Dissertations / Theses on the topic 'Aniões'

Doutoramento em Química
O objectivo deste trabalho foi o desenvolvimento de sensores químicos para aniões em solução aquosa. Os sensores basearam-se em cristais piezoelétricos de quartzo revestidos com macrociclos pirrólicos. Sensores com porfirinas, hexafirinas, ftalocianinas e uma rede metalo-orgânica como filmes de reconhecimento foram avaliados no que respeita à reversibilidade, sensibilidade, seletividade e tempo de vida. A sensibilidade aos aniões presentes nas águas minerais destinadas ao consumo humano dos sensores com macrociclos pirrólicos dependia dos grupos substituintes na periferia do macrociclo. A presença de grupos substituintes NH potenciou a sensibilidade, sendo o valor mais elevado obtido com o grupo NH-tosilo. Técnicas espectroscópicas permitiram mostrar que a principal interação entre o anião e o composto se fazia por meio de pontes de hidrogénio entre o anião e o grupo NH. A sensibilidade destes compostos dependia ainda da quantidade do composto depositado sobre o cristal. Nenhum dos sensores era específico, mas apresentavam variações na seletividade com o composto pirrólico sobre o cristal. O sensor com uma membrana polimérica que incorporou uma rede metalo-orgânica construída com moléculas de uma ftalocianina de magnésio com grupos NH-tosilo ligados por iões cobre apresentou coeficientes de seletividade muito diferentes de todos os restantes sensores. Uma língua eletrónica construída com três dos novos sensores foi capaz de determinar simultaneamente as concentrações dos iões HCO3-, Cl- e SO42- em amostras de água mineral engarrafada, não tendo os valores obtidos sido estatisticamente diferentes (α=0,05) daqueles que foram obtidos por cromatografia iónica ou volumetria.
The aim of this work was the development of chemical sensors for anions in aqueous solution. The sensors were based on piezoelectric quartz crystals coated with pyrrolic macrocycles. Sensors with porphyrins, hexaphyrins, phthalocyanines and a metal-organic framework as recognition films were evaluated with regard to reversibility, sensitivity, selectivity and lifetime. Sensitivity to anions present in mineral waters for human consumption of sensors with pyrrolic macrocycles depended on the substituent groups on the periphery of the macrocycle. The presence of substituent groups NH potentiates sensitivity. The highest sensitivity value was obtained with NH-tosyl groups. Spectroscopic data showed that the main interaction between the anion and the pyrrolic compound consisted in hydrogen bonds between the anion and the NH group. The sensitivity of these compounds also depended on the amount of the compound deposited on the crystal. None of the sensors was specific, but did show differences in selectivity according to the pyrrolic compound on the crystal. The sensor with a polymeric membrane which incorporated a metal-organic framework constructed with molecules of a magnesium phthalocyanine with NH-tosyl groups bonded with copper ions showed selectivity coefficients very different from all the other sensors. An electronic tongue constructed with three of the new sensors was able to simultaneously determine the concentrations of HCO3-, Cl- and SO42- ions in bottled mineral waters. Results were not statistically different (α = 0.05) from the ones obtained by ion chromatography or volumetry.

Doutoramento em Química
A aplicação de simulações de mecânica e dinâmica molecular ao estudo de sistemas supramoleculares tem adquirido, ao longo dos últimos anos, enorme relevância. A sua utilização não só tem levado a uma melhor compreensão dos mecanismos de formação desses mesmos sistemas, como também tem fornecido um meio para o desenvolvimento de novas arquitecturas supramoleculares. Nesta tese são descritos os trabalhos de mecânica e dinâmica molecular desenvolvidos no âmbito do estudo de associações supramoleculares entre aniões e receptores sintéticos do tipo [2]catenano, [2]rotaxano e pseudorotaxano. São ainda estudados complexos supramoleculares envolvendo receptores heteroditópicos do tipo calix[4]diquinona e pares iónicos formados por aniões halogeneto e catiões alcalinos e amónio. Os estudos aqui apresentados assentam essencialmente em duas vertentes: no estudo das propriedades dinâmicas em solução dos vários complexos supramoleculares considerados e no cálculo das energias livres de Gibbs de associação relativas dos vários iões aos receptores sintéticos. As metodologias utilizadas passaram por dinâmica molecular convencional e REMD (Replica Exchange Molecular Dynamics), para o estudo das propriedades em solução, e por cálculos de integração termodinâmica e MMPBSA (Molecular Mechanics – Poisson Boltzmann Surface Area), para a computação das energias livres de associação relativas. Os resultados obtidos, além de terem permitido uma visão mais detalhada dos mecanismos envolvidos no reconhecimento e associação dos vários receptores aos aniões e pares iónicos abordados, encontram-se, globalmente, de acordo com os análogos determinados experimentalmente, validando assim as metodologias empregadas. Em jeito de conclusão, investigou-se ainda a capacidade de um dos receptores heteroditópicos estudados para assistir favoravelmente na migração do par iónico KCl através da interface água-clorofórmio. Para tal, foram utilizadas simulações SMD (Steered Molecular Dynamics) para a computação do perfil de energia livre de Gibbs associada à migração do par iónico através da interface.
The use of molecular mechanics and molecular dynamics simulations in the study of supramolecular systems has gained enormous relevance in the recent years. Its use not only has lead to a better understanding of the formation mechanisms of those systems, as has supplied a mean to the development of new supramolecular architectures. In this thesis are reported the molecular mechanics and molecular dynamics studies undertaken in the course of the investigations related with the supramolecular associations between several anions and synthetic receptors such as [2]catenanes, [2]rotaxanes and pseudorotaxanes. In addition, supramolecular complexes involving heteroditopic receptors, derived from calix[4]diquinone moieties, and ion-pairs formed by halide anions and ammonium and alkali cations are also studied. The studies hereby reported are essentially based on two approaches: on the study of the dynamical properties of the considered supramolecular complexes in solution and on the computation of the Gibbs relative association free energies of the several ions to the synthetic receptors. The methodologies employed encompass conventional molecular dynamics and REMD (Replica Exchange Molecular Dynamics) simulations, for the study of solution properties, and thermodynamic integration and MM-PBSA (Molecular Mechanics – Poisson Boltzmann Surface Area) calculations, for the computation of the relative association free energies. The obtained results, apart from allowing for an insightful understanding of the mechanisms involved in the recognition and association processes of the receptors to the anions and ion-pairs under study, are found, globally, to be in close agreement with experimentally determined counterparts, thus validating the employed methodologies. Finally, the capability of one of the studied heteroditopic receptors to favourably assist the migration of the KCl ion-pair through a water-chloroform interface was also evaluated. For that purpose, SMD (Steered Molecular Dynamics) simulations were employed for the computation of the Gibbs free energy profile associated with the migration of the ion-pair through the interface.

Doutoramento em Química
No âmbito desta dissertação são apresentados novos recetores sintéticos baseados na plataforma macrocíclica tetraazacalix[2]areno[2]triazina incorporando bases de purina ou unidades de aminoácidos naturais. Estes recetores foram preparados tendo como objectivo o reconhecimento seletivo de fármacos e aniões biologicamente relevantes. No primeiro capítulo é apresentada uma revisão bibliográfica sobre recetores derivados de tetraazacalix[2]areno[2]triazina demonstrando-se que a funcionalização desta plataforma, nos anéis de triazina ou nos anéis benzénicos, encontra-se ainda na infância bem como a investigação das suas afinidades para aniões. Subsequentemente, considerando os aniões principais estudados nesta tese, aniões carboxilatos alifáticos, aromáticos e aminoácidos é apresentada uma revisão bibliográfica sobre os estudos de reconhecimento molecular reportados na literatura, entre derivados de calix[4]areno e este tipo de aniões. No segundo capítulo descrevem-se as sínteses de recetores com uma ou duas unidades de aminoácido, L-alanina (AC1A, AC2A) e L-triptofano (AC2T), ancoradas nos anéis benzénicos da plataforma tetraazacalix[2]areno[2]triazina. Como demostrado no capítulo 3, os grupos N-H dos azotos em ponte são locais de reconhecimento de aniões. Neste contexto, estes macrociclos foram também metilados nos azotos em ponte (Me4AC2A e Me4AC2T) de modo a direcionar o reconhecimento cooperativo de aniões exclusivamente através dos grupos N-H das unidades de aminoácidos. A lipofilicidade destas moléculas foi alterada por substituição dos átomos de cloro das triazinas por dihexilamina. Os compostos sintetizados foram caracterizados através de técnicas espetroscópicas complementadas em alguns compostos por difração de raios X de cristal único. No capítulo 3 apresentam-se os estudos de reconhecimento molecular entre os recetores sintetizados e aniões derivados de ácidos carboxílicos (mono, di e tricarboxílicos) alifáticos, aromáticos, isoméricos e aniões inorgânicos. Estes estudos foram efetuados em DMSO-d6 ou em CDCl3 por titulações de RMN de 1H com determinação das respetivas constantes de associação. Para os recetores AC1A e AC2A o reconhecimento da maioria dos aniões estudados ocorre simultaneamente através dos grupos N-H dos azotos em ponte e do N-H da amida do braço da L-alanina. Contudo, no caso do isoftalato e tricarboxilato, com dois e três grupos carboxilato em posição meta, ocorre preferencialmente através dos dois braços de L-alanina como sugerido por estudos de dinâmica molecular em DMSO. Os estudos de associação realizados para os macrociclos que contêm unidades de L-triptofano, AC2T e Me4AC2T, mostraram que o reconhecimento de aniões é efetuado preferencialmente através de ligações de hidrogénio estabelecidas com os grupos amida e amina do grupo indole dos braços de aminoácido em detrimento das aminas em ponte como em AC1A e AC2A. Para a série dos carboxilatos alifáticos verifica-se que o recetor Me4AC2A tem maior afinidade com o anião glutarato (K= 389 M-1, DMSO-d6) enquanto o recetor Me4AC2T associa-se mais fortemente com o anião oxalato (K= 776 M-1, CDCl3). Todas as Job plots efetuadas confirmaram que as entidades estudadas obedeciam a uma estequiometria recetor/anião de 1:1.
In this thesis new synthetic receptors based on a tetraazacalix[2]arene[2]triazine macrocyclic platform incorporating purine bases or amino acid derivatives are presented. These macrocycles were prepared to act as selective recognition receptors of drugs or biological relevant anions. The first chapter reviews previous work about derivatized tetraazacalix[2]arene[2]triazine receptors, showing that the functionalization of either the triazine or the benzene rings for this platform is still in its infancy, which also applies for the investigation of its affinity to anions. Considering the anions studied in this thesis, carboxylate anions such as aliphatic, aromatic and amino acids, a bibliographic revision about molecular recognition between calix[4]arenes and this type of anions is also presented. The second chapter discusses the synthesis of receptors with one or two unities of amino acids, L-alanine (AC1A, AC2A) and L-tryptophan (AC2T), anchored to the benzene rings of the tetraazacalix[2]arene[2]triazine platform. As shown in the chapter 3, the bridged NH groups act as recognition sites for anions. In this context, the bridged nitrogen atoms (Me4AC2A e Me4AC2T) of the macrocycles were methylated to direct the cooperative recognition of the anions towards the NH group units of the amino acids. The lipophilicity of these molecules changed with the substitution of the chlorine atoms on the triazine by di-hexylamine. The compounds were characterized by spectroscopic techniques and in some cases by single crystal X-ray analysis. In chapter 3, molecular recognition studies between the synthesized receptors and carboxylic acid derivatives (mono, di and tricarboxylics) such as aliphatic, aromatic, isomeric, amino acids and inorganic anions are presented. These studies were performed either in DMSO-d6 or CDCl3 by 1H NMR titrations followed by determination of association constants. For the receptors AC1A and AC2A the recognition of the majority of the anions is done by the NH bridged groups and the NH group of the L-alanine amide. However, in the case of the isophtalate and the tricarboxylate anions, containing respectively two and three carboxylate groups in the meta position, the recognition occurs preferentially with the two arms of the L-alanine, as suggested by molecular dynamic studies in DMSO. The association studies performed on the macrocycles derivatized with L-tryptophan, AC2T and Me4AC2T, showed that the recognition of the anions occurs, preferentially, by hydrogen bonding with the amide and the pyrrole groups of the amino acid arms instead of the bridged amines as verified for AC1A and AC2A. For the aliphatic carboxylates it was observed that the receptor Me4AC2A as higher affinity for the glutarate (K= 389 M-1, DMSO-d6) anion while the receptor Me4AC2T associates more strongly with the oxalate anion (K= 776 M-1, CDCl3). Every Job plots show that the entities formed obey a 1:1 receptor/anion stoichiometry.

