-pp-SWNT and H2P -pp-SWNT). The results indicated that the stability of the complexes is directly related to the presence of Zn(II) ion, in addition, the push-pull groups also contribute to the overall stability. By taking the average stabilization energy throughout the series of isomers, the following stability order was established: ZnP-pp-SWNT>ZnPSWNT~H2P-pp-SWNT>H2P-SWNT. The carbon nanotubes functionalization with porphyrins enhance the ONL response. The β values increase significantly when the SWNT is functionalized with the H2P-pp and ZnP-pp molecules if compared to the free porphyrins. The results obtained in this work indicate that hybrid nanocomposites, such as those represented by H2P-pp-SWNT and ZnP-pp-SWNT, might be an important alternative to the proposition of interesting new materials with ONL responses.

La recherche présentée dans cette thèse traite de la synthèse, propriétés et applications optoélectroniques de matériaux nanohybrides basés sur le greffage d’une porphyrine donneur d’électron et d’un dérivé du fullerène sur des nanoparticules de ZnO.Ces molécules sont accrochées à la surface de l’oxyde métallique grâce à une fonction acide carboxylique. L'effet du rapport molaire porphyrine / fullerène, de la polarité du solvant et la forme des nanoparticules sur les propriétés optiques des nanohybrides ont été étudiés. Les interactions porphyrine / fullerène à l’échelle moléculaire apparaissent pour un rapport de 1:2 à l'état co-greffé sur des nanobâtonnets de ZnO. Cela est indiqué par le fort décalage bathochrome du pic de Soret des porphyrines et de l’extinction de sonémission de fluorescence. Toutefois, à cette valeur du rapport, le complexe de transfert de charge n'est pas détectable. La formation de ce complexe requiert à la fois les molécules donneur et accepteur d’électron d'être d’être maintenues à proximité, ce qui est réalisableen augmentant le rapport stoechiométrique à 1:3 et au-delà. Dans l’acétonitrile, une bande d’absorption de transfert de charge de faible intensité apparaît vers 700-800 nm, ainsi qu’une bande d'émission à 800 nm, caractérisant la complexation supramoléculaire à la surface de l’oxyde métallique. Lorsqu'ils sont utilisés pour la fabrication de la couche active dans une cellule solaire à hétérojonction hybride, les nanobâtonnets de ZnO fonctionnalisés montrent une efficacité de conversion lumineuse pour des valeurs faibles du rapport porphyrine / fullerène, mais l’augmentation du taux de fullerène tend à diminuer le rendement de conversion photovoltaïque. Cet effet a été relié à l’apparition de défauts morphologiques dans les films minces induite par l’agrégation des nanotubeslié au taux et rapport de greffage des molécules organiques. / The research presented in this dissertation deals with the synthesis, properties andoptoelectronic applications of the nanohybrids based on dye and fullerene functionalizedZnO nanoparticles. These molecules being acid functionalized, were co-grafted on thesurface of ZnO nanoparticles. The effect of changing ratio of donor to acceptor, polarityof the solvent and shapes of the nanoparticles on porphyrin/fullerene interaction werestudied. The molecules were found appreciably interacting at a ratio of 1:2 under the cograftedstate on ZnO nanorods. This was indicated by the strong bathochromic shift of thesoret peak of porphyrin and quenching of its fluorescence however, at this ratio chargetransfer complex is not detectable. The complex formation requires both the donors andacceptors to be enough close to each other to undergo Van der Waal’s type interactionwhich is achievable by raising the stoichiometric ratio to 1:3 and beyond. Weak CTabsorption (700-800 nm) and emission bands (800 nm) characterizing supramolecularcomplexation, were noticed only in polar solvent acetonitrile. When applied as acomponent of the active layer in bulk heterojunction hybrid solar cells, the dyefunctionalized ZnO nanoprods raised the efficiency of the solar cells at lowconcentrations but addition of fullerene had an inverse effect. This was investigated to bedue to the morphological defects induced by the clusterization of nanorods.

