The interaction of small molecules with DNA has been extensively studied and has produced a large catalogue of molecules that non-covalently bind to DNA though groove binding, intercalation, electrostatics, or a combination of these binding modes. Anthracene, acridine, and carbocyanine-based chromophores have been examined for their DNA binding properties and photo-reactivities. Their planar aromatic structures make them ideal chromophores that can be used to probe DNA structural interactions and binding patterns. We have studied DNA binding and photocleavgage properties of a bisacridine chromophore joined by a 2,6-bis(aminomethyl)pyridine copper-binding linker (Chapter II), a series of 9-aminomethyl anthracene chromophores (Chapters III and IV), both under conditions of high and low ionic strength, as well as a series of pentamethine linked symmetrical carbocyanine dyes (Chapter V). In Chapter II we present data showing that high ionic strength efficiently increases copper(II)-dependent photocleavage of plasmid DNA by the bisacridine based chromophore (419 nm, pH 7.0). In Chapters III and IV, using an pyridine N-substituted 9-(aminomethyl)anthracene (Chapter III), a bis-9-(aminomethyl)anthracene, and its mono 9-(aminomethyl)anthracene analogue (Chapter IV), pUC19 plasmid DNA was photo-converted to highly diffuse DNA fragments (350 nm, pH 7.0) in the presence of 150 mM NaCl and 260 mM KCl. Spectroscopic analyses suggest that the combination of salts promotes a change in DNA helical structure that initiate a switch in anthracene binding mode from intercalation to an external or groove binding interactions. The alteration in DNA structure and binding mode leads to an increase in the anthracene-sensitized production of DNA damaging reactive oxygen species. Finally, in Chapter V, pUC19 plasmid DNA is converted to its nicked circular and linear forms following irradiation of a series of pentamethine linked symmetrical carbocyanines (red light, pH 7.0). The data suggest that the relative levels of photocleavage arise from the different substituents on the nitrogen alkyl side chain and the pentamethine linker.

Au cours de la dernière décennie, les chalcogénures (Q=S, Se et Te) d'élément de transition ont fait l'objet d’un fort regain d’intérêt, notamment en raison de la découverte de supraconductivité à haute température critique dans les composés à base de fer et de sélénium. Dans ce contexte, l'objectif de ce travail de thèse est de découvrir et d'étudier de nouveaux composés chalcogénures à base de fer et de nickel dans l'espoir de révéler des propriétés électroniques nonconventionnelles. Pour cela, nous avons utilisé plusieurs approches de conception rationnelle de nouveaux composés, comme la prédiction structurale par des calculs ab initio (USPEX), le concept d'assemblage de sous-unités structurales 2D ou des méthodes de chimie douce. Plusieurs nouveaux composés lamellaires ont été ainsi découverts. Par exemple, nous avons réussi à obtenir de nouveaux composés dont les structures résultent d'un assemblage de blocs fluorines, associés soit avec un plan de fer et de sélénium comme dans Ba2F2Fe1.5Se3, soit avec un plan de chalcogène contenant des chaines de sélénium (Ba3F4Se1.66) ou des paires de soufre (Ba2F2S2). Nous avons ensuite montré que de tels composés, utilisés comme précurseurs, permettent l’intercalation topotactique d’éléments de transition M, qui réagissent avec la paire (S2)2- pour former de nouvelles entités MxSy. Ce résultat ouvre donc une nouvelle voie de synthèse générale jouant sur la chimie des paires de chalcogène. En utilisant ce concept, nous avons pu découvrir de nouveaux composés lamellaires possédant des plans MxSy originaux. / During the last decade, an upsurge of interest was dedicated to chalcogenides (Q = S, Se and Te) of transition elements, particularly because of the discovery of superconductivity at high critical temperature in compounds based on iron and selenium. In this context, the aim of this thesis work is to discover and explore new chalcogenide compounds based on iron and nickel in the hope of revealing unconventional electronic properties. We used several approaches of rational design of new compounds, such as structural prediction based on ab initio calculations (USPEX), the concept of assembly of two-dimensional Secondary Building Units or soft chemistry methods. Several new lamellar compounds were thus discovered. For example, we succeeded to obtain new compounds which structures result from an assembly of fluorite blocks associated with either an iron selenide layer, such as in Ba2F2Fe1.5Se3, or with a chalcogen layer containing selenium chains (Ba3F4Se1.66) or sulfur pairs (Ba2F2S2). We then showed that such compounds, used as precursors, allow the topotactic intercalation of transition elements M, which react with (S2)2- pairs to form new MxSy layers. This result paves the way for a new general synthetic route playing on the chemistry of chalcogen pairs. Using this concept, we have discovered several new lamellar compounds exhibiting original MxSy layers.