Doutoramento em Química
A presente dissertação descreve, essencialmente, o desenvolvimento de novos métodos de funcionalização de calix[4]pirróis. O uso desses calix[4]pirróis, bem como o de porfirinas e ftalocianinas, como sensores de aniões, incluindo a determinação das suas constantes de afinidade é igualmente discutido. Esta dissertação encontra-se dividida em três partes distintas. Na primeira é feita uma revisão bibliográfica acerca das metodologias de síntese dos calix[4]pirróis, bem como das suas características e aplicações. A segunda parte encontra-se subdividida em diversos pontos de acordo com o tipo de funcionalização realizada nos calix[4]pirróis. No primeiro ponto desta parte encontram-se discutidos a síntese e a caracterização do mesooctametilcalix[ 4]pirrol-2-carbaldeído e do 3-(meso-octametilcalix[4]pirrol-2- il)propenal bem como os resultados obtidos da funcionalização destes aldeídos por reacções de cicloadição 1,3-dipolar. Esses aldeídos foram usados para gerar iletos de azometino, os quais foram “apanhados” com diversos dipolarófilos, tais como o fumaronitrilo, o fumarato de dimetilo, a N-(4- metoxifenil)maleimida, a 1,4-benzoquinona e a 1,4-naftoquinona. Ambos os calixpirróis com grupo formilo deram origem a aductos de cicloadição 1,3- dipolar com rendimentos moderados ou bons, principalmente quando se utilizou fumaronitrilo, fumarato de dimetilo ou N-(4-metoxifenil)maleimida como dipolarófilos. Neste estudo verificou-se que quando as quinonas eram utilizadas como dipolarófilos apenas eram obtidos os cicloaductos do 3-(mesooctametilcalix[ 4]pirrol-2-il)propenal. No segundo ponto descrevem-se as reacções de condensação aldólica e de Knoevenagel do mesooctametilcalix[ 4]pirrol-2-carbaldeído e do 3-(meso-octametilcalix[4]pirrol-2- il)propenal. Verificou-se a ausência de resultados para as reacções de condensação aldólica mas resultados muito satisfatórios para as reacções de Knoevenagel. Foram utilizados como compostos metilénicos activados a indano-1,3-diona, o 1,3-bis(dicianometilideno)indeno, o malononitrilo, o cianoacetato de etilo, o malonato de dietilo e o ácido de Meldrum. No penúltimo ponto encontram-se discutidas as reacções dos dois aldeídos com aminas bem como a sua redução e posterior tentativa de funcionalização dos calixpirróis com grupo hidroxilo. Em ambas as tentativas os resultados foram pouco satisfatórios. No último ponto da segunda parte descrevem-se, pormenorizadamente, os métodos de síntese, purificação e caracterização estrutural dos diversos compostos sintetizados. Na terceira parte são descritos os testes dos novos calix[4]pirróis sintetizados e também de outros derivados tetrapirrólicos, nomeadamente porfirinas e ftalocianinas, com aniões. Os calix[4]pirróis sintetizados demonstraram capacidade de interagir com diferentes aniões, e a sua capacidade de interacção é dependente dos grupos funcionais introduzidos. Verificou-se que os compostos com grupos ciano conjugados com um anel pirrólico do macrociclo apresentam constantes de afinidade mais elevadas para os aniões. A concluir esta dissertação encontra-se uma revisão da literatura sobre a utilização de porfirinas como sensores de aniões. Apresentam-se também os resultados obtidos com duas porfirinas e uma ftalocianina em tal aplicação. As porfirinas testadas apresentam elevadas constantes de afinidade com os iões fluoreto e di-hidrogenofosfato. No caso da ftalocianina verificou-se que esta interage com vários aniões, bem como com metanol e sulfóxido dimetílico, originando soluções de cores muito diferentes.
The present document reports mainly the functionalization of calix[4]pyrroles and their application as anion sensors. This work is organized into three distinct parts. In the first one, through a review of the literature, we discuss the general characteristics of calix[4]pyrroles and the synthetic methodologies used for their synthesis. The second part is subdivided in several points according to the type of functionalization done in the calix[4]pyrrole. In the first point we describe the synthesis and structural characterization of meso-octamethylcalix[4]pyrrole-2- carbaldehyde and 3-(meso-octamethylcalix[4]pyrrol-2-yl)propenal and their subsequent participation in 1,3-dipolar cycloaddition reactions. The reaction of these aldehydes with sarcosine generated azomethine ylides which were trapped with several dipolarophiles such as fumaronitrile, dimethyl fumarate, N- (4-methoxyphenyl)maleimide, 1,4-benzoquinone and 1,4-naphthoquinone. The use of fumaronitrile, dimethyl fumarate and N-(4-methoxyphenyl)maleimide as dipolarophiles lead to the corresponding cycloadducts in moderate to good yields, with both calix[4]pyrroles. When quinones were used, the cycloadducts were obtained only with 3-(meso-octamethylcalix[4]pyrrol-2-yl)propenal. In the second point we describe the use of the two calix[4]pyrrole aldehydes in aldol condensations and Knoevenagel reactions. It was observed the absence of results for the aldol condensations but very satisfactory results for the Knoevenagel reactions. Indan-1,3-dione, 1,3-bis(dicyanomethylidene)indane, malononitrile, ethyl cyanoacetate, diethyl malonate and Meldrum's acid were used as active methylene compounds. The reactions of formyl calix[4]pyrroles with amines, the reduction of the formyl groups of the calix[4]pyrroles and the subsequent functionalization of the resulting hydroxyl groups are also discussed. In both cases the results were unsatisfactory. In the last point of this part, we describe in detail the synthesis, purification and structural characterization of the new synthesized compounds. In the third part of this thesis we describe the tests performed with the new synthesized calix[4]pyrroles and with other tetrapyrrolic derivatives, namely porphyrins and phthalocyanines, with anions. The results show that the ability of the synthesized calix[4]pyrroles to interact with different anions is highly dependent on the introduced functional groups. The cyano groups conjugated with one pyrrole of the macrocycle increase the affinity of these compounds to anions. At the end of the document, it can be found the results obtained with two new porphyrins and a phthalocyanine acting as anion sensors. The porphyrins showed higher affinity constants for fluoride and dihydrogenophosphate anions. The phthalocyanine used showed high affinity constants for a set of anions, as well as for neutral molecules such as dimethyl sulfoxide and methanol, displaying sharp color variations.
FCT - SFRH/BD/32219/2006
FCT - PTDC/QUI/74150/2006

Mestrado em Química Orgânica e Produtos Naturais
O trabalho apresentado ao longo desta dissertação teve como objetivo a síntese de novos calix[4]pirróis contendo grupos sulfonamida de modo a torná-los mais seletivos na complexação com aniões. Esta dissertação está dividida em três capítulos essenciais. O primeiro apresenta uma breve introdução focando as características, métodos de síntese e funcionalização bem como as aplicações dos calix[4]pirróis. No capítulo que se segue encontra-se descrito o trabalho de síntese, purificação e caracterização de novos compostos, tais como dipirrometano, calix[4]pirróis e calix[4]firinas. A caracterização dos compostos obtidos foi realizada recorrendo a espectroscopia de ressonância magnética nuclear e espectrometria de massa. Nesta parte também são descritos e apresentados os estudos onde se verifica a capacidade dos calix[4]pirróis e dos dipirrometanos sintetizados atuarem como sensores de aniões. Esta deteção é feita recorrendo à leitura da absorvância das soluções na zona do visível e utilizando o método indireto. No último capítulo descreve-se, pormenorizadamente, os métodos de síntese e de purificação e caracterização estrutural dos compostos sintetizados.
The work presented in this dissertation lays on the synthesis of new calix[4]pyrroles with sulfonamide groups aiming to obtain novel selective sensors for anion binding applications. This dissertation is the combination of three essential chapters. The first one introducing the subjects of characterization, synthetic routes and functionalization, as well as the applications of calix[4]pyrroles. The following chapter describes the synthesis implemented for the proposed work, purification and characterization of the new compounds, such as dipyrromethanes, calix[4]pyrroles and calix[4]phyrines. The compounds were characterized by nuclear magnetic resonance (1H NMR, 13C NMR, and bidimensional techniques when required) and mass spectrometry techniques. It is also presented the anion binding tests using compounds 31, 35a, 35b, 37a and 37b. The ability of such compounds to act as anion sensor was followed by UV-Vis spectroscopy using the indirect method. The last chapter describes the experimental procedures and the structural characterization of synthesized compounds.

