Two classes of ion-channels comprising 22 members were prepared. Three members were linear oligo-esters with terephthalate core designed to span both leaflets of the bilayer; these were prepared in a modular synthesis in three linear steps. 19 half-channels based on cyclodextrins with functionalized primary-rims were prepared by the Huisgen Cu+-catalyzed [3+2]-cyclization; three distinct synthetic protocols were established to be applicable to these substrates. The voltage-clamp experiment was used to characterize the ion transport properties of these 22 compounds as well as 5 oligo-esters previously prepared by solid-phase synthesis. All but two were active in bilayers, with the majority of these compounds showing highly complex conductance activities. Exponentially voltage-dependent currents were observed for two compounds (both terephthalate-derived); exclusive “square-top” activities were observed for one solid-phase–derived compound and one cyclodextrin-based channels; fractal openings were observed for at least two cyclodextrin-based channels. An “activity grid” notation was proposed as an empirical, coarse, but model-free method of treating the complex data. Through an exhaustive analysis of previously published synthetic ion channels, disparate compounds were found to share modes of activity. Supporting software were developed to facilitate the preparation of activity grids from current traces acquired for the aforementioned 27 compounds. Resulting activity grids for individual experiments were collated to generate an activity profile for each compound, from which a structure–activity map was established and could be compared to the literature data. Four core findings emerged. First, the activity grid notation is sufficiently expressive to denote highly complex mixture of activities. Second, systematic application of the notation reduces selection bias in data analysis. Third, many synthetic ion channels share highly sim- ilar activities and suggests the participation of the lipids, water, and ions in pore-formation. Lastly, the cyclodextrin half-channels are generally membrane active, and their activities are clearly modulated by structural variations. / Graduate

"Multi-functionalized Side-chain Supramolecular Polymers:A Methodology Towards Tunable Functional Materials". Even as we see a significant growth in the field of side-chain supramolecular polymers in the last ten years, systems employing multiple non-covalent interactions have been scarcely studied. Non-covalent multi-functionalization provides unique advantages such as rapid optimization via reversible functionalization as well as for the tuning of materials properties by exploiting the differences in the nature of these reversible interactions. This thesis involves the design principles, synthesis & methodology of side-chain multi-functionalized polymers. The combination of the principles of a functionally tolerant & a controlled polymerization technique such as ROMP with multiple noncovalent interactions such as hydrogen bonding, metal coordination & Coulombic self-assembly has been used to synthesize multi-functionalized polymers. Furthermore, the orthogonality between hydrogen bonding, metal coordination & ionic self-assembly in random/block copolymers has been studied in detail. In order to validate the viability of this multi-functionalization methodology towards materials design non-covalent crosslinking of polymers was used as a potential application. Three classes of crosslinked networks have been studied: complementary multiple-hydrogen bonded networks, multiple-metal crosslinked networks, & multi-functionalized hydrogen bonded & metal coordinated networks. By using non-covalent multi-functionalization, important materials properties & its responsiveness towards chemical agents have been tuned & controlled to yield novel materials which would be difficult to be obtained via traditional covalent techniques or by using single non-covalent interactions.

