Os objetivos da tese são, investigar (i) as estruturas terciária e quaternária de diversas proteínas em solução e (ii) as mudanças conformacionais de proteínas induzidas por ligantes e/ou temperatura, variando-se a concentração dos mesmos, etc. A principal técnica utilizada foi a de espalhamento de raios X a baixos ângulos (no inglês SAXS de mall-angle X-ray scattering), associada a outras metodologias como cristalografia e modelagem de proteínas. As contribuições dos estudos realizados de várias proteínas de interesse científico foram as seguintes: (i) propôs-se pela primeira vez um modelo de um receptor nuclear (RXR) composto por dois domínios, um de ligação ao ligante e outro ao DNA; (ii) elucidou-se o estado configuracional da fosfo-enol-piruvato carboxoquinase em solução; (iii) foi determinado o efeito de agregação e mudança conformacional induzido por ligantesna isoenzima fosfofrutoquinase e (iv) determinou-se a estrutura em solução da interleucina humana 22 e propôs-se modelos de interação com seus receptores. Além disso, (i) foi desenvolvido um método para determinar o estado oligomérico de uma proteína em solução, em quaisquer condições de tampão e concentração, utilizando medidas de SAXS em escala relativa, e (ii) mostrou-se que a densidade das proteínas é uma função do seu peso molecular, contrariando conceitos clássicos, tendo as proteínas pequenas (< 20kDa) uma densidade mais elevada que as maiores. / The purpose of this thesis is to investigate (I) the tertiary and quaternary structure of several proteins in solution and (II) conformational changed that such proteins undergo when they bind to ligands or temperature, pH, etc. conditions are varied. The main experimental technique utilized in this study was Small Angle X-Ray Scattering (SAXS) associated to other techniques and approaches like protein crystallography and homology modeling. The main contributions related to this work are: (i) for the first time a model for a nuclear receptor (RXR) containing two domains was proposed, one DNA binding domain and one ligand binding domain; (ii) the oligomeric state of the phosphor-enol-pyruvate caboxykynase in solution was detennined; (iii) the conformation changed induced by ligants to the isoenzyme phosphofructokinase was determined and (iv) the solution structure of human interleukin revealed and a model with its receptor proposed. Additionally, (i) a method for determining the oligomeric state of a protein in solution under any buffer conditions and concentration using SAXS in relative scale is proposed and (ii) it was also shown that proteins density is a molecular weight dependent function, where small proteins with less than 20kDa have in average a larger density than bigger ones.

Orientadores: André Luiz Barboza Formiga, Maria Isabel Felisberti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-20T16:07:14Z (GMT). No. of bitstreams: 1 Jannuzzi_SergioAugustoVenturinelli_M.pdf: 35610656 bytes, checksum: f2dffeb8cf285399ac0996a04b2601a7 (MD5) Previous issue date: 2011 / Resumo: O presente trabalho ocupa-se da síntese, caracterização e aplicação de um material híbrido orgânico-inorgânico em que o bloco orgânico é o polímero poli(4-vinilpiridina) e o bloco inorgânico é o pentacianoferrato(II) de sódio. A primeira parte trata da influência do polímero nas propriedades do complexo, e vice-versa. A segunda parte ilustra a aplicação do metalopolímero na produção de estruturas análogas ao azul da Prússia (AP) pela reação de Fe com as unidades pentacianoferrato. A banda de transferência de carga metal-ligante do pentacianoferrato do metalopolímero em solução desloca-se para energias menores na medida em que aumenta a fração de meros livres da cadeia polimérica, indicando que a fração do bloco orgânico modula a polaridade do ambiente químico do complexo. Por outro lado, a crescente quantidade de complexo ligado às cadeias poliméricas aumenta viscosidade das soluções de metalopolímeros, evidenciando que o pentacianoferrato expande o novelo macromolecular. Estruturas tipo azul da Prússia sintetizadas a partir do metalopolímero exibem elevada estabilidade coloidal quando comparadas aos compostos isentos de polímero e apresentam banda de intervalência em menores energias do que o frequentemente reportado para esse tipo de estrutura, provavelmente em virtude do envolvimento das partículas de AP pelo polímero / Abstract: This work comprises the synthesis, characterization and application of a hybrid organic-inorganic metallopolymer, in which the organic block is the polymer poly(4-vinylpyridine) and the inorganic block is the complex sodium pentacyanoferrate(II). The first part presents the influence of the polymer on the properties of the complex and vice-versa. The second part illustrates an application of the metallopolymer on the production of Prussian blue (AP) analogs based on the reaction of Fe with the pentacyanoferrate moieties. The metal-to-ligand charge transfer band of the polymer-bound