Foram realizadas pesquisas em uma série de condutores iônicos que apresentam aplicações na área dos dispositivos eletroquímicos de estado sólido, utilizando-se basicamente a técnica de Ressonância Magnética Nuclear (RMN). A primeira parte deste trabalho é dedicada aos compostos de intercalação baseados na matriz de dissulfeto de molibdênio (MoS2) onde as espécies intercalantes (íons de lítio e moléculas de aminas) são inseridas num espaço de dimensionalidade reduzida gerado pela matriz. Já a segunda parte envolve os condutores iônicos poliméricos do tipo compósitos, nos quais foram utilizadas nanopartículas de carbono (Carbon Black) e titânio (TiO2) no eletrólito formado pelo poli(óxido de etileno) (POE) e o perclorato de lítio (LiClO4). Todos estes sistemas apresentam, em geral, uma considerável complexidade estrutural, o que significa que os movimentos moleculares e de difusão iônica se produzem num meio semicristalino (caso dos compósitos) ou num meio de dimensionalidade reduzida (caso dos intercalados). A espectroscopia de RMN dos núcleos de 7Li e 1H é uma técnica conveniente para o estudo destes materiais, pois é possível avaliar, através dos resultados obtidos das medidas dos tempos de relaxação e formas de linha, os efeitos provocados pela baixa dimensionalidade dos movimentos em estruturas laminares (caso dos intercalados), bem como identificar e aferir as interações e os mecanismos de relaxação resultantes dos diferentes graus de liberdade dos movimentos (iônicos e moleculares), fornecer parâmetros estruturais (distâncias interatômicas) que auxiliam na proposta de possíveis modelos estruturais e caracterizar completamente a escala temporal dos movimentos iônicos e moleculares. / Nuclear Magnetic Resonance (RMN) techniques were used to study a series of ionic conductor materials, which present applications in the area of the solid-state electrochemical devices. The first part of this work is dedicated to the study of intercalation compounds based on the molybdenum disulfide matrix (MoS2), where the intercalated species (lithium ion and amine molecule) are inserted in the low-dimensionality space generated by the matrix. The second part involves the study of a composite polymer electrolyte, employing fillers like Carbon Black and titanium dioxide (Tio2) nano particles in the electrolyte formed by the poly(ethy1ene oxide) and a lithium salt (LiClO4). In general, these systems present a considerable structural complexity, meaning that the molecular movements and ionic diffusion are produced in a semicrystalline environment (case of the composites) or in an environment of reduced dimensionality (case of intercalates). The 7Li and 1H NMR spectroscopy is a convenient technique for the study of these materials. Relaxation time and line shape measurements may provide a tool to investigate the effects provoked by the low-dimensionality of the movements in laminate structures (case of intercalate), to identify the interactions and relaxation mechanisms of the ionic and molecular motions, to supply structural parameters (interatomic distances) that would help the proposal of possible structural models, and finally, to characterize the time scale of the ionic and molecular movements completely.