Doutoramento em Química
Nesta tese, desenvolvida no âmbito do Programa Doutoral em Química da Universidade de Aveiro, foram desenvolvidos novos receptores sintéticos construídos a partir da plataforma macrocíclica tetraazacalix[2]areno[2]triazina ou do fragmento de isoftalamida. Ambas as unidades estruturais foram decora-das com grupos de reconhecimento molecular baseados em grupos amida e/ou ureia com o objectivo de actuarem como receptores selectivos de aniões com importância biológica ou farmacológica, incluindo acetato, oxalato, malo-nato, succinato, glutarato, diglicolato, L- e D-NHBoc-alanina, (S)- e (R)-fenilpro-panoato, (S,S)- e (R,R)-tartarato, fumarato, maleato, Cl-, HCO3-, H2PO4-, HSO4- e SO42-. No Capítulo 1 é efectuada uma revisão bibliográfica dos desenvolvimentos recentes na síntese, caracterização estrutural e aplicações de receptores fun-cionais relacionados com os desenvolvidos no âmbito desta tese, com especial incidência para aqueles que foram estudados como receptores de aniões. Neste domínio, enquanto que receptores derivados da isoftalamida têm sido bastante estudados ao longo das últimas décadas, o desenvolvimento de receptores de aniões inspirados em heteracalix[2]areno[2]triazinas ainda se encontra a dar os primeiros passos. No Capítulo 2 é apresentada a síntese de quatro novos macrociclos derivados de tetraazacalix[2]areno[2]triazina incorporando um ou dois braços de L-alanina (A1, A2) ou de L-leucina (L1, L2) nos anéis benzénicos, e derivados com grupos amida como unidades de reconhecimento. Adicionalmente, são também apresentados dois novos azacalix[2]areno[2]triazinas contendo um (U1) ou dois (U2) braços com grupos ureia substituídos com um grupo (S)-metilbenzílico. Foram ainda preparados os macrociclos A2Me4 e U2Me4 por metilação dos átomos de azoto em ponte de A2 e U2, os quais foram posterior-mente utilizados em estudos de associação. Os compostos sintetizados foram caracterizados através de técnicas espectroscópicas, complementadas por difracção de raios X de cristal único no caso de U2Me4. O Capítulo 3 contempla os estudos de reconhecimento molecular entre os macrociclos A2Me4 e U2Me4 e os aniões derivados de ácidos mono- e dicarbo-xílicos alifáticos, ácidos carboxílicos isoméricos (enantiómeros e isómeros geométricos), aminoácidos e polioxaniões acima referidos, excepto HCO3-. Os estudos de associação foram realizados através de técnicas de titulação por RMN 1H com determinação das respectivas constantes de afinidade. Todas as associações estudadas apresentaram uma estequiometria receptor-substrato 1:1 com excepção das associações formadas entre A2Me4 e U2Me4 com H2PO4- (1:2). Os complexos A2Me4∙SO42- e U2Me4∙(H2PO4-)2 são os mais estáveis com constantes de associação de 7,4 × 104 M-1 e superior a 105 M-2, respectivamente. O reconhecimento dos dicarboxilatos ocorreu através dos dois braços do macrociclo, com os aniões com grupos carboxilato separados por cadeias alifáticas mais compridas (glutarato e diglicolato) apresentando um melhor ajuste aos braços de A2Me4 e U2Me4. Não foi observado reconheci-mento enantiosselectivo de aniões. Em contraste, as constantes de afinidade para as associações com os aniões dos isómeros cis (maleato) e trans (fumarato) do ácido but-2-enodióico, de 89 e 4920 M-1 para A2Me4 e 481 e 4007 M-1 para U2Me4, respectivamente, sugerem selectividade de ambos os receptores para o fumarato. No Capítulo 4 é descrita a síntese de nove receptores acíclicos incorporando a unidade de isoftalamida (Iso-1 a Iso-9) e braços laterais com grupos de reconhecimento de aniões. Enquanto que o receptor Iso-1 possui como unida-des de reconhecimento apenas grupos amida, os receptores Iso-2, Iso-3, Iso-5, Iso-6, Iso-7 e Iso-9 possuem grupos amida e ureia, e os derivados Iso-4 e Iso-8 grupos amida e sulfonilureia. Em cada um destes compostos, os grupos de reconhecimento estão separados por uma cadeia etilénica cuja flexibilidade confere um melhor ajuste com os aniões. Os derivados de isoftalamida preparados foram caracterizados através de técnicas espectroscópicas. No Capítulo 5 são apresentados os estudos de associação realizados por técnicas de titulação por RMN 1H entre Iso-1, Iso-2, Iso-4, Iso-6 e Iso-8 com os aniões H2PO4-, HCO3-, Cl- e oxalato. Os receptores Iso-1, Iso-2 e Iso-6 apresentaram maior afinidade para o dianião, com valores de Kass de 6100, 7800 e 9800 M-1 respectivamente, e menor para Cl- (17 < Kass < 19 M-1). Foram sempre formadas associações mais estáveis com H2PO4- (294 < Kass < 427 M-1) comparativamente a HCO3-, sendo que a associação mais forte com este últi-mo foi determinada com Iso-2 (Kass = 95 M-1). As moléculas de Iso-4 e Iso-8 sofreram desprotonação dos grupos sulfonilureia na presença de todos os aniões excepto de Cl-. No Capítulo 6 apresentam-se as conclusões gerais e no Capítulo 7 descrevem-se os procedimentos experimentais e também os dados espectroscópicos dos produtos obtidos.
In this thesis, developed within the PhD Program in Chemistry of the University of Aveiro, new synthetic receptors containing the macrocyclic platform tetraazacalix[2]arene[2]triazine or the isophthalamide scaffold were synthesized. Both structural units contain amide and urea as binding units for pharmacologically or biologically relevant anions, such as acetate, oxalate, malonate, succinate, glutarate, diglycolate, L- and D-alanine, (S)- and (R)-phenylpropanoate, (S,S)- and (R,R)-tartarate, fumarate, maleate, Cl-, HCO3-, H2PO4-, HSO4- and SO42-. Chapter 1 is dedicated to the state of art in the synthesis, structural characterization and applications of functional receptors related with the synthetic molecules developed within the scope of this thesis, with special attention to the ones that have been studied as anion receptors. While isophthalamides have been quite exploited in the anion recognition chemistry throughout the last 20 years, receptors inspired in the azacalix[2]arene[2]triazine moiety are still giving their first steps. In Chapter 2 is presented the synthesis of four new azacalix[2]arene[2]triazines bearing one or two L-alanine (A1, A2) or L-leucine (L1, L2) arms based in amide groups as recognition units, which are attached to the macrocyclic benzyl rings. Two other azacalix[2]arene[2]triazines containing one (U1) or two (U2) arms bearing urea groups, previously prepared by coupling (S)-methylbenzyl isocyanate and ethanolamine, are also presented. The bridging NH groups of azacalixarenes A2 and U2 were subsequently methylated, yielding A2Me4 and U2Me4. Only the anion affinity of these two molecules was investigated. The synthesized compounds were characterized through spectroscopic techniques, complemented by single crystal X ray diffraction in the case of U2Me4. The 3rd Chapter comprises the molecular recognition studies between both macrocycles A2Me4 and U2Me4 and the anions derived from mono- and dicarboxylic aliphatic acids, isomeric carboxylic acids (enantiomers and geometrical isomers), amino acids and also polioxanions, except for HCO3-. These studies were carried out through 1H NMR titration techniques with determination of their binding constants. All associations presented a 1:1 receptor-substrate stoichiometry except for the ones between A2Me4 and U2Me4 with H2PO4- (1:2). It was determined that the most stable complexes were A2Me4∙SO42- and U2Me4∙(H2PO4-)2, with stability constants of 7,4 × 104 M-1 and higher than 105 M-2, respectively. The recognition of the aliphatic dicarboxylates occurred through both arms of the macrocycle, with the carboxylate groups separated by the longest aliphatic chains (glutarate and diglycolate) yielding the best fine-tuned associations. No enantiosselective recognition was observed with the studied chiral anions. In contrast, the affinity constants for the associations with both the cis (maleate) and trans (fumarate) anionic isomers of but-2-enedioic acid, of 89 and 4920 M-1 for A2Me4 and 481 and 4007 M-1 for U2Me4, respectively, suggest that both receptors show selectivity towards fumarate. In Chapter 4 is described the synthesis of nine new acyclic isophthalamide receptors (Iso-1 – Iso-9) bearing lateral arms with anion recognition groups. While Iso-1 has recognition units based only on amide groups, Iso-2, Iso-3, Iso-5, Iso-6, Iso-7 and Iso-9 have both amide and urea units, and Iso-4 and Iso-8 have amide and sulfonylurea as binding units. All of these compounds contain a flexible ethylene spacer between the recognition groups of each arm, thus furnishing fine-tuned adjustments with the anions. The synthesized isophthalamide derivatives were characterized by spectroscopic techniques. Chapter 5 covers the 1H NMR association studies carried out between Iso-1, Iso-2, Iso-4, Iso-6 and Iso-8 with Cl-, H2PO4-, HCO3- and oxalate anions. Iso-1, Iso-2 and Iso-6 formed the strongest associations with oxalate, with association constants (Kass) of 6100, 7800 and 9800 M-1, respectively, and the weakest with Cl- (17 < Kass < 19 M-1). H2PO4- always formed stronger associations (294 < Kass < 427 M-1) than HCO3-, with the latter assembling preferably with Iso-2 (Kass = 95 M-1). The sulfonylurea groups of Iso-4 and Iso-8 were deprotonated in the presence of all anions, apart from Cl-. In Chapter 6, the main conclusions from this PhD research program are presented, and, at last, Chapter 7 describes all experimental procedures as well as the spectroscopic data of the synthesized compounds.

Doutoramento em Química
Nesta tese, realizada no âmbito do Programa Doutoral em Química da Universidade de Aveiro, foram desenvolvidas duas famílias de receptores sintéticos: macrocíclicos baseados na plataforma tetraazacalix[2]areno[2]triazina; e acíclicos construídos a partir de diaminas simples. A plataforma macrocíclica foi decorada nos átomos de azoto em ponte com unidades de reconhecimento molecular contendo fragmentos com grupos amida para o reconhecimento de aniões ou com grupos ácidos carboxílicos para a coordenação de metais de transição. Os receptores acíclicos foram obtidos por acoplamento de diaminas (etilenodiamina, orto-fenilenodiamina ou 2-aminobenzilamina) com uma unidade lipofílica incorporando um anel heterocíclico (derivados de oxadiazole ou furano) e com um derivado isocianato. Estas moléculas assimétricas com um grupo amida e um grupo ureia como unidades de reconhecimento molecular foram avaliadas como receptores e transportadores transmembranares de aniões biologicamente relevantes (Cl- e HCO3-). Os resultados experimentais obtidos serão descritos ao longo de três capítulos, após um primeiro capítulo bibliográfico. No Capítulo 1 começa-se por fazer uma revisão bibliográfica sucinta sobre o desenvolvimento recente de receptores funcionais baseados em azacalixarenos bem como das suas aplicações, designadamente no reconhecimento molecular. Numa segunda parte apresenta-se uma revisão sucinta de receptores derivados de (tio)ureias, relacionados com os receptores sintetizados no âmbito desta tese e com propriedades de reconhecimento e transporte transmembranar de aniões. No Capítulo 2 reporta-se uma série de macrociclos novos com os átomos de azoto em ponte de tetraazacalix[2]areno[2]triazina funcionalizados com bromoacetato de metilo. Foram preparados três novos macrociclos com quatro grupos éster, como braços pendentes, a partir de percursores tetraazacalix[2]areno[2]triazina com os anéis de triazina substituídos com cloro, metilamina ou hexilamina. Os grupos acetato foram hidrolisados em condições básicas, tendo cada um dos derivados dialquilamina originado um composto com quatro grupo carboxílicos, enquanto o análogo diclorado originou uma mistura de compostos com dois grupos carboxílico e com os átomos de cloro substituídos por grupos hidroxilo. Subsequentemente, as propriedades de coordenação dos derivados alquilamina para cobre(II) foram avaliadas por espectroscopia de UV-Vis, tendo-se obtido constantes de estabilidades semelhantes (logk ≈ 6,7). No Capítulo 3 descrevem-se três macrociclos obtidos através da funcionalização dos átomos de azoto em ponte de tetraazacalix[2]areno[2]triazina com grupos amida derivados de N-Boc-etilenodiamina, benzilamina e (S)-metilbenzilamina. A afinidade destes receptores para a série de aniões carboxilato (oxalato, malonato, succinato, glutarato, diglicolato, pimelato, suberato, fumarato, maleato, ftalato e isoftalato) e inorgânicos (Cl-, H2PO4- e SO42-) por titulação de RMN de 1H, foi avaliada. Estes macrociclos conjuntamente com os descritos no Capítulo 2 são os primeiros exemplos reportados na literatura de receptores sintéticos baseados na plataforma de tetraazacalix[2]areno[2]triazina com grupos funcionais nos azotos em ponte. O receptor derivado de N-Boc-etilenodiamina, com oito grupos N-H, entre os três receptores, é o que apresenta maior afinidade para os aniões estudados. No Capítulo 4 é descrita a síntese 59 compostos acíclicos (vide supra) obtidos em três passos de síntese com bons rendimentos. No design desta biblioteca de moléculas a afinidade para aniões dos grupos ureia foi modelada pela inserção de diferentes substituintes arilo ou alquilo, com propriedades electrónicas distintas. A introdução destes grupos em conjugação com um anel de oxadiazole ou furano permitiu também modelar a lipofília destes compostos. A afinidade destes receptores para aniões cloreto e bicarbonato, e em alguns casos para fumarato e maleato, foi investigada por titulação de RMN de 1H. Estes compostos apresentaram constantes de associações compatíveis com o transporte transmembranar de cloreto. Por outro lado estes receptores apresentaram afinidades elevadas para fumarato e maleato, com seletividade para este último. São também discutidos os resultados dos ensaios de transporte de cloreto por estes receptores através de vesículas de em POPC. No Capítulo 5 encontram-se as conclusões gerais desta tese de Doutoramento. No Capitulo 6 encontram-se os dados espectroscópicos e os restantes detalhes experimentais para todos os compostos sintetizados.
This Ph. D. thesis was carried out under the scope of the Doctoral Program in Chemistry held at Universidade de Aveiro. Two families of synthetic receptors composed of macrocycles based on tetraazacalix[2]arene[2]triazine platform, and acyclic derivatives built from diamine spacers, were produced. The tetraazacalix[2]arene[2]triazine was decorated with molecular recognition units appended at the nitrogen bridging atoms. These units incorporate suitable amide moieties for anion binding or carboxylic groups for transition metal coordination. The acyclic derivatives were obtained through the coupling of diamine spacers (ethylenediamine, ortho-phenylenediamine, or 2-aminobenzylamine), lipophilic entity, incorporating a heterocyclic aromatic ring (oxadiazole or furan), and an isocyanate derivative. These molecules have an asymmetric structure with three NH binding units composed of an amide and urea groups. The anion affinities of these small molecules towards biological relevant anions were evaluated, as well as their anion transmembrane transport abilities. The experimental results obtained in this thesis are described throughout three chapters, which were preceded by a first chapter focused on the state of the art. Chapter 1 starts with a brief review on recent synthetic developments of functional azacalixarene receptors and their applications, namely molecular recognition. The second half of this chapter reports a concise bibliographic revision focused on small (thio)urea based molecules used to assist the anion transport across cellular membrane models. Chapter 2 reports a new series of tetraazacalix[2]arene[2]triazine macrocycles functionalized on the bridging nitrogen atoms with methyl bromoacetate. Three new macrocycles with four pendant ester arms and both triazine rings substituted with chlorine, dimethylamine or dihexylamine were prepared. Subsequently, the carboxymethyl appendages were hydrolyzed in basic conditions, arising two new compounds with four carboxylic acid groups from dialkylamine precursors, and a mixture of isomeric compounds from the dichlorinated predecessor with two carboxylic groups and the triazine rings substituted with hydroxyl groups. Thereafter, the coordination properties of both dialkylamine derivatives for copper (II) were assessed by UV-Vis spectroscopy and similar stability constants (logk ≈ 6.7) were calculated. The Chapter 3 describes the synthesis of three new macrocycles obtained by the functionalization of the tetraazacalix[2]arene[2]triazine nitrogen bridges with N-Boc-ethylenediamine, benzylamine and (S)-methylbenzylamine derivatives. The affinity of these receptors towards a series of dicarboxylate (oxalate, malonate, succinate, glutarate, diglicolate, pimelate, suberate, fumarate, maleate, phthalate and isophtalate) and inorganic (Cl-, H2PO4- and SO42-) anions was evaluated by means of 1H-NMR titrations. These macrocycles together with ones aforementioned in chapter 2, were the first examples of synthetic receptors based on the tetraazacalix[2]arene[2]triazine platform incorporating functional recognition entities attached to the nitrogen bridging atoms. Furthermore, among these amide receptors, the N-Boc-ethylenediamine derivative, with eight N-H binding groups, exhibit the better affinity towards all studied anions. Chapter 4 begins with the synthesis of an extensive series composed of 59 new acyclic compounds (vide supra), which were straightly obtained in three steps and in good yields. In the design of this library of small molecules, the anion affinity of the urea groups was properly modulated by the insertion of different substituents bearing distinct electronic properties, ranging from aryl groups with halogen substituents to alkyl chains. The assembly of these fragments together with an entity containing a heterocyclic aromatic ring also enabled the tuning of the lipophilicity of these compounds. The affinity of these receptors for chloride and bicarbonate, and for some receptors, for fumarate and maleate, was evaluated by 1H-NMR titration. The chloride association constants for these compounds were consistent with the chloride transmembrane transport. In addition, these receptors displayed high affinity constants for fumarate and maleate anion, being selective for the latter. Also, the results obtained for transport essays of chloride through POPC membranes are presented. The conclusions obtained throughout this Ph. D. thesis are outlined in Chapter 5. Chapter 6 comprises the experimental proceedings, the spectroscopic data for all synthesized compounds.