pentacyanoferrate in solution shifts towards lower energies whereas the free monomers fraction arises. It indicates that the organic block fraction tunes the polarity of the pentacyanoferrate chemical environment. On the other side, the increasing fraction of complex bound to the polymer chain increases the metallopolymer solution viscosities. This is an evidence that the pentacyanoferrate expands the macromolecular coil. Prussian blue-type structures synthesized from metallopolymers exhibit enhanced colloidal stability when compared to the polymer-free compounds. They also present intervalence bands at lower energies than those frequentlly reported for this type of inorganic structure. The reason is probably the polymer wrapping of the particles / Mestrado / Quimica Inorganica / Mestre em Química

Dans ce travail, la chimie supramoléculaire est utilisé pour créer des polymères triarylamine auto-assemblées affichant l’auto-assemblage, la conduction, et les propriétés plasmoniques. Deux classes de polymères triarylamine auto‐assemblées sont décrits en détail, y compris leurs propriétés d'auto-assemblage, structure à empiler, ainsi que le comportement électrochimique. En outre, l'application de ces matériaux à l'égard des cellules solaires organiques et spintronique moléculaire est examinée. Enfin, la capacité de ces fibres pour être utilisé dans des applications plasmoniques est détaillé, dans lequel les assemblages supramoléculaires sont présentés à quelques résonances plasmoniques de nanoparticules, agissent comme guides plasmoniques, et induisent l'ordre des nanoparticules plasmoniques à une interface liquide-liquide. Ces propriétés émergentes sont intimement liés aux interactions supramoléculaires démontrant ainsi de nouvelles applications de polymères supramoléculaires. / In this work, supramolecular chemistry is used to create self-assembled triarylamine polymers displaying novel self-assembly, conduction, and plasmonic properties. Two classes of self-assembled triarylamine polymers are described in detail, including their self-assembly properties, stacking structure, as well as electrochemical behavior. Additionally, the application of these materials towards organic solar cells and molecular spintronics is examined. Finally, the ability of these fibers to be used in plasmonic applications is detailed, wherein the supramolecular assemblies are shown to couple plasmonic nanoparticle resonances, act as plasmonic waveguides, and induce the ordering of plasmonic nanoparticles at a liquid-liquid interface. These emergent properties are intimately linked to the supramolecular interactions thereby demonstrating novel applications of supramolecular polymers.

La synthèse supramoléculaire permet de dépasser le jeu du hasard dans les rencontres intermoléculaires en programmant l’assemblage des briques moléculaires selon des stratégies déterministes. De telle prédispositions architecturales sont d’un intérêt majeur en nanosciences pour l’obtention de nano-objets moléculaires et leur organisation à l'échelle nanométrique.On peut imaginer réaliser des dispositifs de taille nanométrique en dotant de propriétés particulières les synthons de ces assemblages. Le travail présenté dans cette thèse de doctorat illustre en intégralité cette démarche, de la synthèse à la caractérisation des propriétés magnétiques de baguettes dinucléaires et grilles tétranucléaires dont les sites métalliques sont paramagnétiques. Une étude approfondie des conditions d’obtention de ces objets a été effectuée en utilisant des méthodes de caractérisation physico-chimiques. L’étude de leurs propriétés magnétiques a été menée principalement par Résonance Paramagnétique Électronique pour étudier les complexes formés en solution. Les contraintes géométriques qui sont exploitées par la synthèse supramoléculaire présentent un intérêt pour l’obtention de propriétés magnétiques particulières. / The elaboration of well-defined geometrical molecular arrangements is a key issue of supramolecular chemical synthesis. This ability is of major interest in the field of nanosciences in order to get well organized supramolecular architectures at the nanoscale. Upon endowing with peculiar physical and/or chemical properties the molecular synthons of such architectures one may think of building original devices. Such a strategy is actually the driving force of this PhD work, which reports on the synthesis and the subsequent characterization of dinuclear stick and tetranuclear grid complexes with paramagnetic metal ions. A comprehensive study of the stability in solution of these supramolecular objects has been carried out with the help of various spectroscopic methods. A thorough investigation of their magnetic properties has been performed in solution by Electron Paramagnetic Resonance spectroscopy. Thanks to its geometrical rules, the efficiency of the supramolecular synthetic strategy is demonstrated to determine the magnetic properties of the studied complexes.