Compostos de vanádio são extensivamente estudados, devido suas propriedades redox, eletroquímicas, catalíticas, magnéticas e biológicas. Nesta dissertação tivemos como foco de nosso trabalho o composto VOPO4.2H2O que apresenta uma forma lamelar com suas lamelas unidas por interações de Van der Waals. Essas fracas interações interlamelares fazem do fosfato de vanadila e de seus componentes análogos excelentes matrizes para a síntese de compostos de intercalação. A morfologia do VOPO4.2H2O mostrou-se sensível a alterações de temperatura e tempo durante síntese. Através da alteração destes parâmetros obtivemos um sólido lamelar com um grau de organização inferior a matriz sintetizada à 130oC e 16 horas, devido a existência da fase II-VOPO4 que foi constatada por difração de raios-X. A quantidade de dois mols de água por mol de VOPO4 manteve-se constante segundo as análises termogravimétricas. As imagens de microscopia eletrônica de varredura confirmaram a estrutura lamelar dos produtos, no entanto uma forma rosácea foi constatada em VOPO4/160oC, sugerindo a presença da fase VOHPO4.0,5H2O, precursora da fase (VO)2P2O7 que atua como catalisador seletivo na reação de oxidação do n-butano à anidrido malêico. A intercalação de íons lantanídeos na matriz VOPO4.2H2O produziu sólidos lamelares com cristalinidade inferior a matriz hospedeira, devido a distorção dos octaedros ocasionado pela redução dos íons vanádio (V) à (IV) apresentando uma diminuição na distância interlamelar com concomitante inserção de íons lantanídeos visando o balanceamento de carga na matriz. A reação de intercalação da matriz VOPO4.2H2O utilizando os tensoativos CTAB e CPC apresentaram resultados satisfatórios confirmados por difração de raios-X e espectrofotometria na região infravermelho. A intercalação de poli(óxido de etileno) assistida com brometo de cetiltrimetilamônio mostrou-se mais adequada apresentando sólidos organizados devido as moléculas de CTAB atuarem como agente diretivo. / Vanadium compounds are intensively studied due to their electrochemical, catalytic, magnetic and biological properties. In this work, our goal was to investigate the VOPO4.2H2O (vanadyl phosphate), which has a lamellar structure formed by VOPO4 sheets interconnected by weak interactions. Taking advantage of this structure, it is possible to synthesize several different intercalation compounds in which the guest species can vary from simple ions to polymeric species. The morphology of VOPO4.2H2O is very sensitive to temperature and time of reaction changes. By varying both parameters, several lamellar matrices have been synthesized. X-ray diffraction, thermal analysis and scanning electronic microscopy showed that depending on the synthetic conditions the arrangements VOPO4.2H2O can change the shape. For instance, in one of the experiments, a rose-like structure was produced, suggesting the presence of VOHPO40.5H2O phase, precursor of (VO)2P2O7 phase, which acts as oxidation catalyst of the n-butane to maleic anhydride. Intercalation of lanthanide ions leads to lamellar solids with low crystallinity in relation to the matrix due to octahedric distortion caused by reduction of vanadium ions (VV to VIV). Besides, it was observed a decrease of the interlamellar distance in function of the electroneutrality balance between the lamellar sheets. Intercalation compounds were produced by reacting surfactants molecules directly with the matrix under hydrothermal conditions. Surfactant-assisted intercalation of poly(ethylene oxide) into VOPO4.2H2O was conducted under soft conditions with the surfactant/matrix compound as a suspension in an aqueous polymer solution.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第15672号 / 工博第3330号 / 新制||工||1502(附属図書館) / 28209 / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 垣内 隆, 教授 井上 正志 / 学位規則第4条第1項該当

Le mémoire porte sur l’étude et la mise au point d’un nouveau procédé électrochimique pour la valorisation d’effluents minéraux liquides. Il se fonde sur une exploitation originale des réactions d’intercalation réversibles de cations dans les phases de Chevrel Mo6X8 (avec X = S, Se). Le développement initial du travail a été de vérifier le transfert électrochimique de cations d’une solution source vers un électrolyte de valorisation à travers une jonction électrochimique de transfert (JET). L’élaboration de disques (diamètre 25 mm, épaisseur de 2 à 4 mm) de matrice active de forte compacité (98%) en Mo6X8 est obtenue par pressage réactif à haute température. Sa mise en fonction aboutit