Doutoramento em Química
O trabalho descrito nesta dissertação envolve a síntese e caracterização de novos macrociclos tetrapirrólicos e afins com potencial aplicação como quimiossensores de aniões, tanto em solução como quando suportados em diferentes materiais. As porfirinas e ftalocianinas ocupam um lugar de destaque nesta dissertação, pelo que no primeiro capítulo, é feita uma revisão bibliográfica acerca das suas metodologias de síntese bem como das suas principais características e aplicações, nomeadamente como quimiossensores de aniões. No segundo capítulo é discutida a síntese e caracterização dos compostos porfirínicos e ftalocianinicos com grupos amina ou poliamina, posteriormente utilizados como hospedeiros de aniões. Descrevem-se, pormenorizadamente, os métodos de síntese, purificação e caracterização estrutural dos diversos compostos sintetizados. No terceiro capítulo realizaram-se os estudos de complexação com aniões em solução e determinaram-se as respetivas constantes de afinidade. Os compostos sintetizados apresentam capacidade de interagir com diferentes aniões. As porfirinas testadas apresentam elevadas constantes de afinidade para o anião di-hidrogenofosfato, mesmo em soluções aquosas quando testadas com cristais piezoelétricos. No caso das ftalocianinas verificou-se que estas interagem com vários aniões e apresentam propriedades cromogénicas, podendo mesmo distinguir aniões cianeto em soluções contendo água. No quarto capítulo estudou-se a imobilização dos quimiossensores, que demonstraram maior eficácia nos estudos de reconhecimento em solução, em diferentes materiais. Primeiro foi estudada a imobilização dos quimiossensores em nanopartículas de sílica (com e sem núcleo magnético) e testada a sua capacidade como sensor de aniões em solução. Numa segunda parte foi estudada a imobilização em fibras óticas. Estas, além das suas excecionais propriedades físico-químicas, têm a vantagem de poderem ser integradas em diferentes estruturas e/ou equipamentos de análise. Na ultima parte desta dissertação encontra-se a descrição da síntese e caracterização de novos conjugados porfirina-C60-OligoDNA com potencial aplicação em transferência eletrónica. Foram sintetizados e caracterizados novos compostos porfirina-OligoDNA e C60-OligoDNA. Esta parte do trabalho foi realizada no “Institute of Advanced Energy” na Universidade de Quioto, Japão.
The present document reports the synthesis and characterization of new tetrapyrrolic macrocycles and analogues with potential application as chemosensor for anions. The chemosensors were tested in solution and also supported in different materials. Porphyrins and phthalocyanines have a prominent role in this document. In the first chapter through a review of the literature, is discussed the synthetic methods of porphyrins and phthalocyanines as well as their characteristics and applications, particularly as quimiossensores of anions. In the second chapter we discusses the synthesis and characterization of porphyrins and phthalocyanines with amino or polyamine groups to be used as anion chemosensors. It is describe, in detail, the methods of synthesis, purification and structural characterization of the several synthesized compounds. The third chapter describes the interactions studies of the chemosensors with different anions in solution. Were performed several titrations and the respective affinity constants were determined. The synthesized compounds have the ability to interact with different anions. The tested porphyrins have high affinity constant with the dihydrogenophosphate anion, even in aqueous solutions when tested on piezoelectric crystals. In the case of phthalocyanines it was determined that they interact with various anions and have chromogenic properties, displaying sharp color variations, which can even distinguish cyanide anions in solutions containing water. In the fourth chapter of this thesis we studied the immobilization of the chemosensors, which demonstrated better efficacy in the solutions binging studies, in different materials. First was studied the immobilization of the chemosensors in silica nanoparticles (with and without magnetic core) and tested its ability in solution as anion sensor. In the second part was studied the immobilization on optical fibers. These, in addition to their exceptional physical and chemical properties, have the advantage that can be integrated in different structures and/or analytical equipment. In the last part of this thesis is described the synthesis and characterization of new porphyrin-[C60]-OligoDNA conjugates with potential application in electronic and energy transfer. They were synthesized and characterized new porphyrinoligo-DNA and new [C60]-OligoDNA compounds. This part of the work was held at the "Institute of Advanced Energy" at the University of Kyoto, Japan.

Doutoramento em Química
O trabalho descrito insere-se no âmbito da Química Supramolecular e consistiu no desenvolvimento de receptores artificiais, na forma protonada ou complexada, para o reconhecimento molecular de substratos aniónicos derivados de ácidos carboxílicos incluindo os herbicidas PMG2-, ATCP- e 2,4-D-. Foram investigadas duas séries de aniões, uma alifática (ox2-, mal2-, suc2-, glu2-, adip2-, cit3- e cta3-) e outra aromática (bzc-, naphc-, anthc-, pyrc-, ph2-, iph2-, tph2-, btc3-, dihyac2-, 4,4-dibzc2-, 3-nitrobzc- e 4-nitrobzc-). Foram sintetizados sete novos ligandos macrocíclicos simétricos constituídos por anéis aromáticos piridina ou fenantrolina ligados por cadeias de poliaminas saturadas. O comportamento ácido-base destes macrociclos foi investigado em solução aquosa e as constantes de protonação correspondentes determinadas por métodos potenciométricos e de RMN de 1H. As propriedades de complexação destes ligandos com os iões metálicos Ni2+, Cu2+, Zn2+, Cd2+ e Pb2+ foram também estudadas por métodos potenciométricos nas mesmas condições experimentais, tendo revelado que os macrociclos de dimensão média são capazes de acomodar um ou dois iões metálicos. O complexo dinuclear de Cu(II) derivado do macrociclo com dois grupos piridina foi utilizado como receptor de aniões carboxilato originando complexos ternários. Todos os complexos foram caracterizados em solução por espectroscopias de UV/vis/IVpróx e de RMN. As espécies paramagnéticas foram também caracterizadas por espectroscopia de RPE. A formação de espécies ternárias foi ainda investigada por espectrometria de massa ESI-MS e ESI-MS/MS. As estruturas cristalinas de alguns dos complexos foram determinadas por difracção de raios-X. As formas protonadas dos macrociclos foram utilizadas como receptores de uma grande variedade de aniões carboxilato. O reconhecimento molecular entre os receptores e os substratos aniónicos foi investigado em solução por métodos potenciométricos e de espectroscopia de RMN com determinação das constantes de associação. Os agregados supramoleculares foram caracterizados no estado sólido por difracção de raios-X. Finalmente as associações supramoleculares foram estudadas em solução por métodos de dinâmica molecular com determinação dos termos entrópicos e entálpicos das energias livres de ligação. Em resumo, nesta tese apresentam-se os resultados de estudos realizados com duas famílias de macrociclos: desde a síntese dos compostos, passando por estudos em solução e finalizando com simulação molecular. Este estudo sistemático através da conjugação de metodologias complementares permitiu caracterizar ao nível macroscópico e microscópico as associações moleculares.
The described work is included in the Supramolecular Chemistry field and it comprises the development of artificial receptors, in the protonated or complexed forms, for the molecular recognition of carboxylate anionic substrates among them two herbicides PMG2-, ATCP- e 2,4-D-. Two series of anions, one aliphatic (ox2-, mal2-, suc2-, glu2-, adip2-, cit3- e cta3-) and the other aromatic (bzc-, naphc-, anthc-, pyrc-, ph2-, iph2-, tph2-, btc3-, dihyac2-, 4,4-dibzc2-, 3-nitrobzc- e 4-nitrobzc-) were investigated. Seven new symmetric macrocyclic ligands containing two pyridine or two phenanthroline aromatic fragments linked by saturated polyamine chains were synthesized. The acid-base behaviour of these macrocycles was investigated in aqueous solution and the corresponding protonation constants determined by potenciometric and 1H NMR methods. The complexation properties of these ligands with the metal ions Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ were also studied by potentiometric methods under the same experimental conditions. The results showed that the macrocycles of medium size are able to accommodate one or two metal ions. The dinuclear copper(II) complex derived from the macrocycle with two pyridine rings was also used as receptor for the binding of carboxylate anions leading to the formation of ternary complexes. All complexes were completely characterized in solution using UV/vis/NIR and RMN spectroscopies. The paramagnetic species were also characterized by EPR spectroscopy. The dinuclear species were also studied through ESI-MS and ESI-MS/MS. The single crystal structures of some metal complexes were determined by X-ray diffraction. The protonated forms of the macrocycles were used as receptors for the binding of various carboxylate anions. The molecular recognition process between the receptors and the anionic substrates was investigated in solution by potentiometric methods and NMR spectroscopy with the consequent determination of the binding association constants. The supramolecular aggregates were characterised by single crystal X-ray diffraction. Finally the supramolecular associations were studied, in solution, via molecular dynamic simulations with calculation of the enthalpic and entropic contributions for the binding free energies. In conclusion, in this thesis the results of the studies carried out with two families of macrocycles were presented: starting from the synthesis to solution studies and finishing with molecular dynamic simulations. This comprehensive study, comprising several complementary techniques, allowed the full characterization at the macroscopic and microscopic levels the supramolecular associations.