In this study, the templating role of bimolecular triple hydrogen bonded honeycomb network consisting perylene-3,4,9,10-tetracarboxydi-imide and melamine is investigated, using scanning tunneling microscopy. Although the stability of the network upon modification is a major obstacle toward higher complexity, three different approaches in this work highlight formation of successful architectures in a sequential way. 1. Insertion of pore modifier star shaped molecules based on tri(phenylene ethynylene)benzene core in the pores to construct a new template. 2. Insertion of iodinated molecules in the pores to study the network as a nanoreactor. 3. Electrochemical deposition of metals in the pores. Self-assembly monolayer of four different molecules based on tri(phenylene ethynylene)benzene core on uniform gold surface revealed different structures. The degree of the order within the structures depends highly on the symmetry of the molecules, and hence asymmetric molecule formed disordered structure. Upon insertion into the pores of the network, one of molecules did not match the pores size, while others fitted and illustrated rotation depending on the strength of their interaction with the network components and the substrate. The rotation is significantly reduced by modifying the molecules. These new architectures are used as templets hosting C₆₀ molecules which resulted in isolated single C₆₀ molecules. Self-assembly of iodinated molecule under different conditions on uniform gold surface leads to formation of different structures including monomers and dimers. Upon thermal treatment on the uniform surface oligomers are formed, whereas for the molecules confined in the pores of the network, the covalent bond formation was limited to dimerisation. Electrochemical copper deposition into the pores of the network under acidic condition (pH = 1 - 2) is not possible because of the stability of the network. However, by increasing pH of the electrolyte (pH = 5 – 7), a bilayer of Cu and anion is formed in the pores of the network, confirmed by scanning tunneling microscopy and X-ray photoelectron spectroscopy.

Doctor Of Philosophy / Department of Chemistry / Christer Aakeröy / Crystal engineering, or non-covalent synthesis in the solid state, requires an understanding of intermolecular forces, and the hydrogen bond has become a reliable non-covalent tool in the construction of supramolecular architectures. In the same way that synthetic chemists refer to a “yield” to quantify a desired product, crystal engineers typically determine the successful formation of a supramolecular product according to the frequency or occurrence of preferred intermolecular interactions between molecules under certain reaction conditions, thus, the supramolecular yield. These non-covalent reactions can be effectively carried out using supramolecular reagents (SR’s). A family of ditopic bis-imidazol-1-yl/benzimidazol-1-yl compounds were synthesized and used as SR’s in combination with a variety of dicarboxylic acids to produce binary solids in 100% yield through the primary acid···imidazol-1-yl/benzimidazol-1-yl synthons even in the presence of potentially disruptive intermolecular interactions. We furthermore noted that secondary C–H···O interactions within and between 1-D chains were of equal structural importance based upon an analysis of the metrics displayed by these interactions. The use of these SR’s as ligands with neutrally charged metal complexes was also investigated. SR’s containing benzimidazol-1-yl and carboxamide moieties were synthesized and combined with two different carboxylic acids to make ternary solids through acid···benzimidazol-1-yl and carboxamide···acid hydrogen bonds using a hierarchical approach – the best donor-best acceptor, second best donor-second best acceptor guidelines. These SR’s were also employed as ligands for high-yielding syntheses of linear metal complexes where neighboring complexes are linked via carboxamide···carboxamide hydrogen bonds. Asymmetric SR’s possessing two different N-heterocycles were synthesized and employed in the construction of ternary supermolecules with a high degree of structural selectivity and specificity when introduced to two different carboxylic acids. The stronger acid interacts at the more basic site, while the weaker acid hydrogen-bonds with the less basic nitrogen atom. Finally, an SR containing three different binding sites was designed and synthesized with the aim of producing quaternary co-crystals.