Orientador: Prof. Dr. Wendel Andrade Alves / Tese (doutorado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2016. / Conjugados de moleculas organicas geralmente se arranjam em sistemas complexos multifasicos que sao muito sensiveis ao processamento e ao ambiente quimico local. E alem disso, as interacoes intermoleculares e presenca de moleculas assimetricas introduzem variacoes estruturais no empacotamento molecular e no ordenamento em maiores escalas, o que diretamente afeta as mais diferentes propriedades fisico-quimicas e processos associados ao material estudado. Nesta tese duas abordagens envolvendo a formacao de materiais hibridos baseados em estruturas supramoleculares de polimeros e peptideos foram estudadas. A primeira trata da obtencao de blendas polimericas baseadas em poli-(¿Ã)-caprolactona (PCL) com polianilina (PANI) dopada pelo aminoacido N-Acetil-L-Cisteina (NAC) pelos metodos de solution casting e eletrofiacao. Os materiais foram caracterizados acerca das suas propriedades morfologicas, estruturais e moleculares em diferentes escalas. A partir dos resultados foi obtida a relacao entre a variacao das propriedades da blenda em relacao a diferentes concentracoes de NAC. Os resultados indicam que a NAC aumenta a organizacao e cristalinidade da blenda, alem de mostrar a relacao entre o processamento e a micro-nanoestrutura interna. E mostrado tambem o processo de dopagem da PANI pela acido conjugado da NAC, o qual favorece a formacao de diferentes formas de PANI. Os resultados indicam a formacao de uma estrutura supramolecular mantida por interacoes intermoleculares do tipo enxofre-¿Î (SH-¿Î) entre a PANI e a NAC. O segundo topico e sobre o estudo da formacao de matrizes conjugadas de estruturas supramoleculares de L,L-difenilalanina (FF-MNSs) em duas diferentes estruturas cristalinas, hexagonal P61 e ortorrombica P22121, com microperoxidase-11 (MP11) e o polieletrolito poli(alilamina hidroclorada) (PAH). Com o uso de tecnicas espectroscopicas discute-se o papel da estrutura cristalina na interacao entre as FF-MNSs e a MP11. E por eletroquimica o papel do PAH no sistema e elucidado. Com auxilio de simulacoes computacionais e observada a dopagem do material com estrutura ortorrombica por moleculas de PAH, diminuindo a energia de band-gap em ~1 eV. A cinetica da reacao de catalise de reducao de H2O2 e estudada, e entao e mostrado o processo de deteccao de glicose pela enzima glicose oxidase suportada na matriz hibrida formada. Os resultados presentes nesse trabalho contribuem com o estudo de novos conjugados supramoleculares de peptideos e polimeros. Assim a interacao entre as diferentes moleculas, e os fatores que levam a essas interacoes sao discutidas, trazendo consigo novas consideracoes sobre a formacao de materiais supramoleculares. / Organic molecules conjugates usually arrange itself in complex multiphasic systems that are very sensitive to processing and the local chemical environment. Beyond that, the intermolecular interactions and the presence of asymmetric molecules introduces structural variations in the molecular packing and larger scales order, which directly affects different physical-chemical properties and processes associated with the studied materials. In this thesis, two approaches involving the formation of hybrid materials based on supramolecular structures of polymers and peptides were studied. The first one deals with the obtaining of polymer blends based on poly-(å)-caprolactone (PCL) with polyaniline (PANI) doped by the amino acid N-Acetyl-L-Cysteine (NAC) by the solution casting and electrospinning methods. The materials were characterized by its morphologic, structural and molecular properties in different size scales. From the obtained results, the relation between the changes on the blends properties and different NAC concentration was achieved. The results indicate that NAC enhances the organization and the crystallinity index of the blends, and shows the relation between the obtaining method and the internal micro-nanostructure. Later it is shown that NAC also modify the molecular properties of PANI. Using spectroscopic techniques, the doping process of PANI by the conjugate acid of NAC was studies, showing that NAC favors the formation of different PANI forms. The results indicate the formation of a supramolecular structure maintained by sulfur-ð (SH-ð) interactions between PANI and NAC. The second topic is about the formation of conjugated matrixes of supramolecular structures of L,L-diphenylalanine (FF-MNSs) in two different crystal structures, the hexagonal P61 and the orthorhombic P22121, with microperoxidase-11 (MP11) and the polyelectrolyte poly(allylamine hydrochloride) (PAH). Using spectroscopic techniques, the role of the crystal structure in the interaction between the FF-MNSs and MP11 is discussed. And with electrochemical experiments the role of PAH is elucidated. And using computational simulations it is observed the doping of the orthorhombic structure by PAH molecules, decreasing the band-gap energy in about 1eV. The kinetics of the catalytic reduction reaction of hydrogen peroxide was studies, and is shown as proof of concept the detection of glucose by the enzyme glucose oxidase supported in the obtained hybrid matrix. The presented results in this work contribute with the study of novel supramolecular conjugates of peptides and polymers, and the factors that lead to those interactions are discussed, bringing with it new considerations about the formation of supramolecular materials.

