As two of the most abundant natural polymers, chitin and lignin not only play critical roles in fungal and plant cell walls but are also important functional materials and promising feedstocks for a variety of chemicals. This study investigated the interactions of chitin and lignin thin films with several other molecules via a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). Interactions between chitin and family 18 chitinases are vital for understanding bacterial invasion of fungi and human defense against fungal infection. Regenerated chitin (RChitin) thin films were prepared via chemical conversion and spin-coating. Changes in their mass and viscoelasticity were monitored by a QCM-D in real time during incubation with family 18 chitinases. The optimal temperature for the activity of chitinases on surfaces was lower than bulk solution studies in the literature. Family 18 chitinases showed greater activity on dissolved chitin oligosaccharides while family 19 chitinases showed greater activity on RChitin films, which was attributed to chitin-binding domains in family 19 chitinases. Catechyl lignin (C-lignin) is a promising substrate for lignin valorization. Films of C-lignin were synthesized via adsorbed horseradish peroxidase-catalyzed dehydrogenative polymerization (DHP) of caffeyl alcohol (C-alcohol), and degraded through Fenton chemistry with all processes observed by a QCM-D and AFM. The synthetic rate and yield for C-DHP films was lower than DHP films made from coniferyl alcohol (G-alcohol) and p-coumaryl alcohol (H-alcohol). The C-DHP film underwent complete Fenton mediated degradation in contrast to the G-DHP and H-DHP films regardless of their thicknesses. Conventional lignin suffers from recalcitrance to degradation. Copolymer lignin films were synthesized through surface-initiated copolymerization of C and G or C, G and H monolignols. As the concentration of C-alcohol increased, the percentage degradation of the synthesized DHP copolymer films increased. Almost all the CG-DHP or CGH-DHP films were degraded when the percentage of the C-alcohol in the polymerization feed was ≥ 75% and ≥ 60% for CG-DHP and CGH-DHP, respectively. / Doctor of Philosophy / Natural polymers are widely considered as an alternative to fossil fuels for the production of biofuels, biochemicals, and biomaterials. The features of their biodegradability, biocompatibility, and sustainability can significantly alleviate concerns about environmental pollution and energy security. The surfaces of natural polymers are critical to their properties and applications. This dissertation focuses on the study of interfacial behaviors occurring at two of the most abundant natural polymers, chitin and lignin, via surface analysis techniques, a quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM). When an endosymbiont bacteria enter a fungal host, they secrete chitinases to soften and loosen the chitin layer in the fungal cell wall. Small chitin fragments will be released from digestion of the chitin layer of the fungal cell wall by chitinases in humans suffering from fungal infections. In order to fully understand the interactions between the fungal chitin layer and chitinases, a chitin thin film was fabricated to mimic the chitin layer, and the changes of the chitin film in mass, viscoelasticity, and morphology during treatment with family 18 chitinases were studied at various temperatures and pH using a QCM-D and AFM. Family 19 chitinases produced greater degradation of chitin thin films than family 18 chitinases, even though the family 18 chitinases had greater activity in solution. Greater surface activity for family 19 chitinases were attributed to chitin-binding domains in their chemical structure that are absent in family 18 chitinases. Millions of tons of lignin are produced in the lignocellulosic biorefinery and are discarded every year due to their recalcitrance to degradation as a result of their heterogeneous and complex structure. A newly discovered lignin, catechyl lignin (C-lignin), has potential for enhancing degradation on account of its simple linear structure. In this dissertation, C-lignin thin films were synthesized on gold-coated QCM-D sensor surfaces via surface-initiated dehydrogenative polymerization of caffeyl alcohol (C-alcohol). Their enzymatic and chemical degradation was investigated. It was found that the C-lignin films underwent complete chelator-mediated Fenton degradation in contrast to conventional lignin films. Although the C-lignin promises to be an ideal substrate for lignin valorization, its narrow distribution in nature severely limits its wide application. In view of this limitation, some people are trying to incorporate C units into conventional lignin through genetically engineered plants. This dissertation demonstrates the successful copolymerization of C-alcohol with conventional monolignols and the improved degradation of the synthesized C unit-containing copolymer lignin films relative to conventional lignin films. The results are expected to inform the design of lignocellulosic biomass for greater utilization.