Doutoramento em Química
Expanded porphyrins are synthetic analogues of porphyrins, differing from the last ones and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core, with a minimum of 17 atoms, while retaining the extended conjugation features that are a tremendous feature of these biological pigments. The core expansion results in various systems with novel spectral and electronic features, often uniques. Most of these systems can also coordinate cations and/or anions, and in some cases they can bind more than one of these species. In many cases, these molecules display structural features, such as non-planar structures, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. This work will discuss several synthetic approaches for the synthesis of expanded porphyrins, namely the construction of new building blocks by Michael addition, as well as potential synthetic routes towards expanded porphyrins. The synthesis of smaller oligopyrrolic compounds namely, bipyrroles and dipyrromethanes, not only were developed for the synthesis of expanded porphyrins as they were also used in Knoevenagel condensations furnishing chromogenic compounds able to recognize different anions in solution. Also, an approach to the synthesis of novel expanded porphyrins namely sapphyrins has been done by aza-Michael additions. Several synthetic routes towards the synthesis of pyridyl and pyridinium N-Fused pentaphyrins and hexaphyrins have been explored in order to achieve compounds with potential applications in catalysis and PDI, respectively. Studies on the synthesis of compounds with potential anion binding properties, led to the structural characterization and NMR anion binding studies of [28]hexaphyrins functionalized with several diamines in the para position of their pentafluorophenyl groups. These compounds allow NH hydrogen bond interactions with various anions. All synthesized compounds were fully characterized by modern spectroscopic techniques.
Porfirinas expandidas são análogos sintéticos das porfirinas, diferindo destes apenas por possuírem um core contendo no mínimo 17 átomos. A expansão do core resulta em vários sistemas com novas características electrónicas e espectrais, e numa extraordinária química de coordenação. Em muitos casos é também possível interação supramolecular com um ou vários aniões. Outra característica interessante é a possibilidade destes macrociclos acomodarem mais do que um estado de oxidação variando as suas características de aromaticidade e planaridade sem antecedentes na química de macrociclos tetrapirrólicos e derivados. Este trabalho discute diversas rotas de síntese de macrociclos expandidos e sua derivatização, bem como a síntese de precursores bipirrólicos sobejamente conhecidos pela sua utilização como precursores na síntese de Porfirinas expandidas. Para este fim, unidades do tipo bipirrolico foram funcionalizadas através de adições de Michael. Estes pequenos compostos foram também derivatizados através de condensações de Knoevenagel para aplicação em coordenação de aniões demonstrando reconhecimento de diferentes aniões mediante uma variação de cor específica. No seguimento destes estudos de reactividade por Diels-Alder e/ou adições de Michael obtiveram-se novos derivativos do tipo safirina com substituições no interior do macrociclo. Tendo em vista a síntese de compostos com reconhecimento de aniões e potencial aplicação em PDT/PDI e catálise, macrocrociclos do tipo pentafirina e hexafirina foram derivatizados com diversos nucleófilos. Neste último, a introdução de grupos amino na sua periferia conduziu a um aumento drástico da capacidade de interação com aniões em solventes polares. Estudos de RMN com os compostos capazes de reconhecer aniões possibilitou a sua total caracterização estrutural demonstrando estruturalmente os grupos que participam no reconhecimento de aniões. Todos os compostos presentes sintetizados foram caracterizados estruturalmente com recurso a diversas técnicas espectroscópicas, nomeadamente: à ressonância magnética nuclear de protão, carbono 13 e de flúor 19, à absorção no Ultravioleta-Visível, à espectrometria de massa e sempre que possível a análise de raio-X de monocristal.

Mestrado em Química
The chloride transport across the phospholipid bilayer assisted by small synthetic molecules were studied by computational methods including quantum calculations followed by molecular dynamics simulations and free energy calculations. A series of twelve tris-thiourea aryl substituted putative transporters, with three different six-membered rings as scaffolds (desmethyl cyclohexane, hexamethyl cyclohexane and benzene) and each of them with four possible aryl substituents (3,5-trifluoromethyl, p-trifluoromethyl, p-nitro and phenyl), were studied in silico in order to understand the experimental transport data previously reported for these molecules. The computational study started with the DFT optimization of twelve chloride complexes in gas phase and in DMSO at the M062X/6-31+G** theory level. The strength of the N-H···Cl- interactions were ascertained through the E2 values obtained from the second order perturbation theory, the Wiberg bond Indexes and the most positive value of the electrostatic potential (VS,max). Overall, these descriptors increases with the binding affinity constants reflecting the electron withdrawing character of the aryl substituents. Thus, the 3,5-trifluoromethyl substituted transporters presented the highest values for the quantum descriptors as well as the highest binding affinity for chloride anion, indicating that these molecules are able to successfully uptake the anion from the water phase and further proceed to its transport across the phospholipid bilayer. Subsequently, the passive diffusion of these chloride complexes were then investigated by MD simulations positioning them either in the bilayer core and water phase. Overall, the MD simulation runs reveal that the transporters were able to promote chloride uptake and release events, consistent with anion carrier transport mechanism. Furthermore, free energy profile for 3,5-trifluoromethyl hexamethyl cyclohexane complex and free chloride were constructed from the potential mean force calculations. The chloride complex has to surpass an energy barrier to cross the middle of the phospholipid bilayer of 2 kcal mol-1 while for the free chloride this energy increases to 19.5 kcal mol-1 indicating that the chloride transport assisted by this receptor is energetically favoured. Another remarkable feature from the MD simulations is that the chloride complexes fit comfortably well below the membrane’s interface which seems to indicate that the receptors are able to operate as a chloride shuttle without leaving the phospholipid bilayer.
O transporte de cloreto pela bicamada fosfolipídica, assistido por pequenas moléculas sintéticas, foi estudado através de métodos computacionais, incluindo cálculos quânticos, simulações de dinâmica molecular e cálculos de energia livre. As propriedades de transporte de um conjunto de doze tris-tioureias contendo um anel central de seis membros (cicloexano, cicloexano hexametilado e benzeno) derivatizado com grupos arilo (3,5-trifluorometilo, p-trifluorometilo, pnitro e fenilo), foram estudados in silico tendo como objetivo a compreensão de dados experimentais de transporte reportados. O estudo computacional iniciou-se com a otimização dos doze complexos em fase gasosa e em dimetilsulfóxido (DMSO), ao nível de teoria de M06-2X/6- 31+G**. A força das interações NH···Cl- foi determinada através dos valores de E2 obtidos da teoria de perturbação de segunda ordem, dos índices de ligação de Wiberg e do valor mais positivo de potencial electroestático (VS,max). Estes descritores aumentam com as constantes de afinidade, refletindo o carácter electroatractor dos substituintes arilo. Assim, os três transportadores com grupos 3,5-trifluorometilo apresentaram os valores mais altos para estes descritores e para afinidade ao cloreto, demonstrando que estas moléculas conseguem de facto capturar um anião da fase aquosa e proceder ao seu transporte através da bicamada fosfolipídica. Seguiu-se o estudo do processo de difusão passiva para estes três complexos por dinâmica molecular, tendo estes sido colocados tanto na fase aquosa como no centro da bicamada fosfolipídica. Estas simulações revelaram que os transportadores eram capazes de promover os processos de captura e libertação de cloreto. Além disso, os perfis de energia livre para o complexo do ligando cicloexano hexametilado derivatizado com 3,5-trifluorometilo e para o cloreto livre foram obtidos através de cálculos de potencial de força média. O complexo tem que superar uma barreira energética de 2 kcal mol-1 para atravessar o meio da bicamada enquanto o cloreto livre tem que ultrapassar uma barreira de energia livre de 19.5 kcal mol-1, i.e. o transporte assistido pelo recetor é energeticamente mais favorável. Outra caraterística importante das simulações está relacionada com o facto dos complexos de cloreto de inserirem confortavelmente abaixo da interface da membrana, indicando que os recetores conseguem operar como transportadores de cloreto sem sair da bicamada fosfolipídica.

Doutoramento em Química
Nas últimas décadas, os líquidos iónicos (ILs) têm sido alvo de elevado interesse quer por parte da academia como a nível industrial. Isto deve-se em grande parte às suas propriedades únicas, assim como à possibilidade de, através de uma apropriada combinação dos seus iões, ser possível ajustar as suas propriedades para uma dada aplicação. Assim, os ILs têm vindo a ser considerados uma abordagem inovador para a “Química verde” e para a sustentabilidade. Contudo, a sua solubilidade em água faz com que estes possam facilmente chegar ao ecossistema aquático, podendo representar um perigo para este. O principal objetivo deste trabalho é estudar novos ILs, mais sustentáveis, assim como algumas das suas potenciais aplicações. Assim, foram investigados ILs como sendo antioxidantes, seletores quirais, hidrótopos, surfactantes, compostos magnéticos, assim como novos compostos hidrofóbicos. Para cada classe de ILs, foi estudada a sua síntese, caracterização físico-química e perfil de ecotoxicidade. Os novos ILs antioxidantes preparados neste trabalho foram avaliados quanto à sua solubilidade em água, estabilidade térmica, citotoxicidade e ecotoxicidade. Foram também estudados vários ILs quirais, quer baseados em aniões quirais (derivados de vários aminoácidos e do ácido tartárico), quer em catiões quirais (derivados da quinina, L-prolina e L-valina), no que respeita à sua estabilidade térmica, rotação ótica e ecotoxicidade. Além disso, foi avaliado o impacto de diferentes estruturas químicas dos ILs, assim como da sua concentração, na solubilidade de fármacos com reduzida solubilidade em água, a fim de analisar o seu comportamento enquanto hidrótopos cataniónicos. Entre as estruturas mais hidrofóbicas referidas neste trabalho estão vários ILs com natureza surfactante e um IL hidrofóbico baseado no anião per-fluoro-tertbutóxido. Relativamente aos ILs com carácter surfactante, foram preparados ILs pertencentes à família dos imidazólios, amónios quaternários e fosfónios, sendo posteriormente avaliados quanto à sua natureza de agregação, propriedades térmicas, ecotoxicidade, e à sua capacidade em promover disrupção celular. Por sua vez, o IL baseado no anião per-fluoro-tert-butóxido foi estudado relativamente às suas propriedades físicas, tais como a sua densidade, viscosidade e tensão superficial, assim como à sua toxicidade. Por fim, 24 ILs magnéticos foram preparados conjugando o catião colínio com diferentes aniões magnéticos ([FeCl4]-, [MnCl4]2-, [CoCl4]2- and [GdCl6]3-), sendo seguidamente avaliados quanto à sua ecotoxicidade. Visando o desenho racional de novos ILs, foi desenvolvido um modelo preditivo QSAR, onde foram utilizandos os dados de ecotoxicidade medidos neste trabalho. As previsões deste modelo relativamente à não toxicidade de um certo número de novos ILs foram testadas com êxito através da síntese destes compostos e posterior avaliação da sua ecotoxicidade utilizando o bioensaio Microtox.
Due to their unique properties, ionic liquids (ILs) have attracted an increased scientific and industrial attention in the last decades. The possibility of tailoring their properties for a specific task by the adequate combination of their ions, makes these ionic compounds good candidates for a wide range of different applications. Actually, ILs have been described as an innovative approach to the “Green Chemistry” and sustainability principles. However, their solubility in water allows their easy access to the aquatic compartment, which makes them potentially hazardous compounds to aquatic organisms. The main goal of this work is to study new, more environmental friendly, IL structures and their main applications. ILs as antioxidants, chiral selectors, hydrotropes, surface-active compounds, with magnetic properties, as well as, new hydrophobic compounds are investigated. The synthesis, physico-chemical characterization and ecotoxicity profile were studied for the various classes of task specific ILs evaluated. New cholinium-based ILs with antioxidant nature were studied regarding their solubility in water, thermal stability, cytotoxicity, and ecotoxicity. Moreover, a large range of chiral ILs (CILs) based on several chiral anions (derived from chiral amino acids and tartaric acid) and chiral cations (based on quinine, L-proline and L-valine), was investigated and their thermal stability, optical rotation and ecotoxicity evaluated. Furthermore, the impact of different ILs structures and concentrations on the solubility of poorly water-soluble drugs was studied, and their role as catanionic hydrotropes investigated. Among the most hydrophobic structures reported in this work are several surface-active ILs and a hydrophobic IL based on the per-fluoro-tert-butoxide anion. The tensioactive ILs, belonging to the imidazolium, quaternary ammonium and phospholium families were tested in terms of their aggregation behavior, thermal properties, ecotoxicity, and their capacity to promore cell disruption. On the other hand, the per-fluoro-tert-butoxide-based IL was evaluated regarding its physical properties, such as density, viscosity, and surface tension and toxicity. Finally, 24 magnetic ILs belonging to the cholinium family and using [FeCl4]-, [MnCl4]2-, [CoCl4]2- and [GdCl6]3- as anions were investigated and their ecotoxicity evaluated. Aiming at the rational design of ILs, a predictive QSAR model was developed with our help, and using ecotoxicity data measured in this work. The predictions of this model concerning the non-toxicity of a number of novel ILs were successfully tested by synthesizing these compounds and evaluating their toxicity using the Microtox bioassay.