à un mini pilote de laboratoire qui permet d’établir les performances et de situer les limites du processus sur les cations Co2+, Fe2+, Ni2+, Cd2+, Zn2+, Mn2+ ,Cu2+. Les expérimentations démontrent que le transfert résulte d’un simple processus galvanique entre deux électrodes auxiliaires situées dans chacun des compartiments. Les rendements faradiques sont de 100% jusqu’à une densité de courant de 1,6 mA cm-2. Pour établir une modélisation du transport des ions, les coefficients de diffusion des différents cations dans chacune des matrices polycristallines ont été mesurés par différentes techniques électrochimiques. Les mobilités de chacun des cations sont proches et les coefficients de diffusion de l’ordre de 10-9 cm2.s-1 sauf pour la matrice séléniée à travers laquelle ions de la triade Fe, Co, Ni ne sont pas transférables. Les propositions de modèle de mode de transfert conduisent à envisager, pour l’optimisation des vitesses, des conditionnements en stœchiométrie des JET et de recourir à des épaisseurs faibles pour les jonctions. Les études se sont portées sur les conditions de transferts sélectifs à partir de mélanges de cations dans la solution source. Des séparations remarquables comme Cd / Zn, Co/Ni avec Mo6S8, Zn / Ni, Cd / Ni, Zn / Mn avec Mo6Se8 ont été obtenues. Elles sont transférables directement pour le traitement d’effluents industriels. Les résultats présentés confirment la potentialité de ce nouveau mode de traitement et permet d’envisager un transfert de technologie au niveau de la valorisation de co-produits et rejets industriels / The aim of this work is the study of a new electrochemical process. The industrial activity generates large amounts of liquid waste containing heavy metals. Processes used for treating this kind of materials are precipitation, solvent extraction or ion exchange. The limits of such treatments are due to their selectivity towards cations mixtures. A new original electrochemical way is purposed as an alternative of these techniques. This work deals with the extraction and the selective transfer of metal ions contained in liquid effluents or in lixiviats of industrial processes. This technique is based on the reversible redox reactions of insertion and deinsertion of cations in mineral host lattice matrices. The mineral matrix consist in a ternary molybdenum chalcogenides MxMo6X8 (where M = ternary metal cation and X= S, Se) known as Chevrel. This disc is obtained by a technique of synthesis at high temperature. The electrochemical transfer junction ETJ consists of a Mo6S8 or Mo6Se8 disc compacted by hot pressing. This method consists with a synthesis by reactive hot pressing, from mixture of powder of composition adapted for the stoichiometry of desired material. We have obtained a disc (thickness = 4mm, diameter = 25mm) with a compactness rate about 98%. The electrochemical junction allowed a good mechanical behaviour. All experiments were then carried out in a laboratory cell which allow to establish the performances and to locate the limits of the process on the cations Co2+, Fe2+, Ni2+, Cd2+, Zn2+, Mn2+, Cu2+. These experiments show that the transfer results from a simple galvanic process between two auxiliary electrodes located in each compartment. The transfer faradic yields about 100% were achieved until a current density of 1.6 mA.cm-2. The results confirm the feasibility of a transfer process. The real operations of the selective transfer are shown with applications for remarkable separations as Co/Ni, Cd/Ni with Mo6S8 and Zn/Ni, Ni/Cd, Mn/Zn with Mo6Se8. The extraction of a solution of cation by an electrolytic process could open many ways of application in the mineral liquid waste management. This process is now being developed for investigations of real industrial liquid wastes. To establish an ion migration modeling, the diffusion coefficients of the various cations in each polycrystalline matrix were measured by various electrochemical techniques. Mobilities of each cation are close and the diffusion coefficients about 10-9 cm2.s-1 except for the selenious matrix through which ions Fe, Co, Ni are not transfer. The proposals of transfer mode for the optimal speeds result in considering, the conditionings in stoichiometry of the ETJ and to resort to low thicknesses for the junctions. The results presented confirm the potentiality of this new mode of treatment and allow considering a technology transfer for the valorization of industrial wastes

