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Tailored fluoropolymers remain the leading choice for a wide variety of advanced high-performance applications, including electronic/optical and energy conversion, owing to their unique blend of complementary high-performance properties. Amorphous semi-fluorinated polymers exhibit improved solubility and melt processability when compared to traditional perfluoropolymers. A leading class of semi-fluorinated aryl ether polymers includes perfluorocyclobutyl (PFCB), perfluorocycloalkenyl (PFCA), and fluoroarylene vinylene ether (FAVE) polymers. Monomers containing aromatic trifluorovinyl ethers (TFVE) are used to synthesize PFCB polymers via radical-mediated [2+2] cyclodimerization. On the other hand, FAVE and PFCA polymers are polymerized via base-mediated nucleophilic addition/elimination of bisphenols with TFVE monomers and decafluorocyclohexene respectively. The use of different monomer cores (aromatic, aliphatic, contorted, and renewable) should help to develop general structure/property relationships for this versatile and expanding approach to semi-fluorinated aryl ether polymers. The enchainment of polycyclic aromatic hydrocarbon (PAH) cores with functional fluorocarbon groups (or segments) recently afforded a new class of semi- fluorinated polymers in the continuing quest for novel organic materials for potential applications in optoelectronic, gas-separation, and advanced composites. Chapter 2 details the incorporation of commercially available acenaphthenequinone was achieved to afford PFCB aryl ether polymers with excellent solubility, high thermal stability, and film-forming capability. Chapter 3 represents base-promoted nucleophilic addition/elimination of commercial bisphenols with TFVE-triphenylene monomers affording FAVE aryl ether polymers possessing excellent solution processability, high thermal stability and photostability. In addition, triphenylene-enchained FAVE polymers exhibit extreme thermal-oxidative photostability and emit blue light after heating in air at 250 °C for 24 h. Further, time-dependent density functional theory (TD-DFT) computations were performed to understand electronic polymer structures. In one case, post-polymerization Scholl coupling converted the central triphenylene core to afford a hexabenzocoronene containing semi-fluorinated polymer with new optoelectronic properties. Chapter 4 demonstrates synthesis and characterization of renewable semi-fluorinated polymers obtained using aliphatic diol isosorbide. This renewable diol readily polymerizes with bis-TFVE derivatives of bisphenol A and 6F to provide high molecular weight thermoplastics exhibiting excellent solubility and tough, transparent film-forming capability. Finally, Chapter 5 presents synthesis of TFVE enchained corannulene which gave blue-light emission and outstanding processability. Synthesis and characterization, including the new materials' optical, thermal, and electronic properties, is presented.

Este estudo foi realizado para testar técnicas de ressonância magnética funcional (RMf) para investigar aspectos funcionais da pineal humana. Foram coletadas imagens funcionais e amostras de sangue total para a dosagem da melatonina plasmática antes, durante e após a apresentação de estímulo com luz azul quase monocromática em indivíduos saudáveis. Os participantes realizaram o exame de tomografia computadorizada do crânio sem o uso de contraste endovenoso (TC), para a avaliação qualitativa do grau de calcificação pineal. As conclusões foram: a) não houve ativação da pineal em resposta à aplicação da luz; b) não houve diferenças estatisticamente significativas entre as condições pré-estímulo, durante o estímulo ou pós-estímulo usando diferentes métodos de análise dos dados de RMf, porém, observou-se tendência de maior poder espectral na pineal durante a aplicação do estímulo luminoso do que nas condições pré e pós-estímulo; c) foi identificada a conectividade funcional da pineal, que poderá ser melhor avaliada em estudo futuro. / This study aimed to test the functional magnetic resonance imaging (fMRI) techniques in order to investigate the functional aspects of human pineal gland. Some functional images and total blood samples for dosing the plasmatic melatonin concentration were collected before, during and after the presentation of a monochromatic blue light stimulation in healthy individuals. All subjects were examined by a brain CT scan, with no the administration of endovenous contrast, for the qualitative assessment of the pineal calcification level. The conclusions were the following: a) there was no pineal activation in response to the application of light; b) there were no statistically significant differences between the pre-, during and poststimulation conditions with different analysis methods of fMRI data, however, there was a trend of greater spectral power in the pineal gland during the luminous stimulation application than under the other conditions; c) the functional connectivity of the pineal could be identified, which should be better assessed in a future study.