Magister Pharmaceuticae - MPharm / The author’s objective was to follow the product life-cycle process of a novel antiretroviral, nevirapine formulation in South Africa, to generate and compile data to pursue market registration. Five supramolecular co-crystals, viz. nevirapine-saccharin (NVSC), nevirapine-DL-tartaric acid (NVTTA), nevirapine-maleic acid (NVMLE), nevirapine-glutaric acid (NVGLT) and nevirapine-salicylic acid (NVSLI) were reproduced and confirmed by powder X-ray diffraction (PXRD). A pre-formulation study ensued to identify the most appropriate co-former candidate to formulate a tablet dosage form comparative to the proprietor brand, Viramune®. The co-crystals were synthesized by the co-precipitation and solvent-drop grinding techniques and identified by hot stage microscopy (HSM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), fourier transform infra-red spectrophotometry (FTIR), PXRD and single X-ray diffraction (SXRD). The solubility, dissolution and antiviral activity profiles of these co-crystals were assessed and compared to pure NV and NV:co-former mixtures in a 1:1 ratio. The preliminary dissolution analysis applied the BP 2005 rotating-basket method with water as dissolution medium. Initially, the dissolution samples were assayed with UV/VIS spectrophotometry which led to a more convincing quantitative approach where dissolution samples were assayed by HPLC. Solubility data revealed a fivefold increase in solubility of NV co-crystallized with maleic acid. Dissolution data, however revealed NVGLT as the best performing co-crystal with a 59 % NV drug release in water (dissolution media) with the remaining 4 co-crystals all indicating an enhanced aqueous solubility of NV. The antiviral activity of all 5 co-crystals performed by the National Institute of Communicable Diseases of South Africa determined whether the co-crystals had an improved antiviral activity against HIV-1 compared to pure NV. The results indicated that NVSC and NVSLI had the greatest antiviral activity compared to pure NV and the remaining co-crystals. The pre-formulation results formed the basis for the selection of the best co-former candidate for a NV co-crystal tablet formulation by direct compression. All solid dosage form quality control tests according to the USP 364 was performed on the prototype co-crystal tablet and the Viramune® tablet. Comparative dissolution analysis to evaluate bioequivalence was conducted and assayed by HPLC. The dissolution analysis utilized 3 media, viz. HCl buffer (pH 1.2), acetate buffer (pH 4.5) and a phosphate buffer (pH 6.8) which displayed no similarity in the dissolution profile of the prototype and the proprietor brand. Solution stability of NV in these buffered media was assessed after 4 weeks exposure of the dissolution samples to cold chain (2 - 8 °C, 0 % RH) and accelerated environmental conditions (40 °C, 75 % RH). The results indicated no significant degradation of NV in the prototype co-crystal tablet and the proprietor brand during the accelerated stability tests. Cytotoxicity against a host cell 293T and antiviral activity against the pseudo-HIV-1 virus of the prototype and proprietor brand was further determined. The antiviral activity results were favourable for both the prototype co-crystal and the proprietor brand tablet.

La conception de matériaux aux propriétés mécaniques caractéristiques de polymères à la température d'usage, mais capables de s'écouler comme des liquides simples lorsqu'ils sont chauffés demeure l'un des défis les plus importants de la chimie supramoléculaire. La combinaison de ces propriétés antagonistes est hautement souhaitable afin d'assurer au matériau durabilité, malléabilité, et recyclabilité. Ici, nous explorons une nouvelle stratégie basée sur des réactions de polycondensation, dans le but de concevoir des matériaux polymères supramoléculaires avec une contrainte à la rupture supérieure à 10 MPa et une viscosité en fondu inférieur à 1 Pa.s. Nous décrivons notamment la synthèse et les propriétés rhéologiques et mécaniques (essais de traction uniaxiale) de polymères supramoléculaires basés sur une architecture de type polyamide multibloc. La flexibilité des réactions de polycondensation permet de contrôler la distribution de la taille des chaînes. L'établissement de liaisons hydrogène et la cristallisation des groupements associatifs aux extrémités de chaînes et des segments cristallisables en milieux de chaînes permettent d'atteindre les propriétés ciblées. Une seconde famille de polymères supramoléculaires, basée sur un squelette de PMMA, a été synthétisée par polymérisation radicalaire contrôlée (ATRP ou RAFT). Cette dernière permet un contrôle précis des masses moléculaires, et la modification chimique des oligomères post-polymérisation permet d'obtenir des chaînes de PMMA supramoléculaires terminées aux deux extrémités par des groupements associatifs. Les propriétés thermiques, mécaniques et rhéologiques de ce polymère supramoléculaire sont décrites. / Design of materials with polymer-like properties at service temperature but able to flow like simple liquids when heated remains one of the important challenges of supramolecular chemistry. Combining these antagonistic properties is highly desirable to provide durability, processability, and recyclability of materials. Here, we explore a new strategy based on polycondensation reactions to design supramolecular polymer materials with stress at break above 10 MPa and melt viscosity lower than 1 Pa·s. We describe the synthesis and rheological and mechanical properties (uniaxial tensile tests) of supramolecular polymers based on a multiblock polyamide architecture. The flexibility of polycondensation reactions made it possible to control the molecular size distribution, the strength of hydrogen bonds, and the crystallization of middle and end groups and to achieve targeted properties. A second family of supramolecular polymers, based on a PMMA backbone, was designed and synthesized by ATRP or RAFT polymerization. Controlled radical polymerization enabled precise control over molecular weight and chemical modification of the oligomers allowed us to obtain supramolecular PMMA terminated at both ends by associative groups. Thermal, mechanical and rheological properties of this supramolecular polymer are described.