This thesis investigates the use of bromine intercalation of graphite as a method to simulate and investigate irradiation damage. In particular this study investigates the effects of intercalation on dimensional change on the macro and micro scales and how these changes combine to affect Young’s modulus. Highly Orientated Pyrolytic Graphite has been used to gather data as a close approximation to single crystal graphite. Three different grades of polycrystalline nuclear graphite have been used to investigate the effect of different microstructure on intercalation and subsequent property changes. The graphites have been characterized by optical microscopy, pycnometry and x-ray powder diffraction and texture measurements. A number of bespoke rigs were designed and manufactured to carry out sorption, tomography and laser vibrometry experiments.The results indicate that the rate of dimensional change for polycrystalline graphites is significantly lower than for single crystal graphites. Modelling of dimensional change suggests that the difference in expansion is due to closure of porosity. Closer investigation of the dimensional change within the microstructure shows that the majority of the dimensional change is driven by expansion of filler particles.The young’s modulus results show an initial increase in modulus followed by a decrease, which corresponds with empirical evidence for irradiated samples. It is postulated that the initial increase in modulus is due to crystal expansion and that the subsequent decrease is due to crack growth. After experimentation some samples show significant cracking which would appear to support this assertion.

This research aimed to develop technology and processes to further beneficiate two southern African bentonites for applications in polymer/clay nanotechnology. The bentonites were from the Koppies mine in South Africa, and the Boane mine in Mozambique. The work was divided into two parts: (i) preparation of organomodified nanoparticulate smectite clays, and (ii) preparation of their poly(ethylene-co-vinylacetate) nanocomposites. Nanoparticulate organobentonites were prepared using purified bentonites. The conventional organomodification process uses a very low concentration of bentonites at 80 oC. In this study, a novel method was developed: concentrated slurries of naturally occurring Ca-bentonite partially activated with soda ash in the presence of a proprietary dispersant were contacted at ambient temperature with quaternary ammonium surfactants. A known amount of bentonite dispersion was placed in a planetary mixer before the mixture. Likewise, a known amount of surfactant, up to 50% excess, based on the estimated cation exchange capacity (CEC) of the bentonites, was added while mixing the dispersion. The surfactants added were either in solution or in powdered form. The intercalated bentonite was recovered by centrifugation and washed repeatedly with water until halide ions could not be detected using a 1M silver nitrate solution. The solids were dried at ambient temperature and humidity, and then crushed and milled into a fine powder using a mortar and pestle. Several instrumental techniques were used to characterise and examine the properties of the bentonite samples before and after organic treatment.The X-ray diffraction (XRD) results were consistent with: (i) paraffin-type extended chain intercalation; and (ii) interdigitated monolayer intercalation of the C12 and C14 single-chain alkyl surfactants and bilayer intercalation of the single-chain C16 surfactant and the surfactants with double alkyl chains. Fourier transform infrared (FTIR) spectroscopy analysis of the organobentonite powders confirmed disordered chain conformations. XRD also detected significant amounts of cristobalite in the samples of Boane bentonite (from Mozambique). This impurity could not be removed cost-effectively. The onset decomposition temperature ofthe present organobentonites was around 200 ºC, which is within the typical range of polymer/organoclay processing temperatures. The thermal stability of the organobentonites was independent of both the number of alkyl chain substituents and their length, and also independent of the degree of clay intercalation. SURFACTANT INTERCALATED KOPPIES AND BOANE BENTONITES FOR POLYMER NANOTECHNOLOGY ii Poly(ethylene-co-vinylacetate) nanocomposites were prepared with South African Koppies bentonite, organomodified with single-chain C12 (and polar 2-hydroxyethyl side chain) and double-chains C18 alkyl ammonium cationic surfactants. The later surfactant was intercalated both below