Die lichtaktivierte Kinase Phototropin aus Chlamydomonas reinhardtii, die photoaktivierte Adenylatcyclase (PAC) aus Euglena gracilis und das BLUF-Protein Slr1694 aus Synechocystis sp. PCC 6803 wurden in Hinblick auf die molekularen Details der primären photochemischen Prozesse sowie der Signalweiterleitung untersucht. Phototropin wurde mit Hilfe von Arginin aus Escherichia coli in Milligramm Mengen isoliert. Ohne Arginin wurde E. coli cAMP Rezeptorprotein assoziiert aufgefunden, welches eine hohe Homologie zu einer cAMP aktivierten Kinase aus C. reinhardtii besitzt. Volllängen Phototropin bildet wie einzelne LOV-Domänenkonstrukte ohne Kinasedomäne den Flavin-Triplettzustand und das kovalente Cysteinyl-Addukt. Der Zerfall des Signalzustandes ist in Anwesenheit von ATP beschleunigt und deutet auf Photorezeptor-Kinase Interaktion hin. Strukturelle Änderungen in der Kinasedomäne wurden durch FTIR-Differenzspektroskopie gezeigt. Über ELDOR-Spektroskopie wurde der Abstand der Photorezeptordomänen auf etwa 25 Angstrom bestimmt. Mutationen in Slr1694 an S28, N31 und W91 zeigten keine konservierten Einfluss auf die Dynamik des Signalzustands. Die Entfernung der Seitenkette von S28 führte zu einer 15 nm Rotverschiebung des Absorptionsspektrums aufgrund veränderter Wasserstoffbrückenkoordination des Kofaktors. Die Einführung von positiv geladenen Seitenketten an Stelle von N31 erhöhte die Kofaktorbindung von phosphorylierten Flavinen. Künstliche Kofaktoren wie Roseoflavin konnten in Slr1694 durch Koexpression eines prokaryotischen Flavintransporters erreicht werden. Die Rolle von M152 in PAC für die Signalweiterleitung wurde anhand der lichtaktivierten cAMP Synthese-Aktivität gezeigt. Durch ultraschnelle IR-Spektroskopie wurde die Beteiligung der Seitenketten von Y8 sowie Q50 bestätigt und eine genauere Beschreibung der Wasserstoffbrücken im langlebigen Signalzustand ermöglicht. / The light activated kinase Phototropin from Chlamydomonas reinhardtii, the photoactivated adenylylcyclase (PAC) from Euglena gracilis and the BLUF protein Slr1694 from Synechocystis sp. PCC 6803 were investigated concerning the molecular details of the primary photochemistry as well as signal transduction. Phototropin was isolated from Escherichia coli in mg amounts after solubilization with arginine. Without arginine E. coli cAMP receptor protein, which shows high homology to a cAMP activated kinase from C. reinhardtii, was copurified. Full length Phototropin shows similar photochemistry to LOV-domain containing proteins without the kinase including triplet and covalent cysteinyl adduct formation. Signaling state decay is accelerated in the presence of ATP and suggests photoreceptor-kinase interaction. FTIR spectroscopy showed light induced structural changes in the kinase domain. The distance of the photoreceptor domains of 25 Angstrom was determined by ELDOR spectroscopy. Mutation of the side chains of S28, N31 and W91 in Slr1694 showed no conserved influence on the dynamic of the signaling state. Removal of the hydroxyl group of S28 lead to a 15 nm red shift of the absorption spectrum as a result of altered hydrogen bond coordination of the cofactor. Introduction of positively charged side chains at the position of N31 strengthened the binding of phosphorylated flavins. An artificial flavin like roseoflavin was introduced in Slr1694 by coexpression of a bacterial flavin transporter. The essential role of M152 in PAC for signal transduction was shown by determination of light activated cAMP synthesis activity. Ultrafast IR spectroscopy confirmed the contribution of Y8 and Q50 in the photocycle and gave a more detailed description of the hydrogen bonding situation in the signaling state.

Este estudo foi realizado para testar técnicas de ressonância magnética funcional (RMf) para investigar aspectos funcionais da pineal humana. Foram coletadas imagens funcionais e amostras de sangue total para a dosagem da melatonina plasmática antes, durante e após a apresentação de estímulo com luz azul quase monocromática em indivíduos saudáveis. Os participantes realizaram o exame de tomografia computadorizada do crânio sem o uso de contraste endovenoso (TC), para a avaliação qualitativa do grau de calcificação pineal. As conclusões foram: a) não houve ativação da pineal em resposta à aplicação da luz; b) não houve diferenças estatisticamente significativas entre as condições pré-estímulo, durante o estímulo ou pós-estímulo usando diferentes métodos de análise dos dados de RMf, porém, observou-se tendência de maior poder espectral na pineal durante a aplicação do estímulo luminoso do que nas condições pré e pós-estímulo; c) foi identificada a conectividade funcional da pineal, que poderá ser melhor avaliada em estudo futuro. / This study aimed to test the functional magnetic resonance imaging (fMRI) techniques in order to investigate the functional aspects of human pineal gland. Some functional images and total blood samples for dosing the plasmatic melatonin concentration were collected before, during and after the presentation of a monochromatic blue light stimulation in healthy individuals. All subjects were examined by a brain CT scan, with no the administration of endovenous contrast, for the qualitative assessment of the pineal calcification level. The conclusions were the following: a) there was no pineal activation in response to the application of light; b) there were no statistically significant differences between the pre-, during and poststimulation conditions with different analysis methods of fMRI data, however, there was a trend of greater spectral power in the pineal gland during the luminous stimulation application than under the other conditions; c) the functional connectivity of the pineal could be identified, which should be better assessed in a future study.