A tese consistiu no estudo por técnicas reológicas da dinâmica de géis e dispersões da gliadina do glúten do trigo em meios de dimetilsulfóxido (DMSO), dimetilformamida (DMF) e formamida puros e em suas misturas com a água. Investigou-se o efeito da temperatura e das concentrações das espécies componentes (proteína e constituintes dos sistemas solventes) sobre o comportamento de fluxo e de deformação dos sistemas. Foram realizados testes em regime estacionário, ensaios transientes e ensaios dinâmicos (oscilatórios). A caracterização da proteína nos diversos meios foi realizada através de técnicas de espalhamento de luz dinâmico e estático e de espalhamento de raios X em baixos ângulos. Esses recursos permitiram descrever a distribuição de populações da proteína nos géis e dispersões, em suas formas livres ou associadas, assim como estimar aspectos de tamanho e mobilidade a partir da determinação dos raios hidrodinâmicos e coeficientes de difusão. As composições de aminoácidos da gliadina, na fração bruta e em uma fração isolada em meio etanólico, foram determinadas por técnicas de CLAE Cromatografia Líquida de Alta Eficiência. Um isolamento preliminar das sub-frações de gliadina foi obtido por outra técnica cromatogrática (FPLC Fast Polymer Liquid Chromatography). Foram ainda desenvolvidos estudos relativos ao efeito de gliadina sobre a bicamada lipídica de vesículas gigantes de fosfolipídio, através da técnica de aspiração por micropipetas, com monitoramento por vídeo-microscopia. O objetivo foi o de se verificar o eventual efeito da proteína sobre a constante de elasticidade, kc, da bicamada. Os resultados obtidos podem ser resumidos como se segue: a) o comportamento viscoelástico apresentado pela gliadina mostrou dependência com a natureza e a composição do meio de dispersão. Foi verificada a ocorrência de comportamento tixotrópico ou reopéxico como função da temperatura e um comportamento cíclico para a viscosidade em função do tempo. b) foi possível correlacionar alguns aspectos da estrutura molecular e polaridade do solvente com a maior ou menor capacidade de formação de gel de gliadina: solventes com regiões apolares mais expressivas, como DMSO e DMF (&#949;= 47,24 e 38,25, respectivamente) induzem a formação de géis rígidos, enquanto um composto como formamida, destituído de um domínio apolar minimamente significativo e &#949; maior que o da água (&#949; = 84), tem capacidade significativamente menor de promover a formação de géis com as mesmas características de rigidez. c) os géis são formados por unidades com raios de giro da ordem de 15Å, além de agregados de tamanhos bem maiores. Considerando-se a massa molar média de 32 350 g/mol para a gliadina em nossa amostra, é de se supor que a proteína encontre-se muito compactada no gel (considere-se que lisozima, com massa molar muito menor, igual a 14300 g/mol, possui raio de giro nesse mesmo valor). Um modelo de enovelamento interpenetrante, proposto em nosso grupo através de métodos de dinâmica molecular para a conformação da gliadina, seria assim compatível com essas observações experimentais. d) gliadina &#969;, seletivamente extraída por tratamento com etanol, mostrou-se capaz de reduzir a elasticidade de membranas de microvesículas de fosfolipídios, aumentando o valor de sua constante de curvatura kc. Um efeito de saturação foi observado, para razões de massa gliadina/DOPC ~2-3%. e) coeficientes de difusão para dispersões de gliadina são da ordem de 10-10 cm2.s-1, com raios hidrodinâmicos na faixa nm-&#181;m. Duas populações dinamicamente distintas foram identificadas nos géis de gliadina. f) o grau de polidispersão e o tamanho dos agregados mostraram dependência com a concentração da proteína nos géis: são gerados agregados menores (diminuição da massa molar média) em tamanhos mais uniformes (menor polidispersão), com o aumento da concentração de gliadina. Essa mesma tendência de variação é observada como função do tempo, indicando a ocorrência de rearranjos estruturais na fase de envelhecimento dos géis. / The thesis consisted in a rheological study of the dynamics of gels and dispersions of gliadin from wheat gluten in pure dimethylsulfoxide, dimethylformamide or formamide and in their mixtures with water. The effect of temperature and that of the concentration of the component species (protein and solvent constituents) on flow behavior and deformation were