aplicació en transformacions enantioselectives amb l’objectiu de desenvolupar nous processos en flux i (b) catàlisi homogènia centrada a millorar reaccions promogudes per anions sulfenat (la formació d’aril sulfòxids catalitzada per pal·ladi i el desenvolupament d’un pre-catalitzador de segona generació per a processos sense metall). La primera part de la feina tracta sobre l’aplicació del polinorbornè com a un suport robust per a immobilitzar catalitzadors homogenis. A tal fi, s’ha seleccionat la reacció aldòlica. El material ha demostrat tenir potencial, amb resultats comparables als obtinguts amb una matriu de poliestirè. Fóra interessant estudiar transformacions alternatives per a aquest tipus de materials, especialment en aplicacions fotocatalítiques i processos de flux continu. En els següents capítols s’han desenvolupat β-fluoroamines suportades en polímer emprant dues aproximacions: copolimerització i química “click”. Tant el mètode d’activació via enamine com el que involucra ions imini s’han tingut en compte per a estudiar reaccions enantioselectives. L’addició asimètrica de Michael d’aldehids a nitroalquens ha estat especialment reeixida, ja que l’aplicació de flux continu ha replicat les enantioselectivitats obtingudes en batch. L’estratègica instal·lació d’un fluorur en lloc del més làbil èter de silici (catalitzador tipus Jørgensen-Hayashi) ha permès una millora substancial dels resultats.
Pel que fa al mode d’activació d’ió imini, s’han estudiat l’epoxidació i l’aziridinació d’aldehids α,β-insaturats. Malgrat tot, caldrà repensar el disseny del catalitzador a causa de l’efecte negatiu en aquestes transformacions del triazole que fa d’unió. Finalment, en el camp de la catàlisi homogènia, s’ha estès la formació d’aril sulfòxids catalitzada per pal·ladi a clorurs d’aril, més assequibles que els corresponents bromurs. A més, s’ha desenvolupat un nou pre-catalitzador per a l’acoblament d’halurs per generar estirens sota catàlisi d’anió sulfenat. Esta Tesis contiene dos secciones: (a) estudios para la síntesis de nuevos organocatalizadores soportados y su aplicación en transformaciones enantioselectivas, a fin de desarrollar nuevos procesos de flujo y (b) catalisis homogénea para la optimización de reacciones de aniones sulfenato (formación de sulfóxidos de arilo catalizadas por Pd y desarrollo de una segunda generación de pre-catalizadores para procesos sin metales). La primera parte de este trabajo se centra en el desarrollo de resinas de polinorborneno robustas como soporte de catalizadores homogéneos. Se han estudiado reacciones aldólicas enantioselectivas con excelentes resultados, comparables a los obtenidos con poliestireno. Podría ser interesante estudiar aplicaciones de estos materiales en transformaciones fotocatalíticas y procesos en continuo. En los siguientes capítulos se presenta el desarrollo de nuevas resinas catalíticas basadas en β-fluoroaminas soportadas en poliestireno preparadas por copolimerización o siguiendo una estrategia de click-chemistry y su empleo en transformaciones asimétricas con activación via enamina e ión iminio. Se han aplicado en la adición de Michael de aldehídos a nitroalquenos, proceso que se ha implementado en flujo continuo con la misma enantioselectividad que en batch. La presencia de flúor, sustituyente más robusto que el lábil éter silílico de los catalizadores tipo Jørgensen-Hayashi, aumenta notablemente la vida útil del catalizador.
estos casos la presencia del triazol que conecta la matriz polímérica y la unidad catalítica tiene un efecto negativo en el proceso, por lo que será necesario rediseñar el catalizador. Finalmente se han estudiado dos procesos de catálisis homogénea. Se presentan metodologías mejoradas para la formación de sulfóxidos de arilo a partir de cloruros de arilo catalizada por Pd y el desarrollo de un nuevo precatalizador para el acoplamiento de haluros para generar estirenos mediada por aniones sulfenato. This Thesis covers two main sections: (a) studies towards the synthesis of new immobilized organocatalysts and their application in a wide range of enantioselective transformations with the main goal of developing new continuous flow processes and (b) homogenous catalysis aimed at improving recently reported reactions of sulfenate anions (a Pdcatalyzed aryl sulfoxide formation, and the development of a second generation pre-catalyst for metal-free processes). The first part of this work is devoted to the application of polynorbornene as a robust support for the immobilization of homogeneous catalysts. To this aim, the aldol reaction has been selected. This material has shown high potential, comparable to the results obtained with a polystyrene matrix. It will be interesting to study alternative transformations for this type of materials, especially in photocatalytic applications and continuous flow processes. In the following chapters, new polymer-supported β-fluoroamines have been developed with two different approaches: copolymerization and click chemistry. Both the enamine and iminium ion activation modes have been considered to study asymmetric transformations.

Orientador: Ana Luiza Bustamante Smolka
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Educação
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Resumo: Esta tese teve como objetivo compreender as relações entre crianças, televisão e dois animes (pokémon e Dragonball Z) em sua intertextualidade, a partir de fundamentos teóricos de L. S. Vygotsky, M. Bakhtin e de contribuições de D. Maingueneau, E. Orlandi e J. Fiske. Participaram deste estudo 8 meninos (com idades entre 11 e 12 anos), que vem se constituindo em condições materiais cotidianas (incluindo suas "experiências televisivas") marcadamente diferentes. O material empírico foi composto por: análises de enunciações das crianças, produzidas ao assistirem e comentarem dois episódios de cada um dos animes, entretecidas com análises sobre estes episódios, os animes como gênero de discurso e sobre a televisão. Estas análises permitiram compreender que as relações intertextuais estão marcadas por complexas e ininterruptas tensões. Entre várias outras, pode ser destacada a existente entre tendência de monofonização dos textos dos animes em relação ao seu mote principal - as lutas - e movimentos de adesão e resistência dos meninos (considerando-se a produção de paráfrases, de outros sentidos - a partir da polissemia de palavras/imagens-, enunciações polifônicas e deslocamentos na centralidade deste mote). Apontadas similitudes e diferenças nas relações íntertextuais (por entendê-Ias como processos social,. cultural e historicamente marcados) problernatizou-se suas relações com as condições de vida destas crianças. Por fim, tendo como sustentação os pressupostos teóricos e as análises que foram construídas, foi possível dialogar com trabalhos que tematizam a televisão, suas produções e/ou as relações das crianças com estes termos e os (des)compromissos das instituições educacionais e escolares em relação a estes temas
Abstract: The present thesis aims at.understanding the relationships among ehildren, television, and two animes (pokémon and Dragonball Z) in their intertextuality, based on the theoretical grounds of L.S, Vygotsky, M, Bakhtin and the contributions of D. Maingueneau, E. Orlandi and Fiske. Eight boys (at ages between 11 and 12 years old), who have been living under distinetively different material eonditions in their daiJy life (ineluding their "television experience"), participated in this study. The empirie material was composedof:the analyses of the children's enunciations, produced as they watched and commented on two episodes, the animes - as diseourse geme - and television. The analyses show that intertextual relationships are eonstituted by complex and uninterrupted tensions. lt may be stressed, among several others, the existing tension between the tendeney towards the monophonization of the texts of the animes in relation to its main motif -the fights - and the joining and resistanee movements of the boys (considering the production of paraphrases, of other meanings - based on the polysemy of wordslimages -, polyphonie enunciations and displacement ofthe centrality ofthis motif). Once similarities and differences were found in their intertextual relationships (those being characterized as social, cultural and historica1 processes), questions related to their life conditions were raised. At last, by supporting on the theoretieal presuppositions and on the analyses that were constructed, it was possible to dialogue with works that deal with television, their productions and/or ehildren's relationships with these terms and the (non)commitment on the part of schools and educational institutions regarding these themes
Doutorado
Educação, Conhecimento, Linguagem e Arte
Doutor em Educação

Each of my four main areas of work is concerned with the formation and further reactions of organic fluorinated anions. a) We have investigated the fluoride ion induced reactions of 2H-pentafluoropropene with some perfluoro-aromatic compounds, forming a series of aryl substituted carbon acids and their corresponding carbanions. Also included is a study of an unusual product that was formed with pentafluoronitrobenzene as the aromatic substrate. b) Some fluorinated dienes have been generated from the fluoride ion induced reactions of dimethylacetylenedicarboxylate with a series of cyclic fluorinated alkenes. With perfluorocyclohexene, a variable temperature n.m.r. investigation indicated that one of the products was fluxional at room temperature. Products derived from, perfluorocyclopentene were then further reacted with mono- and bi-functional nucleophiles forming some new products including some interesting polycyclic compounds. c) We have studied the fluoride ion induced reactions of malononitrile and phenylsulphonylacetonitrile with a range of polyfluorinated aromatic and heteroaromatic systems. This study has yielded a series of stable fluorinated organic caesium salts which could be crystallised. Acidification of these salts yielded a series of conjugate acids and some acidity measurements were made. Analysis of n.m.r. data has shed some light on the n.m.r. consequences of tautomerisation which was observed in some of the conjugate acids. A highly unusual carbon-13 n.m.r. concentration effect was studied for several pyrimidyl salts in perdeuteroacetone solution. d) The reaction of bifunctional carbon acids with fluorinated dienes has been used to develop a route to new pentadienyl anions, cyclopentadienes, and cyclopentadienyl anions. FAB mass spectroscopy has proved to be an important tool in the study of our anionic species. Some unusual thermal isomerisation behaviour of the new cyclopentadienes has also been observed and investigated.

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Universidade Federal de Minas Gerais
The interest by the outbreak of a group of people that are admirers of the Japanese pop culture - especially by the comic books (mangas) and the cartoons (animes) is what led me to the developing of this research, in which my goal is to understand the logic of the sociability among the consumers of these medias, through the use of some very important anthropological concepts, such as the sociability, the cultural consume and life style. To do so, I started a study that began at the mangas and animes conventions, where the otakus meet to participate in contests and workshops, as well as to watch the animes and musical presentations, and also to discuss their own stories. Beyond the merely social nature, these conventions have eventually became the first step to those who wish to enter the pop culture universe, besides being a way of assertion of a specific juvenile condition to those who are already a part of it.
O interesse pelo surgimento de um grupo aficionado pela cultura pop japonesa especialmente pelas histórias em quadrinhos (mangás) e pelos desenhos animados (animes) , me levou ao desenvolvimento dessa pesquisa na qual busco compreender a lógica da sociabilidade existente entre os consumidores dessas mídias tangenciando alguns conceitos caros à antropologia, tais como a sociabilidade, bem como o consumo cultural e o estilo de vida. Para tanto dei início a uma etnografia que teve como ponto de partida as convenções de mangás e animes, nas quais os otakus se encontram para participar de concursos, oficinas, para assistirem aos animes e apresentações musicais e trocarem experiências. Para além do caráter puramente comercial, essas convenções acabaram se tornando espaços de iniciação para aqueles que desejam ingressar neste universo de cultura pop, além de serem espaço de afirmação de uma dada condição juvenil para aqueles que já fazem parte dele.

Novel synthetic applications of ambident azo-anions derived from hindered hydrazones have been investigated. Reaction with electrophiles occurred predominantly at carbon as the N-addition pathway was sterically retarded. Trityl, diphenyl-4-pyridylmethyl (DPP) benzhydryl, and t-butyldiphenylmethyl (BDP) hydrazones of various aldehydes and ketones were prepared in good yields from the corresponding hydrazines and carbonyls in aqueous methanol. The lithium salts derived from trityl and DPP hydrazones, by treatment with methyl lithium at -55°C, reacted with aldehydes and ketones to generate azo-alkoxides. These could be diverted to alcohols,by sequential protonation and spontaneous homolysis (about -20°C) in the presence of ethanethiol, or to alkenes,by treatment with phosphorus trichloride at -78 G followed by azo-homolysis. The reactions enabled efficient reductive cross-coupling of aldehydes and ketones. The mechanism of the alkene forming reaction was investigated. Anions of benzhydryl hydrazones were found to react inefficiently by a G-addition pathway giving mainly N-addition products. Anions of BDP hydrazones conveniently gave excellent yields of azo-alkanes upon treatment with alkyl halides,but no products were obtained on reaction with carbonyl electrophiles. The azo-alkanes could be isolated and purified and acted as key intermediates for several synthetically useful transformations. Homolysis in refluxing benzene with thiophenol gave alkanes in good yields. Phenylselenenyl-, bromo-, and chloro-alkanes,and β-alkylstyrenes were generated when thiol was replaced by diphenyl diselenide, N-bromosuccinimide, N-chlorosuccinimide and β-nitrostyrene respectively. Treatment of the azo-alkanes with trifluoroacetic acid generated benzophenone alkylhydrazones. These were dissolved in ethanol with concentrated hydrochloric acid, thereafter hydrolysis yielded alkylhydrazines or treatment with hydrogen (1 atm., 50°C, 20h) over 10% Pd/C generated primary amines by a novel use of carbonyls as α-aminocarbanion equivalents.