Visant des applications en électronique moléculaire, de nouveaux édifices moléculaires combinant quatre dithiényléthènes (DTEs) et une porphyrine ont été synthétisés par de nouvelles voies de synthèse. Les études en solution par photochimie ou spectroélectrochimie des édifices tetraDTEs-porphyrine métallée ou base livre ont montré l’efficacité (62-88 pourcent) des photochromes en tant qu’interrupteurs et la possibilité de lire l’état des DTEs par la fluorescence de la porphyrine. Pour mieux comprendre les interactions électroniques DTEs- porphyrines, des édifices plus simples, bis(porphyrine)DTE, déjà partiellement étudiés dans la littérature, ont été explorés. L’ensemble de ces études à mis en évidence l’impact des métaux sur la capacité photochromique des édifices dithiényléthène – porphyrine. / The main purpose of this thesis was the synthesis of new molecular structures, combining dithienylethenes and porphyrins, for applications in molecular electronics and spintronic. Metallated and free base porphyrins bearing four DTEs were characterizes and studied in solution by photochemistry and spectroelectrochemistry. The efficiency of switching of our systems reach 88 percent and strong quenching porphyrin’s fluorescence was reported. New synthetic pathways were investigated to prepare a broader scope of tetraDTEs-porphyrin derivatives. Moreover, to better understand the electronic communications between DTEs and porphyrins, a simpler bis(porphyrin)DTE molecular structure was synthetized and studied. These studies demonstrated showed the important role of the metal on photochromic behavior of dithienylethene – porphyrin architectures.

Le cancer colorectal (CCR) est le troisième cancer le plus commun diagnostiqué dans le monde entier. Les limites de la chimiothérapie à base de cisplatine ont incité les scientifiques à rechercher de nouveaux médicaments anti-cancéreux à base de métal. Les complexes à base d’or(III) ont été parmi les plus largement étudiés puisqu’ils ont montré une plus importante cytotoxicité in vitro que le cisplatine ainsi que des activités anti-cancéreuse in vivo dans le CCR, mais leur utilisation clinique a été limitée en raison de leur faible stabilité dans des conditions physiologiques. De nouveaux complexes à base d’or(III) couplés à la porphyrine [or(III)/chlorure d’adamantane-porphyrine (SN1) et or(III)/chlorure de mono-acétateporphyrin (SN2)] avec une stabilité en solution aqueuse améliorée ont été synthétisés. SN1 et SN2 réduisent la survie des lignées humaines HT-29 et HCT-116 de CCR, causent l'arrêt du cycle cellulaire en phase G2/M, et nous avons observé une diminution de l'expression de la cycline B1 et de la kinase « cyclindépendant 1 » (Cdk1) avec une surexpression de la forme active de p53, p21 et de « Bcl-2-associated X » (Bax). En outre, SN1 et SN2 induisent l’apoptose par la voie intrinsèque, puisqu'ils mènent au clivage de la caspase 9, la caspase 3 et la poly(ADP-ribose) polymérase (PARP) tout en augmentant l’expression de Bax. La phosphatidylinositol-3-kinase/protéine kinase B (PI3K/Akt), le facteur nucléaire κB (NF-κB) et l’ « extracellular signal-regulated kinase » (ERK) sont importants pour la survie cellulaire et la prolifération. SN1 et SN2 entrainent une diminution de l'activité d'Akt où la forme phosphorylée diminue avec le temps, mais aussi ils causent une diminution importante dans la phosphorylation d'ERK et l'activité de NF-κB. Finalement, les complexes SN1 et SN2 ciblent la voie p38/« mitogen-activated protein kinase » (MAPK) entrainant une augmentation de l'expression de la cyclooxygenase-2 et de son produit enzymatique la prostaglandine E2. / Colorectal cancer (CRC) is the third most common cancer diagnosed worldwide. The limitations of cisplatin-based chemotherapy have prompted intense interest among scientists to search for alternative metal-based anticancer medicines. Gold(III) complexes have been among the most widely investigated since they showed higher cytotoxicity than cisplatin and promising in vitro and in vivo anticancer activities in CRC but their clinical usefulness has been limited by their poor stability under physiological conditions. A novel gold(III) porphyrin complexes [gold(III) porphyrin-adamantane chloride (SN1) and gold(III) porphyrin mono-acetate chloride (SN2)] with improved aqueous stability were synthesized. SN1 and SN2 reduced the survival of human CRC HT-29 and HCT-116 cell lines, caused cell cycle arrest in G2/M phase, and we observed downregulation of the expression of cyclin B1 and cyclin-dependent kinase 1 (Cdk1) along with up-regulation of the active form of p53, p21 and Bcl-2–associated X (Bax). Furthermore, SN1 and SN2 induced apoptosis by the intrinsic pathway, since they lead to the cleavage of caspase 9, caspase 3 and poly(ADP-ribose) polymerase (PARP), and up-regulating Bax. Phosphatidylinositol-3-kinase/protein kinase B (PI3K/Akt), nuclear factor-κB (NF-κB) and extracellular signal-regulated kinases (ERK) are important for cell survival and proliferation. SN1 and SN2 lead to decrease in the activity of Akt where thephosphorylated form decreased with time as well as they caused an important decrease in the phosphorylation of ERK and activity of NF-κB. Finally, SN1 and SN2 complexes affected p38/mitogenactivated protein kinase (MAPK) pathway then we recorded an increase in the cyclooxygenase-2 expression and its enzymatic product prostaglandin E2.