evaluated. Steady-state, transient and dynamical (oscillatory) tests were performed. Protein characterization in the various media was performed through dynamic and static light scattering and small angle X ray scattering techniques. The application of techniques allowed to describe the distribution of protein populations in the gels and dispersions, in their free and associated forms, as well as to estimate their size and mobility, through the determination of the hydrodynamical radii and diffusion coefficients. The amino acid compositions of gliadin, both in the crude protein and in an isolated fraction in ethanol, were determined by HPLC technique. A preliminary isolation procedure of gliadin sub-fractions was achieved by another chromatographic technique (FPLC). The effect of gliadin on the phospholipid bilayer of giant vesicles was studied through the technique of micropipet aspiration coupled to videomicroscopy. The aim was to verify the possible effect of protein on the elasticity constant, kC of the bilayer. Results obtained can be summarized as follows: a) the viscoelastic behavior presented by gliadin was found to be dependent on the nature and composition of the dispersing media. Temperature-dependent tixotropic or rheopexic behavior were observed, as well as a cyclic behaviour for viscosity as a function of time. b) it was possible to correlate some aspects of solvent molecular structure and polarity with its greater or lesser capacity of gel formation: solvents with more expressive apolar regions, such as DMSO and DMF (&#949; = 47,24 and 38,25, respectively) induce formation of rigid gels, whereas a compound such as formamide, devoid of a minimally significant apolar domain and &#949; greater than that of water (&#949; = 84), is significantly less able to promote gel formation with the same characteristics of rigidity. c) gels are formed by units with gyration radius around 15Å and also by aggregates of greater size. Considering that the average molar mass in our sample for gliadin is 32350, one can assume that the protein is very densely packed in the gel (consider for instance that lysozyme, with a much lower molar mass, 14300 g/mol, has a gyration radius of this same size). A compact, interpenetrating folding model for gliadin, developed in our group through molecular dynamics, is compatible with such experimental observations. d) &#969; gliadin, selectively extracted in ethanol, was found to be able to reduce membrane elasticity of phospholipid microvesicles, by increasing its elastic curvature constant kC. A saturation effect was observed, for a mass ratio as low as gliadin/DOPC ~2-3%. e) diffusion coefficients for gliadin dispersions are circa 10-10 cm2.s-1, with hydrodynamical radii in the nm-&#181;m range. Two dynamically distinct populations are identified in the gliadin gels. f) gel polydispersity and aggregate size depend on protein concentration: smaller aggregates (lower average molar mass) of more uniform sizes are produced for increasing gliadin concentration. Variation with time followed the same pattern, indicating that structural rearrangements take place during gel aging.

This study expands the role of polythiophenes as an electron donating chromophore within energy harvesting milti-modular donor-acceptor systems. The polythiophene moiety would act as an electron donating spacer group between the donor and acceptor entities, viz., phenothiazine and fulleropyrrolidine, respectively, in the newly synthesized supramolecular triads. The triads 10-{[2,2';5',2"] terthiophene-5-fulleropyrrolidine} phenothiazine and 10-{[2,2'] bithiophene-5-fulleropyrrolidine} phenothiazine were synthesized and characterized through electrochemical and spectroscopic methods to ascertain their structural integrity. the componets of the triads were selected for their established redox parameters. Phenothiazine would act as a secondary donor and would facilitate hole-transfer from the polythiophene primary electron donor, due to its ease of oxidation and yield a long-lived charge separated state. Fulleropyrrolidine would act as an acceptor for ease of reductive capabilities and its ability to hold multiple charges. Finally, occurrence of photoinduced electron transferleading to the anticipated charge separated states is established from advanced transient spectroscopic techniques on these novel supramolecular systems.