This thesis is principally concerned with the synthesis of a range of dipyrromethane based receptors and their ability to bind anions, in particular carboxylates of amino acid derivatives. Chapter I provides a general introduction to the field of Supramolecular Chemistry and its applications. In this chapter a series of receptors for anions are presented their properties discussed. A particular attention is given to the aromatic heterocycles based receptors and to enantioselective receptors. Chapter II describes the synthesis of a series of acyclic receptors which are the results of subsequent modifications of a simple tweezer, based on a dipyrromethane unit coupled with two butyl amines, previously studied by the group.1 The binding properties with a series of anions are presented and, for the chiral receptors, the binding properties with Nprotected amino acids were investigated. Chapter III describes the synthesis and the binding properties of a series of macrocycles obtained by modifications of the tweezer receptors. The binding properties of the macrocyclic receptors with a series of anions and amino acids are also presented.

Several recent results of a time-resolved photoelectron imaging experiment are presented. Following a broad introduction into the area of femtochemistry and time-resolved photoelectron spectroscopy, a detailed description of the spec- trometer is given. This utilises an electrospray ionisation source, coupled to an electrostatic ion trap. Ions are mass selected using time-of-flight methods and investigated using photoelectron imaging in a velocity-mapping geometry. Ultrafast dynamics are investigated by pump-probe spectroscopy with femtosec- ond laser pulses. Recent results are separated into three distinct projects: (i) The investigation of electron acceptor radical anions based on the quinone backbone. These commonly exhibit electron transfer rates exceeding those pre- dicted by Marcus theory by orders of magnitude. We show that an alternative pathway to electron transfer could involve the participation of electronic excited states, as these couple strongly to the anion ground state. Specifically, for p- Benzoquinone we show that electronic resonances located in the detachment continuum primarily undergo internal conversion via a number of conical inter- sections. (ii) Several polyanions have been investigated in the gas-phase. These systems exhibit unusual electronic properties, due to the presence of multiple excess charges, leading to the formation of a repulsive Coulomb barrier to photode- tachment. We investigate the effect of excess internal energy on this barrier and how it affects outgoing photoelectrons. We show that the trajectories of electrons are strongly influenced by this potential and demonstrate its use as a probe for large amplitude structural dynamics in polyanions. (iii) The isolated chromophore of the green fluorescent protein (GFP) has been studied, and the vertical and adiabatic detachment energies determined for the first time. Using time-resolved spectroscopy the excited state dynamics are in- vestigated. We show that the first singlet excited state of the anion primarily decays through internal conversion, explaining the absence of fluorescence in the gas-phase. Using high level quantum chemistry calculations we show the specific motion involved and hence confirm the function of the protein back- bone in GFP. This thesis is concluded with a few suggested experimental improvements and ideas for future studies of anions using the presented spectrometer.

ESI-MS spectra of Ni(II), Co(III), Mg(III), and Fe(II) porphyrin solutions in methanol show porphyrin monomer species with different charge states, such as [Ni(II)TPPS+H]3-, [Co(III)TPPS]3-, [Mn(III)TPPS]3-, [Mn(III)TPPS+H]2-, [Fe(II)TPPS+H]3-, and [Fe(II)TPPS+2H]2- ions. Collision-induced dissociation (CID) of these monomer species produced primarily losses of neutral SO3 and SO2. The mechanisms, in which these dissociation pathways took place, were investigated by the means of DFT calculations of the corresponding dissociation of neutral and ionized benzenesulfonate (B3-LYP/6-31+G(2d, p) level) and porphyrin monomer (B3-LYP/6-31+G(2d, p)+LANL2DZ//PM7 level). RRKM fitting of the CID breakdown curves showed that the activation energies of the reactions that experience a loss of SO2 from [Co(III)TPPS]3- and [Mn(III)TPPS]3- were similar, but of a lower magnitude than those for a loss of SO3. On the other hand, for [Ni(II)TPPS+H]3- and [Fe(II)TPPS+2H]2-, the activation energies of the reaction leading to a loss of SO2 were also similar, but this time were larger than those leading to SO3 loss. These results are consistent with a mechanism by which the SO2 loss starts with -C6H4SO3-, while the SO3 loss has to begin with -C6H4SO3H. To lose this SO3, extra energy is required for [Co(III)TPPS]3- and [Mn(III)TPPS]3- in order for them to overcome the barrier of H transfer from the porphyrin ring to -SO3-, but this is irrelevant when it comes to [Ni(II)TPPS+H]3- and [Fe(II)TPPS+2H]2- since the C6H4SO3H moiety already exists. In addition, the reaction of [Fe(II)TPPS+H]3- losing H leads to a unique dissociation mechanism.

Sammanfattning Titel: Kärlek till anime – en tillräcklig reseorsak? En kvalitativ studie om anime-fans motiv till att besöka anime-destinationer Författare: Linda Smedberg Handledare: Jasmina Beharic Examinator: Hans Wessblad Ämne: Turismvetenskap III, examensarbete (kandidat) 15 HP, HT 18 Datum: 14/1–2019   Syfte och forskningsfråga Syftet med denna uppsats är att ge en förståelse till vilka resemotiv anime-fans har för att besöka en anime-destination. Uppsatsen förklarar vilka dessa resemotiv är. Således ställdes forskningsfrågan:   Vad motiverar anime-fans att besöka en destination som använts i en japansk animerad serie?   Metod Uppsatsen utgår utifrån en kvalitativ metod och följer en deduktiv ansats. Vilket betyder att teorier presenteras som sedan mynnar ut i en analys av mitt empiriska material. Vilket är grundat i en kvalitativ, webb-baserad enkätundersökning.   Resultat Studiens resultat visar att anime-fans besöker anime-destinationer av flera olika orsaker. Alla dessa är grundade i en förkärlek till anime-kulturen. Resultaten visar också att anime-landskap samt turisternas identitet kan forma och påverka deras resemotiv.
Abstract The purpose of this thesis is to create an understanding of what motivates anime fans to visit an anime destination. This thesis aims to enlighten the reader to what these motives are by trying to answer the question: What motivates anime fans to visit a destination that has been used in a Japanese animated series?   The method used is a qualitative one and the thesis follows a deductive approach. Which means that theoretical theories were first presented. These were then tested in an analysis of my empirical material. The empirical data was collected from a qualitative web-based survey.     The study’s results show that the primary reasons anime fans visit an anime destination is because they love anime. It also shows that destinations and anime landscapes together with one’s identity can influence tourists travel motivations.

Chapter 1 surveys the chemistry and reactivity of Group 14 and relevant Group 15 complexes and introduces the analogies which exist between the well-established ligand behaviour of non-metallic systems and the configuration of donor functionality present in a range of main group metallo-organic compounds. Chapter 2 initially looks at the reactivity of the anion [Sn {μ-N=C(^tBu)Ph}₃]^-, towards a variety of metals with the aim of using this complex as a tripodal ligand. However, the reaction of [Sn{μ-N=C(^tBu)Ph}₃Li.THF] with [CuCl] results in ligand transfer of one of the imido groups, to form [Cu{μ-N=C(^tBu)Ph}]₄.THF] and the presence of PPh₃ fails to block this transfer, thus [Cu{μ-N=C(^tBu)Ph}]₄.2PPh₃-THF is produced. The reaction of [Cp₂Sn] with [2-LiPy] (2-Py = Pyridyl), formed from [ⁿBuLi] with [2-PyBr], yields the Sn(IV) product [ⁿBuSn(2-Py)₃LiBr.0.5THF]. Investigations of this compound demonstrate the efficacy of the [ⁿBuSn(2-Py)₃] moiety as a robust neutral ligand. The reaction of [ⁿBuSn(2-Py)₃LiBr.0.5THF] with CuCl₂ yields the Cu(I) product [ⁿBuSn(2-Py)₃CuBr.0.5THF]. However, an attempt to extend this reactivity to AgNO₃ results in anion exchange, producing [ⁿBuSn(2-Py)₃LiNO₃]. The Pb(II) complex [Pb(2-Py)₃Li.THF] was synthesised from the reaction of [2-LiPy] with [Cp₂Pb]. In Chapter 3, two alternative reaction pathways are identified in the nucleophilic substitution reactions of Group 14 metallocenes with lithiated primary amines [RNHLi]. These are exemplified by the synthesis of the primary tris(amido)stannate [(MANH)Sn(μ-NHMA)₂Li.2THF] obtained from the reaction of [Cp₂Sn] with [(MA)NHLi] (MA = 2-MeOC₆H₄), and the cubanes [ENCy₄] [E = Sn, Pb ; Cy = C₆H₁₁] are prepared from [CyNHLi] and [Cp₂E]. The later furnishes a new route to Group 14 imido cubanes. A study of the effects of two potent nucleophiles in the same molecule, [PhCH₂N(Li)CH₂)]₂, with [Cp₂Sn] was undertaken, yielding the dimer [{PhCH₂N(CH₂)₂NCH₂Ph}Sn]₂.

Thesis (Ph. D.)--University of Oregon, 2008.
Typescript. Includes vita and abstract. Includes bibliographical references (leaves 265-281). Also available online in Scholars' Bank; and in ProQuest, free to University of Oregon users.

This thesis reports a number of novel neutral, hydrogen bond donating anion receptors and describes their anion coordination properties in both the solution and solid states. A set of ten urea/thiourea linked indole/carbazole groups were found to have high affinities for a variety of oxo-anions in highly competitive DMSO solutions. Of these receptors, the diindolylurea motif was found to be excellent for the binding of dihydrogen phosphate. This group of receptors were found to form 1:1 complexes in solution with various anions but more complex 2:1 and 3:1 receptor:anion complexes were observed in the solid state. Deprotonation of the bound protonated oxo-anion was observed with these 2:1 and 3:1 complexes. The basic diindolylurea motif was then extended by the incorporation of further NH bond donor groups from amide, indole and carbazole functionalities. This group of receptors were found to form 1:1 complexes in both the solution and solid states, with the binding mode dependent of the geometry of the anion. These compounds also showed spontaneous crystallisation with sulfate in as little as 20 minutes. These receptors showed high affinities for the oxo-anions and gave the first examples of solution state deprotonation of bound protonated oxo-anions. A set of three dimensional indole-based receptors was also synthesised, utilising the TREN and pin-wheel scaffolds. These receptors contain between six and fifteen NH bond donor groups that give a range of anion binding modes, some too complex to be defined, that generally show a preference for the oxo-anions. Again, an example of deprotonation of the bound protonated oxo-anion was observed.

xx, 281 p. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number.
More than two-thirds of all enzyme substrates and cofactors are anionic, emphasizing the essential role that anions play in biological processes. Moreover, anions can have detrimental effects on the environment by causing ground water contamination when anions such as perchlorate, phosphate and nitrate develop in intolerable levels. Owing to the prevalent nature of anions, traditional strategies employed to target anions--including hydrogen bonding, metal ion coordination and electrostatic interactions--have been extensively studied. An alternative approach to anion binding would complement the powerful array of existing techniques. Recently, in the supramolecular chemistry community, new insight has been cast on how anions attractively interact with electron-deficient arenes, suggesting that aromatic rings are a viable anion binding strategy to balance existing methods. Chapter I provides a historical perspective of anions interacting with electron- deficient arenes. This outlook has its origins in the late 1800s with the discovery of colored charge-transfer complexes between donor and acceptor molecules and continues with the progression of the field leading up to the recent supramolecular fascination. Chapter II represents our initial efforts at measuring anion/arene interactions in solution. In particular, sulfonamide based hydrogen bonding receptors were developed with pendant aromatic rings to test the strength of anion/arene interactions in solution. Complementary computational chemistry and crystallography were utilized to supplement the solution studies. Chapter III describes our quantum calculations and crystallographic efforts at using only electron-deficient arenes to bind halides. A Cambridge Structure Database survey supports our emphasis of understanding multiple anion/arene interactions. Chapter IV illustrates how tripodal anion receptors can be developed to bind anions using only electron-deficient aromatic rings. Furthermore, subtle changes in anion binding geometries are observed with isomeric receptors and corroborated with Density Functional Theory calculations. Chapter V is dedicated to the preparation of electron-deficient anion receptors that are conformationally stabilized by hydrogen bonds. Chapter VI is committed to using our knowledge of anion binding to study a series of ethynyl-pyridine sulfonamides capable of hydrogen bonding to small molecules and anions. In conclusion, Chapter VII is a summary and future prospective for the field of anion/arene interactions. This dissertation includes previously published and co-authored material.
Adviser: Darren W. Johnson