Des films du type polyoxométallates-porphyrines ont été synthetisés et sont basés sur des interactions du types covalentes ou électrostatiques. Les films polyoxométallates–porphyrines sont obtenus par électro-oxydation de l’octaéthylporphyrine de zinc (ZnOEP) ou la 5,15-ditolylporphyrine (H2T2P) en présence de différents types of polyoxométallates (POMs) portant deux groupes pyridyles pendants (py-POM-py) Trois type de systèmes py-POM-py ont été utilises : i) un Lindqvist polyoxovanadate fonctionalisé via deux groupes tris-alkoxo , ii) un derive organosilyl fonctionalisé du type Keggin ou Dawson, et iii) des briques du type Dawson [P2W15V3O62]9− fonctionalisée avec des groupements organiques bis-pyridine de géométrie variée via un greffage diolamide). Tous ces films ont été testé pour la génération de photocourant et la photocatalyse de la réduction de métaux (Ag et Pt). Des films électrostatiques POM-porphyrin ont été également préparés par incorporation de polyanion du type Preyssler [NaP5W30O110]14- sur les films de porphyrine polycationic (poly-ZnOEP) électropolymérisés avec des espaceurs viologènes ou bis-viologènes. [NaP5W30O110]14- agit comme relais d’électron entre une porphyrine excitée ZnOEP* et le viologène (ou le bis-viologène) retardant la recombinaison de charge ce qui permet une augmentation du photocourant. Enfin, des nanoparticules POM@NPs (Pt, Au, Ag) ont été introduites en surface de copolymère polycationique à base de bis-porphyrine par métathèse afin d’augmenter l’efficacité de la génération de photocourant. La résonance de plasmon de surface localisée qui se produit à la surface des nanoparticules d'argent a sensiblement améliorée l'excitation électronique de porphyrine. / Polyoxometalates-porphyrin hybrid films were synthesized based on covalent or electrostatic interactions. Copolymeric polyoxometalate–porphyrin films were obtained by the electro-oxidation of zinc octaethylporphyrin (ZnOEP) or 5,15-ditolyl porphyrin (H2T2P) in the presence of a different type of polyoxometalates (POMs) bearing two pyridyl groups (py-POM-py). Three type of py-POM-py have been used: i) a tris-alkoxo functionalized Lindqvist polyoxovanadate, ii) an organosilyl functionalized Keggin-type [PW11Si2O40C26H16N2]3- and Dawson-type [P2W17Si2O62C26H16N2]6-, and iii) a bis-pyridine-substituted organo-polyoxometallic bricks using [P2W15V3O62]9− diolamide-grafting method with various geometries of the pendant group. All are applied for photocurrent generation and photocatalytical recovery of metals (Ag and Pt). Electrostatic POM-porphyrin films were also prepared by incorporated Preyssler type polyanion [NaP5W30O110]14- onto the electropolymerized polycationic porphyrin (poly-ZnOEP) with viologen or bis-viologen as spacers. [NaP5W30O110]14- as an efficient electron shuttle between the excited ZnOEP and viologen (or bis-viologen) which effectively retarded the fast charge pair recombination and enhanced the photocurrent magnitude. Later, we introduced nanoparticles POM@MNPs to a bis-porphyrin copolymer through metathesis reaction to further improve the efficiency of the photocurrent generation in which the localized surface plasmon resonance that occurs at the surface of silver nanoparticles has substantially enhanced the electronic excitation of surface-anchored porphyrin.