Dans un premier temps, ce travail décrit la méthodologie de synthèse vers de nouveaux coilants bipyridines-bis-α-cyclodextrines comportant deux ou trois unités bipyridines pour la réalisation de systèmes coordinants tétra- ou octaédriques singuliers. La réactivité des différentes étapes a été étudiée et des molécules clés de la synthèse totale des ces systèmes ont été synthétisées grâce à des réactifs ou réactions issus du laboratoire. Dans un deuxième temps, la synthèse d'un nouveau podant tris-bipyridines-α-cyclodextrine a également été réalisée et ses propriétés de complexation avec les cations de transition ont été étudiées par spectroscopie UV-visible et dichroïsme circulaire. La géométrie hélicoïdale fortement chirale a également été résolue dans le cas de certains complexes de ce podant avec des métaux de transition de dureté intermédiaire / Firstly, this work describes the synthesis methodology toward new bipyridines-bis-α-cyclodextrins coilants with two or three bipyridine units for the achievement of tetra- or octahedral coordinant systems. The reactivity has been studied and key molecules have been synthesisedthanks to our laboratory's methodologies. Sedondly, the synthesis of a new tris-bipyridines-α-cyclodextrin podand has also been performed and its complexation properties with transition cations have been studied by UV-visible spectroscopy and circular dichroism. The highly chiral helix geometry has also been resolved in the case of some metal podendates with borderline transition metals

Orientador: Prof. Dr. Wendel Andrade Alves / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2017. / As inovacoes tecnologicas voltadas ao desenvolvimento de biomateriais vem contribuindo na pesquisa por dispositivos de alto desempenho e funcionalidades especificas. O presente projeto de pesquisa teve por objetivo o estudo de processos de automontagem molecular de compostos peptidicos anfifilicos visando a sua aplicacao em catalise estereosseletiva. Em linhas gerais, compostos peptidicos anfifilicos foram sintetizados e posteriormente nanoestruturados e avaliados quanto a sua eficiencia na catalise de reacoes aldolicas diretas em meio aquoso, o que e altamente desejavel do ponto de vista economico e ambiental. De forma geral, os lipopeptideos estudados sintetico GCP (Guanidiniocarbonyl pyrrole), L-triptofano e glicina, ligados covalentemente a uma ou duas cadeias alifaticas longas (16 ou 18 carbonos), levando a moleculas com caracteristicas de surfactante. Estudos de microscopia e espalhamento de raios X a baixos angulos (SAXS) indicaram a formacao de diferentes morfologias. Em seguida, essas estruturas foram aplicadas como sistemas cataliticos supramoleculares na reacao aldolica direta estereosseletiva entre a cicloexanona e o p-nitrobenzaldeido em agua como exclusivo solvente. As nanoestruturas formadas apresentaram-se como sistemas cataliticos excelentes nos testes realizados, nos quais excelentes taxas de conversao (>99%), elevados niveis de diastereosseletividade (ds = 94:6) e bons niveis de enantiosseletividade (ee = 92%) foram obtidos. Esses resultados permitiram um estudo sistematico que demonstrou o potencial de arranjos lipopeptidicos na catalise de reacoes aldolicas promovidas em um meio ambientalmente adequado. Com isso, a sintese estereosseletiva de ¿À-hidroxi-cetonas, que sao importantes fragmentos presentes em produtos naturais com atividade biologica, foi promovida de uma maneira inovadora, elegante e com reducao de residuos quimicos gerados. O presente trabalho conta ainda com uma segunda parte onde sao apresentados os resultados envolvendo os estudos estruturais de anticorpos cataliticos de aldolase. Diversos trabalhos da literatura mostram excelentes resultados envolvendo a aplicacao desses anticorpos como catalisadores de reacoes aldolicas, entao foi promovido um estudo utilizando a tecnica de SAXS acerca das variacoes estruturais que o anticorpo sofre em funcao dos substratos aplicados. / Technological innovations focused on the development of biomaterials have contributed to the research of high performance devices and specific functionalities. This research project had the objective of the study of self-assembling processes of amphiphilic peptides aiming