Cette these porte sur la construction d'interfaces homme-machine animees. A l'heure actuelle, les interfaces graphiques font l'objet de nombreux travaux en ce qui concerne leurs techniques, leur architecture, et les outils pour les mettre en oeuvre. Le son et la video y sont parfois introduits. Mais l'animation y est rarement utilisee, et quand elle l'est, c'est de maniere marginale. Seuls les systemes d'animation d'algorithmes l'utilisent explicitement, mais ce sont des applications tres specifiques, qui sont plus graphiques que vraiment interactives. L'introduction d'animation dans les interfaces passe par l'etude de nombreux aspects. Quelles utilisations pour l'animation? quelles techniques pour concilier animation et interactivite? quels formalismes, quel modeles pour decrire des interfaces animees? whizz est une boite a outils pour realiser des interfaces animees. Elle est construite comme une extension d'x#t#v, une boite a outils pour interfaces a manipulation directe. Le modele propose par whizz repose sur la notion d'objets communiquant entre eux par des flots de donnees et des evenements. Certains de ces objets provoquent le mouvement, d'autres permettent de la decrire, et enfin les objets graphiques utilisent ces informations pour leur evolution. Ce modele permet ainsi de decrire de maniere homogene l'ensemble du comportement dynamique d'une interface, qu'il soit provoque par le temps, l'utilisateur, ou l'evolution des donnees representees. Par ailleurs, ses deux modes de transmission de l'information permettent de rendre compte des phenomenes continus ou ponctuels. Ils offrent aussi un moyen de structurer la communication a l'interieur d'une application interactive. La principale application de whizz a ce jour est witness, un outil de mise au point de programmes. Witness, qui par ailleurs possede les memes caracteristiques que les outils de mise au point habituels, permet la representation animee des donnees d'un programme. Avec witness, un programmateur peut envisager de mettre au point un programme grace a des representations graphiques qu'il aura lui-meme construites avec un outil de dessin

The ultrafast dynamics of a number of molecules have been studied in the gas phase through the use of frequency- angle- and time-resolved photoelecron imaging. A particular emphasis has been applied to the behaviour of biologically relevant molecules following photoexcitation. The gaseous ions were produced from an electrospray ionisation source and interrogated by a purpose-built velocity-map imaging photoelectron spectrometer with a minimum temporal resolution of ~50 fs. Firstly, the details of a global kinetic fitting routine for a time-resolved photoelectron spectrum are presented. Through fitting the constituent photoelectron images to a kinetic fit, the photoelectron angular anisotropy of the constituent features of the time-resolved spectrum is preserved. Secondly, the dynamics of the green fluorescent protein model chromophore following UV excitation were explored, identifying internal conversion of the initially produced excited state population to a lower lying excited state before photodetachment. Thirdly, frequency- and angle-resolved photoelectron imaging is employed to investigate the dynamics of anionic resonances of para-benzoquinone, that have been implicated in facilitating electron attachment to this moiety. Fourthly, the photoelectron spectra of a series of carboxylic acids are presented in order to assess the feasibility of producing anions by attaching carboxylic acids to neutral chromophores. Fifthly, a time-resolved photoelectron spectrum of the biological chromophore and carboxylic acid, all-trans¬-retinoic acid is presented. Finally, highly anisotropic photoelectron spectra of the dianion, antimony tartrate are presented. In order to explain the anisotropy, classical trajectories of electrons on the molecular electrostatic potential energy surface are calculated. From this, the observed anisotropy can be assigned the the shape of the molecular repulsive Coulomb barrier.

Thesis (Ph. D.)--University of Adelaide, Dept. of Chemistry, 1999?
Includes 5 leaves of errata. Includes reprints of author's previously published articles. Includes bibliographical references (leaves 228-245).

Animês e mangás: o mito vivo e vivido no imaginário infantil é uma análise hermenêutico-figurativa do mangá Naruto. O trabalho procura lançar questões sobre a importância da figura do herói do mangá shonen nos processos iniciáticos de crianças e adolescentes estudantes da rede pública paulistana. Para tanto, apoia-se, sobretudo, na teoria do imaginário de Gilbert Durand e da jornada do herói de Joseph Campbell. A pesquisa que teve como corpus de análise a primeira temporada do mangá Naruto e o animê de mesmo título, as produções imagéticas dos estudantes e as diferentes versões de narrativas tradicionais japonesas extraídas de sites otakus e de livros infanto-juvenis sustenta a ideia de que mangás são derivações, por empobrecimento, de mitos japoneses, que enformam as produções imagéticas dos apreciadores desse gênero literário. Com efeito, e por meio do método de convergência simbólica, a análise destaca o simbolismo ambíguo das figuras da raposa e dos meninos-heróis, recorrentes nas narrativas tradicionais e na iconografia japonesa. Importante ressalva é indicar não se tratar de uma abordagem comparativa entre a cultura japonesa e as culturas ocidentais que convivem com este gênero literário. A conclusão a que se chega ao final deste estudo é que o mangá Naruto constitui uma literatura iniciática que presentifica o arquétipo do herói no imaginário infantil e apresenta valor heurístico para pensarmos a construção de uma pedagogia do psiquismo imaginante proposta por Bruno Duborgel, assim como a dinâmica do imaginário de nossa própria época.
Animes and mangas: the living and lived myth in childhood imagination is an hermeneutic-figurative analysis of the Naruto manga, that launches questions about the importance of the shonen manga hero figure in the initiatory processes of children and adolescents students of São Paulo public schools network. For that, it relies, mainly, in the imaginary theory of Gilbert Durand and in the hero journey of Joseph Campbell. The research which had as its analysis corpus the first season of Naruto manga and the anime with the same title, the imagistic productions of students and the different versions of traditional Japanese narratives extracted from otakus sites and books for children and teenagers supports the idea that mangas are derivations by impoverishment of Japanese myths that shape the imagistic productions of enthusiasts of this literary genre. In effect, and by means of the symbolic convergence method, the analysis highlights the ambiguous symbolism of the fox and boy-heroes figures, recurrent in traditional narratives and in the Japanese iconography, although it is not to be confused with an eminently comparative approach between the Japanese culture and occidental cultures that coexist with this literary genre. The conclusion reached at the end of this study is that the Naruto manga constitutes an initiatory literature that makes present the hero archetype in the childhood imagination and that has an heuristic value to make us think about the construction of a pedagogy of imaginative psyche proposed by Bruno Duborgel, as well as the dynamics of our own epochs imaginary.

Cette these presente les differentes approches de l'animation par ordinateur ainsi que les principaux systemes existants. Elle propose ensuite le systeme gemsa, simulateur de comportements du squelette humain dans un environnement representant un appartement. Un modele mathematique de la marche humaine a ete developpe. Pour generer une variete de marches ainsi que des exagerations, nous avons impose a ce modele la parametrisation comme contrainte forte. L'utilisateur de gemsa exprime son scenario avec une formulation orientee-but. La specification des details de l'animation est alors prise en charge par le systeme. L'utilisateur peut, par exemple, demander au systeme de deplacer le squelette d'une piece a une autre ou de le faire asseoir sur une chaise donnee. La planification de chemins dans l'appartement ainsi que la detection et l'evitement d'obstacles sont traites dans cette these

En synthèse d'images, les scènes tridimensionnelles animées sont de plus en plus riches etdétaillées. Mais elles sont actuellement limitées dans les variations de leur échelle d'observation. Par exemple, créer des modèles permettant une ballade interactive passant continûment d'un atome à une galaxie pose de sérieux problèmes. L'objectif de cette thèse est d'y apporter une solution dans le cadre d'une visualisation temps-réel sur un matériel informatique standard. Tout d'abord, nous montrons pourquoi la modélisation multi-échelle procédurale est particulièrement bien adaptée pour résoudre ce problème. Plus précisément, nous utilisons la modélisation par complexification qui décrit un modèle par une représentation grossière et par un ensemble de fonctions qui lui ajoutent localement des détails jusqu'à satisfaire la précision requise par des critères perceptuels. Nous introduisons une nouveau formalisme basé sur le langage C++ capable de décrire un large éventail de modèles 3D animés sur de grandes variations d'échelle. Nous proposons un outil générique qui implémente ce formalisme appelé DynamicGraph. Cet outil offre d'une part une interface graphique dédiée et d'autre part un algorithme de rendu temps-réel qui évalue effcacement la visibilité et de la précision requise. Nous illustrons par différentes études de cas le potentiel de cette approche.

Femtosecond negative-ion photoelectron imaging spectroscopy allows the probing of dynamics resulting from solvation and photodissociation in both the time-resolved and solvent domains. First, the basic premise of photoelectron imaging shall be presented, followed by a discussion of qualitative approaches for interpreting photoelectron angular distributions as illustrated by application to the photoelectron images of S₂⁻ and CS₂⁻. The photoelectron images of CS₂⁻ serve as a reference for interpreting the results for homogeneous and heterogeneous solvation in CO₂ and OCS cluster anions. The effects of solvation upon the photoelectron angular distribution and the photoelectron energy spectrum are discussed in relation to (OCS)n⁻, OCS⁻·H₂O, (CO2)n⁻, and (CO₂)n(H₂O)m⁻. The (OCS)₂⁻ cluster anion images show evidence of competition of excited state decay pathways and coexistence of isomers. The evolution of photoelectron images, resulting from I₂Br⁻ dissociation shows the evolving electronic structure of the I⁻ channel as the anion dissociates.

My Ph.D research is mainly based on ‘calixarene and coordination complex hosts for anion’. The research is to make synthetic chloride ion channels for possible treatment of cystic fibrosis. Our approach is based on derivatives of larger calix[n]arenes. Calixarenes are chalice-shaped molecules that form readily under base catalyzed-condensation of tert-butyl phenol with formaldehyde. We have synthesized calixarenes which were tuned at the lower rim with bromo alkyl nitrile and reduced followed by reaction with a series of different isocyanates bearing fluorescent functional groups capable of binding and sensing chloride and nitrate. We are also interested how the host ligand binds with metal anions in solution and solid state chemistry. We synthesised simple pyridyl urea ligands and isomorphs. Their anion binding studies are discussed in terms of solid state and solution chemistry. Solid state structures based on silver and copper metal forming contact ion pairs with series of anions like nitrate, chloride, bromide, trifluoroacetate and boron tetrafluoride. Their solution based anion binding studies were performed and control titration results show that these hosts bind anions in a one to one fashion which was confirmed with solid state structures. An interesting aspect is that 2-ureidopyridine ligand exists in four different anhydrous crystal forms (I – IV0), which can be crystallized by several techniques. It was found that forms I and II only crystallize without another polymorph from methanol solution or in presence of inorganic salts. Thermoanalysis shows that all the modifications melt without previous transition and applying the heat of fusion rule proves this system to be completely monotropic. The crystal structures show that the molecule forms one intramolecular and two intermolecular hydrogen bonds to give S(6) and dimeric R (8) graph synthons in all four structures. However packing arrangements differ strikingly and since the hydrogen-bonding arrangement is the same for all the four forms, the differences in energy measured by thermoanalytical methods can only be caused by the different packing arrangements involving combinations of the weaker interactions, with the CH.¼S contacts being among the obvious differences. Thus, this system is a clear example in which the presence of robust, reproducible hydrogen bonded synthons does not lead to any control or predictability of polymorphic form.