The development of chiral organometallics for asymmetric synthesis is a topic of significant research in the recent past. The most studied in this class are the chiral organolithium reagents with many reported examples. The primary focus of our research is the development of C_α-chiral Grignard reagents, where the metal bearing α-carbon is the sole source of chirality. Examples of such Grignard reagents are rare owing to the problems associated with their synthesis, and their low configurational stability. We have studied these problems in three different modules of this project. Reactions of 1-magnesio-2,2-diphenyl-cyclopropylcarbonitrile with carbon electrophiles are first attempted in order to expand the utility of this configurationally stable C_α-chiral Grignard reagent in asymmetric synthesis. This reagent has been shown to be non-reactive towards carbon electrophiles at low temperatures. Consequently, we attempt to enhance the reactivity of this compound through two different approaches, Lewis-base activation and the "ate-complex" generation. The Magnesium/Halogen (Mg/X) exchange reactions have been shown to be extremely useful in the synthesis of complex Aryl, alkenyl (sp²) and alkynyl (sp) Grignard reagents. Examples of Mg/X exchange reactions of Alkyl (sp³) halides are, however, rare. Even more rare are such examples with secondary and tertiary alkyl halides, justifying the relative paucity of chiral Grignard reagents. In this module of our project, we study the Mg/X exchange reactions on secondary alkyl halides possessing a γ-hydroxyl group, as an internal activator for such Mg/X exchange reactions. Enantiomerization pathways of chiral organolithium compounds have been widely studied. However, few such studies have been performed on chiral Grignard reagents. In this module of the project, we studied the solvent assisted enantiomerization mechanism of the C_α-chiral 1-magnesio-2,2-diphenyl-cyclopropylcarbonitrile. Rate constant for the enantiomerization of this compound was measured in three different ethereal solvents to study the effect of solvent on the configurational stability. Finally, the order of the enantiomerization process with respect to [Et₂O] was studied in order to predict the mechanism of this process in Et₂O solvent. Our kinetic studies on the enantiomerization process provided us with a definitive picture for the enantiomerization of the C_α-chiral 1-magnesio-2,2-diphenyl-cyclopropylcarbonitrile, where solvation of the Grignard reagent preceded an ion-pair separation step which eventually lead to enantiomerization of the Grignard species. However, the precise structure of all the involved solvated intermediates could not be determined as kinetics was not able to distinguish between these intermediates. We next performed computational calculations to study the effect of solvation on the analogous 1-magnesio-cyclopropylcarbonitrile in order to address the unanswered questions from our kinetic studies. / Ph. D.

Die stöchiometrische Aktivierung von Trifluormethylschwefelpentafluorid mit dem Carben SIMes (1,3-Bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) wird thermisch und photochemisch beschrieben. Beide Formen der Aktivierung führen zur Detektion von 1,3-dimesityl-2,2-difluoroimidazolidin (SIMesF2), 1,3-dimesitylimidazolidin-2-sulfid (SIMes=S) und 1,3-dimesityl-2-fluoro-2-trifluoromethylimidazolidin (SIMes(CF3)F). Die Aktivierung von SF5CF3 wurde mit Radikalabfang-Experimenten untersucht, wobei die Ergebnisse auf die Bildung von CF3-Radikalen in der photochemischen Reaktion, nicht aber in der thermischen Reaktion hindeuten. Mechanistisch wird ein Einelektronentransfer von SIMes auf SF5CF3 postuliert. Weiterhin wurde die Reaktivität von SIMesF2 als Deoxyfluorierungsreagenz für verschiedene organische Substrate beobachtet. Zur mechanistischen Aufklärung der Acylfluorid-Synthese wurde das Imidazolidiniumsalz [SIMes-F]+F(HF)2- synthetisiert. Letzteres reagiert mit Benzoesäure zu Benzoylfluorid. Quantenmechanische Rechnungen bestätigen die These, dass ein externes Polyhydrogenfluorid für die Fluorierung der Benzoesäure verantwortlich ist. Anschließend wurde eine photoredoxkatalytische Trifluormethylierungen von Aromaten entwickelt. Ebenso wie bei der stöchiometrischen SF5CF3 Aktivierung wurde auch im Falle der photoredoxkatalytischen Aktivierung ein Einelektronentransfer auf SF5CF3 durch Oxidation des angeregten Katalysators oder Reduktion des zuvor oxidierten Katalysators vorgeschlagen. Experimentelle Untersuchungen des Mechanismus deuten auf die Entstehung von CF3-Radikalen, SF4 und Schwefel hin. Durch die Zugabe von Octanol zur Reaktionsmischung konnte die Bildung von Fluoroctan neben der Bildung von trifluormethylierten Aromaten erzielt werden. Dies deutet auf die Entstehung von Schwefeltetrafluorid hin und zeigt, dass SF5CF3 gleichzeitig als CF3-Quelle und als Quelle für SF4 dienen kann. / The stoichiometric activation of trifluoromethyl sulfur pentafluoride with the carbene SIMes (1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) is described thermally and photochemically. Both forms of activation lead to the detection of 1,3-dimesityl-2,2-difluoroimidazolidine (SIMesF2), 1,3-dimesitylimidazolidine-2-sulfide (SIMes=S) and 1,3-dimesityl-2-fluoro-2-trifluoromethylimidazolidine (SIMes(CF3)F). The activation of SF5CF3 was investigated by radical scavenging experiments, and the results indicate the formation of CF3 radicals in the photochemical reaction but not in the thermal reaction. Mechanistically, a one-electron transfer from SIMes to SF5CF3 is postulated. Furthermore, the reactivity of SIMesF2 as a deoxyfluorination reagent for several organic substrates was observed. The imidazolidinium salt [SIMes-F]+F(HF)2- was synthesized for the mechanistic investigation of the acyl fluoride synthesis. The latter reacts with benzoic acid to form benzoyl fluoride. Quantum mechanical calculations confirm that an external polyhydrogen fluoride is responsible for the fluorination of benzoic acid. Subsequently, a photoredox catalytic trifluoromethylation of aromatic compounds was developed. As in the case of stoichiometric SF5CF3 activation, a one-electron transfer to SF5CF3 by oxidation of the excited catalyst or reduction of the previously oxidized catalyst was also proposed in the case of photoredox catalytic activation. Experimental studies indicate the formation of CF3 radicals, SF4 and sulfur. The addition of octanol to the reaction mixture results in the formation of fluorooctane in addition to the formation of trifluoromethylated aromatics. This indicates the formation of sulfur tetrafluoride and shows that SF5CF3 can simultaneously serve as a CF3 source and as a source of SF4.