their application in stereoselective catalysis. In general terms, amphiphilic peptides were synthesized and nanostructured and evaluated considering their efficiency in the catalysis of direct aldol reactions in aqueous media, which is highly desirable from an economic and environmental point of view. In general, the studied lipopeptides have the amino acids L-proline, L-arginine or the synthetic amino acid GCP (Guanidiniocarbonyl pyrrole), L-tryptophan and glycine, covalently linked to one or two long aliphatic chains (16 or 18 carbons), leading to molecules with surfactant characteristics. Microscopy and small angle X-ray scattering (SAXS) studies showed the formation of distinct morphologies. These compounds were then applied as supramolecular catalytic systems in the stereoselective direct aldol reaction between cyclohexanone and pnitrobenzaldehyde in water as the solvent. The produced nanostructures acted as excellent catalytic systems in the performed tests, in which excellent conversions (>99%), high diastereoselectivities (ds = 94:6) and good enantioselectivities (ee = 92%) were obtained. These results allowed a systematic study that demonstrated the potential of lipopeptide arrangements in the catalysis of aldol reactions promoted in an environmentally suitable environment. Furthermore, the stereoselective synthesis of â-hydroxy ketones, which are important fragments present in natural products with biological activity, was promoted in an innovative and elegant way, with reduction of the generated chemical residues. The present work also has a second part where the results involving the structural studies of aldolase catalytic antibodies are presented. Several studies of the literature show excellent results involving the application of these antibodies as catalysts of aldol reactions, so a study using SAXS regarding the structural variations that the antibody undergoes as a function of the substrates applied was promoted.

Submitted by isabela.moljf@hotmail.com (isabela.moljf@hotmail.com) on 2017-05-22T15:47:02Z No. of bitstreams: 1 felipemagestescaldini.pdf: 2661212 bytes, checksum: 68339e788685f873502440bba4b26794 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-22T17:40:25Z (GMT) No. of bitstreams: 1 felipemagestescaldini.pdf: 2661212 bytes, checksum: 68339e788685f873502440bba4b26794 (MD5) / Made available in DSpace on 2017-05-22T17:40:25Z (GMT). No. of bitstreams: 1 felipemagestescaldini.pdf: 2661212 bytes, checksum: 68339e788685f873502440bba4b26794 (MD5) Previous issue date: 2013-02-25 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho descreve a síntese e caracterização de oito compostos de coordenação, [Zn(PYA)2(H2O)2]n (1), [Mn(PYA)2(H2O)2]n (2), {[Co(2,5PDC)(H2O)2] .H2O}n (3), [Mn(2,5HPDC)2(H2O)2] (4), [Ni(2,3HPDC)2(H2O)2] (5), {[Cu(3,4HPDC)2(H2O)2] .DMSO}n (6), {[Co(3,4HPDC)2(H2O)2](H2O)(DMSO)}n (7) e {[Cu2(3,4HPDC)2(H2O)5]}n (8) contendo ligantes da família dos ácidos piridinodicarboxílicos, que são N-, O- doadores e podem proporcionar modos de coordenação interessantes frente aos íons metálicos da 1º série de transição selecionados para o trabalho (Mn2+, Co2+, Ni2+, Cu2+ e Zn2+). Os ligantes utilizados foram os ácidos 2,3 piridinodicarboxílico (2,3H2PDC), 2,5 piridinodicarboxílico (2,5H2PDC), 3,4 piridinodicarboxílico (3,4H2PDC), trans-3-(piridil)-acrílico (HPYA) e 3-(2-tienil)acrílico (HTA). Dos oito compostos descritos neste trabalho, apenas três são inéditos. Os compostos inéditos, (6), (7) e (8) foram caracterizados por análise elementar, análise térmica (TG e DTA), espectroscopia vibracional na região do infravermelho, e difração de raios X por monocristal. Nesses três compostos, em acordo com os dados espectroscópicos, a difração de raios X por monocristal mostrou que os ligantes se apresentam na forma parcialmente desprotonada e além disso, observou-se a formação de redes poliméricas. Em todos os casos, os arranjos supramoleculares são formados por ligações de hidrogênio. Todos os compostos apresentam o metal central em geometria octaédrica, com excessão do composto (8) que mostra dois centros de Cu(II), sendo um em geometria octaédrica e outro como pirâmide de base quadrada. Foi feita também a descrição topológica das redes poliméricas formadas, com