and above the clay CEC. Nanocomposites were prepared by twin-screw melt compounding. Transmission electron microscopy (TEM) indicated the presence of mixed nanoand micron-sized clay morphologies. XRD studies revealed that the crystallinity of the particles improved and that the d-spacing values increased on incorporation of the modified bentonites in the polymer matrix. It is postulated that, rather than indicating polymer co-intercalation, this was caused by further intercalation of either excess surfactants or surfactant residues that were released by shear delamination of the clays during compounding. Improved mechanical properties were realised, especially when using the bentonite containing the longer double-chains surfactant intercalated at levels in excess of the CEC of the clay. The nanocomposites showed improved tensile modulus and elongation at break values at the expense of a reduction in impact strength, while tensile strength was about the same as for the neat polymer. / Thesis (PhD)--University of Pretoria, 2013. / gm2014 / Chemistry / unrestricted

Fatty acid intercalated layered double hydroxides were used as additives for Jojoba oil and polymer matrices. The first phase of the study was to intercalate carboxylic acids (C14 to C22). These were successfully intercalated into layered double hydroxides (LDHs), with the formula [Mg0.7Al0.3 (OH) 2](CO3)0. 15•0.5H2O. The one-pot synthesis consistently yielded a bilayer intercalated product for the range of acids employed. The intercalated anions had an orientation tilt angle of 55–63°, depending on the length of the fatty acid chain. However, there is an indication that the anion exchange process employed in this study is accompanied by probable dissolution and recrystallisation of the LDH. This is supported by the different growth habits and sizes of platelets observed through scanning electron microscopy (SEM). Moreover, the organo-LDH platelets were found to have varying MII/MIII compositions, ranging from 1.65 to 6, indicating that the one-pot synthesis yields an array of mixed metal hydroxides. Polymer composites, containing 5% and 10 wt.% of stearate intercalated layered double hydroxides (LDH-stearate) and neat layered double hydroxides (LDH-CO3), were prepared via melt-compounding to explore the use of LDHs as an additive. The stearate modified starting material was bilayer-intercalated clay. During melt compounding, excess stearates were released and the clay reverted to a monolayer-intercalated form. Comprehensive characterisation and study of the fatty acid-intercalated LDH showed that these organoclay hybrids exhibit thermotropic behaviour. This behaviour ultimately leads to the exudation of excess fatty acid. The exuded stearates were found to have lubricating and plasticising effects on the poly(ethylene-co-vinyl acetate) (EVA) and linear low density polyethylene (LLDPE) matrices. Strong hydrogen bond interactions between the chains of poly(ethyleneco- vinyl alcohol) (EVAL) and the clay platelet surfaces overwhelmed the lubrication effect and caused an increase in the melt viscosity of this matrix. The notched Charpy impact strength of this composite was almost double that of the neat polymer. It appears that this can be attributed to the ability of the highly dispersed and randomly oriented nanosized clay platelets to promote extensive internal microcavitation during impact loading. The creation of a large internal surface area provided the requisite energy dissipation mechanism. The study also considered fatty acid-intercalated LDH as an argillaceous mineral for potential use as a rheological additive in Jojoba oil. A minimum of 20 wt.% LDH in Jojoba oil formulation was found to be stable, i.e. it did not form separate layers on standing. The viscosity of the neat Jojoba oil demonstrated Newtonian behaviour, whereas the modified LDH/Jojoba oil formulation shear thinned, which is a typical non-Newtonian behaviour. Viscosity as a function of temperature showed complex rheological behaviour for the long chain fatty acids C16 to C22. The viscosity increase is assumed to be due to a combination of three events, which include the formation and changes of LDH microstructures within the oil, the loss of excess fatty acids into the oil matrix, and the formation of fatty acid crystal networks. Shear action also induced some delamination of the clay platelets. / Thesis (PhD(Eng))--University of Pretoria, 2012. / Chemical Engineering / unrestricted

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