auxilio do programa TOPOS. Dentre os compostos apresentados neste trabalho, apenas os compostos (4) e (5) não formam cadeias ou redes poliméricas. O teste de capacidade de adsorção de gás para o composto polimérico (6) foi feito através das isotermas de N2, utilizando o método BET. / This work describes the synthesis and characterization of eight coordination compounds, [Zn(PYA)2(H2O)2]n (1), [Mn(PYA)2(H2O)2]n (2), {[Co(2,5PDC)(H2O)2] .H2O}n (3), [Mn(2,5HPDC)2(H2O)2] (4), [Ni(2,3HPDC)2(H2O)2] (5), {[Cu(3,4HPDC)2(H2O)2] .DMSO}n (6), {[Co(3,4HPDC)2(H2O)2](H2O)(DMSO)}n (7) and {[Cu2(3,4HPDC)2(H2O)5]}n (8) containing N-,O-donor ligands from pyridinedicarboxylic acids family that can provide interesting coordination modes toward the first row transition metal ions (Mn2+, Co2+, Ni2+, Cu2+ e Zn2+). 2,3 pyridinedicarboxylic (2,3H2PDC), 2,5 pyridinedicarboxylic (2,5H2PDC), 3,4 pyridinedicarboxylic (3,4H2PDC), trans-3-(pyridyl)-acrylic (HPYA) and 3-(2-thienyl)acrylic acid (HTA) were used as ligands. Among the eight compounds described in this work, only three are unpublished. The novel compounds, (6), (7) and (8) were characterized by elemental analysis, thermal analysis (TG and DTA), infrared vibrational spectroscopy, and single crystal X-ray diffraction analysis. In these three compounds, in accordance with the spectroscopic data, single crystal X-ray diffraction analysis showed that the ligands are present in partially deprotonated form and furthermore, the formation of polymeric networks was observed. In all cases, supramolecular arrangements are formed by hydrogen bonds. All compounds show the metal center in octahedral geometry, except compound (8) that has two Cu (II) centers; one in octahedral geometry and other in a square pyramidal geometry. A topological description was also made for the polymeric networks formed, supported by the software TOPOS. Among all compounds presented in this work, only compounds (4) and (5) do not form polymeric chains or networks. The gas adsorption capacity test was realized for the polymeric compound (6), through N2 isothermal, using BET method.

Hydroxyapatite (HAP) coatings are used in orthopaedic surgery for bone regeneration. Current methods of phase quantification of HAP coatings suffer from drawbacks. A novel methodology of quantitative phase analysis of HAP coatings has been devised and validated. This method, based on whole pattern fitting with a fundamental parameters approach, incorporates amorphous calcium phosphate (ACP) and apatite phases into structural refinements. A comparison of the structural and chemical properties of plasma sprayed (PS) and novel electrodeposited (ED) HAP coatings has been conducted. ED coatings contained less ACP and more preferred orientation than the PS coatings, although the stoichiometry was similar. In vitro investigations of PS and ED coatings in simulated body fluid and foetal calf serum revealed that both are bioactive. A carbonated apatite layer produced on the ED coatings was -0.7μm thick with a stoichiometry and chemical constituents similar to that of natural bone apatite. PS coatings produced a nanocrystalline carbonated apatite layer (-4μm). For the first time it has been possible to model crystalline HAP and nanocrystalline apatite as independent phases and obtain accurate lattice parameters for each. A positive linear correlation has been made between microstrain and the solubility of HAP and carbonated apatites. Dissolution studies have shown that the behaviour of HAP and carbonated apatite is dominated by crystallite size at low undersaturation and by crystallite size and microstrain at high undersaturation for crystallites between -30OA- 1000A. Metastable equilibrium occurred for crystallites <_400A at low undersaturation. Carbonate content did not affect the solubility or dissolution behaviour. A novel technology for coating polymeric tape with HAP for potential use in anterior cruciate ligament reconstruction has been devised. Mechanical tests have demonstrated that no adverse properties are induced by the coating technology. Cell culture studies have shown that the HAP layer is capable of enhanced attachment, proliferation and differentiation of osteoblast cells compared to uncoated tape.

Cette thèse se focalise sur la synthèse multi-étape et l’étude par différentesspectroscopies de plusieurs systèmes supramoléculaires photoactifs. Des sondes fluorescentesmoléculaires capables d’éjecter le Ca2+ de façon réversible ont été élaborées afin de modulerl’arrivée et le départ d’ions Ca2+ dans un milieu. Ces photoéjecteurs basés sur le récepteur àCa2+ BAPTA (l’acide 1,2-bis(2-aminophénoxy)éthane-N,N,N’,N’-tetraacétique) et sur desfluorophores photodimérisables, ont été synthétisés. Leurs comportements photochimiquesont été testés. Ensuite, des échangeurs d’ions moléculaires ont été développés afin d’étudier lavariation de Ca2+ et Mg2+ à partir de deux récepteurs synthétiques. Ils sont basés sur deuxrécepteurs hydrosolubles, le BAPTA pour Ca2+ et l’APTRA (l’acide o-aminophénol-N,N,Otriacétique)permettant de complexer sélectivement le Mg2+. Ces récepteurs ont été conçusafin que Mg2+ et Ca2+ ne puissent être complexés simultanément. Enfin, des boites quantiquesdécorées de ligands pyrène ont été synthétisées pour obtenir un senseur optique à oxygène. / This thesis focuses on the multi-step synthesis and study of several photoactivesupramolecular systems by different spectroscopies. Fluorescent sensors capable of reversiblyejecting Ca2+ were developed in order to control the arrival and depart of Ca2+ ions insolution. These photoejectors were synthesized based on the Ca2+ receptor BAPTA (1,2-bis(2-aminophenoxy)ethane-N,N,N’,N’-tetraacetic acid) and on photodimerizable fluorophores andtheir photochemical behaviour was tested. Molecular ion exchangers were developped inorder to study the variation of Ca2+ and Mg2+ with two synthetic receptors. Their molecularstructures hydrosoluble receptors: BAPTA for Ca2+ and APTRA (o-aminophenol-N,N,Otriaceticacid) allowing the selective complexation of Mg2+. Integration of these receptorsensures that Mg2+ and Ca2+ cannot be simultaneously complexed. Finally, quantum dotsdecorated at the surface with pyrene-containing ligands were synthesized to obtain aratiometric optical oxygen sensor.

The development of molecular receptors for anion recognition has become an important aspect of supramolecular chemistry. In this thesis, we focused our attention to the study of systems for fluoride recognition in water. Fluoride is indeed an anion of interest due to its implication in environmental and health related issues. Furthermore, its small size and high hydration energy make its recognition in water particularly challenging.<p>Most of the synthetic systems reported for fluoride recognition have been extensively studied in organic solvents (DMSO, acetonitrile) using tetrabutylammonium fluoride (TBAF) as the source of fluoride. In many cases, titra- tion behaviours are observed that cannot be ascribed to a classical 1:1 binding isotherm, deprotonation problems of Brønsted-Lowry acid type of receptors aside. In the first part of our thesis we investigated, using a uranyl-salophen re- ceptor which recognizes fluoride via Lewis Acide/Base interactions, the origin of the unusual titration behaviour. Via UV/vis, 19F and 1H NMR spectroscopies, we have been able to highlight that the equilibrium between the fluoride and the corresponding bihalide ion, HF−2 ,which is inevitably generated along with the hydroxide anion in situ due to trace amounts of water, can be at the ori- gin of this singular behaviour. Our results put to light that when undertaking titrations with fluoride in DMSO, the fluoride–bihalide equilibrium can affect the data and that the latter species can even be the dominating species at low TBAF concentrations. When varying the solvent from DMSO to acetonitrile, the s-shape titration curves observed by UV/vis are no longer observed for the uranyl-salophene receptor that we studied. The fluoride-bifluoride equilibrium is still present but both of the anions generated in this process are recognised by the uranyl-salophene receptor with similar affinity constants above 10^6 M−1.<p>The second part of our work was devoted to finding ways to solubilize anion receptors that are efficient in organic solvents, into an aqueous environment. Two approaches were investigated: (i) grafting of the receptors onto silica nanoparticles and (ii) the micellar incorporation of the receptors. For the first strategy, we developed two silylated urea-based receptors. These receptors were first studied in organic solvents (DMSO and/or acetonitrile) where they showed selectivity, among halides, towards fluoride. Once grafted on the silica nanoparticles, due to the fact that hydroxyl groups and solvent molecules are present in the silica matrix, fluoride recognition was not possible.<p>We explored it with different simple H-bond based urea receptors in the second srategy. With the cationic surfactants, cetyl trimethyl ammonium chloride and bromide, the counter-ions of the micelles interfere with the fluoride recognition. With the neutral surfactant triton X-100, the incorporation of the anion receptors proved to be difficult. Moreover, the variations observed in the UV/vis spectra upon titrations were too small to be able to make any conclusions about fluoride recognition. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Ce travail de thèse s’inscrit dans le domaine de la chimie métallo-supramoléculaire. Plus particulièrement, nous avons développé une chimie d’auto-assemblage afin de créer des architectures à plusieurs composants formés à partir de motifs TiO4N2. D’un point de vue synthétique, l’objectif de ce travail résidait dans l’analyse des conséquences de modifications structurales apportées à l’un des composants, le ligand azoté bidentate, sur la nature des architectures générées. C’est autour du ligand 2,2’-bipyrimidine que ces variations structurales se sont concentrées. En effet, c’est à partir de ce ligand que l’hélicate circulaire [Ti3(L)3(bpym)3], qui nous a servi de composé de référence tout au long de cette thèse, a été créé. Le premier facteur examiné concernait l’introduction de groupements de taille croissante sur le squelette de la 2,2’-bipyrimidine. Puis, la conséquence d’une réduction de la taille d’un des cycles du ligand azoté bidentate a été évaluée. Enfin, la denticité du ligand azoté a été changée. Le deuxième but de cette thèse était d’explorer l’importance relative des facteurs enthalpiques et entropiques dans des réactions d’auto-assemblage à base de métaux de transition. Nous avons pu ainsi proposer une méthodologie générale de modélisation thermodynamique qui ne fait appel qu’au seul logiciel PACHA, moyennant la connaissance des structures tridimensionnelles des produits de départ et d’arrivée. / The subject of this thesis belongs to the field of metallosupramolecular chemistry. We have developed a self-assembled chemistry in order to create multicomponent architectures formed around TiO4N2 units. From a synthetic point of view, the major goal of this work was to analyse the consequences of structural variations performed on one component on the resulting self- assembled architectures. These variations involved the 2,2'-bipyrimidine ligand as this ligand was employed to create a circular helicate [Ti3(L)3(bpym)3], which was used as a reference compound throughout this thesis. The first factor considered concerns the introduction of groups of different sizes on the backbone of the 2,2'-bipyrimidine. Then, the consequence of a ring size reduction of the nitrogenous bidentate ligand was evaluated. Finally, the denticity of the nitrogenous ligand was changed. The second aim of this thesis was to model the enthalpy and entropy factors governing these self-assembled reactions driven by titanium (IV) centers. We were able to propose a general thermodynamic modeling methodology by using the PACHA software, through the sole knowledge of crystalline structures of the starting and final products.