A brief introduction explaining phosphine ligand properties, Pd catalysed cross-coupling reactions; the importance of the steps involved in the catalytic cycle (oxidative addition, transmetalation & reductive elimination), mechanistic studies and a comparison of various reactions will give an overview of important cross-coupling reactions and their limitations. The development of a “super-concentrated” (5M) Pd catalysed Kumada type coupling reaction has been developed for coupling a range of aryl bromide and chloride substrates with the Grignard reagents ((p-CF₃-C₆H₄)MgBr)) and PhMgBr in methyl-tetrahydrofuran (Me-THF). Using a range of bidentate ligands such as bis-phosphinoferrocenyl ligands, good conversions were achieved using small amounts of solvent; up to 10 times less than typical procedures in THF. The unsymmetrical Pt complexes of the form [Pt(P-P)Br₂], [Pt(P-P)(Ph)Br] and [Pt(P-P)Ph₂] have been synthesised and characterised. The variations of substituents on the ligand system and the steric bulk have been shown to have a dramatic effect on the rate of transmetalation. The results provide one explanation why 1,1’-bis(di tert-butylphosphino)ferrocene (dtbpf), an excellent ligand for certain Suzuki reactions, is quite poor in reactions where transmetalation is more difficult. Palladium dichloride complexes of the ferrocenylphosphine based ligands 1,1’-bis- (diphenylphosphino)ferrocene (dppf), 1,1’-bis-(diisopropylphosphino)ferrocene (dippf) and 1,1’-bis-(di-tert-butylphosphino)ferrocene (dtbpf) have been shown to be active in the Hiyama cross-coupling of p-bromoacetophenone and vinyltrimethoxysilane (CHCH₂Si(OMe₃)) in the presence of TBAF under thermal heating and microwave conditions. Ligands with the optimum balance for promoting the transmetalation, oxidative addition and reductive elimination steps along the reaction pathway have been identified. Competition experiments are consistent with slow transmetalation being an issue with the Hiyama reaction relative to the Suzuki coupling. A novel protocol has been developed for the synthesis of aryl-alkyl ethers via C-O bond activation under Pd catalysed conditions. Utilising the unsymmetrical 1-bis-(ditertbutyl-1’- bis-diphenylphosphino)ferrocene (dtbdppf) under optimised conditions with silicon based nucleophiles and NaOH or TBAF as an activator, the formation of methyl, ethyl, n-propyl and n-butyl ethers with a range of aryl halides was achieved in good yield.

L’étude des transitions structurales dans les protéines est d’un intérêt crucial car ces transformations sont impliquées dans de nombreux processus biologiques essentiels. De tels phénomènes structuraux peuvent être à l’origine de propriétés remarquables dans les protéines flexibles ou désordonnées, propriétés difficilement accessibles par les techniques structurales usuelles. Le marquage de spin couplé à la spectroscopie de résonance paramagnétique électronique (RPE) est une technique bien adaptée pour l’étude de ces transitions structurales. L’insertion d’un radical nitroxyde sur une cystéine, naturelle ou introduite par mutagenèse dirigée, située à un endroit clé de la protéine permet d’obtenir des informations locales sur les changements structuraux éventuels provoqués par l’ajout d’un partenaire.Cette technique a été appliquée à deux systèmes biologiques comportant un degré de flexibilité différent. La flexibilité de la protéine chaperon NarJ, intervenant dans la biogenèse du complexe Nitrate Réductase de la bactérie Escherichia coli, a été étudiée en présence de son peptide partenaire. Ces études ont permis d’une part de déterminer le site d’interaction et d’autre part, de montrer que l’association des deux partenaires entraîne un verrouillage dans une conformation préférentielle de NarJ. Le deuxième sujet d’étude est la protéine CP12 de Chlamydomonas reinhardtii, intervenant dans la régulation d’un complexe supramoléculaire du cycle de Calvin. La CP12 s’apparente à une protéine intrinsèquement désordonnée, ayant la particularité de posséder des cystéines naturelles et fonctionnelles. Le marquage classique a permis de mettre en évidence un nouveau rôle de son partenaire et de montrer que la CP12 garde un caractère désordonné dans le complexe. Par ailleurs, cette protéine a servi de système d’étude pour développer une nouvelle stratégie de marquage sur Tyrosine et démontrer sa faisabilité. / The study of structural transitions in proteins is of crucial interest because these transformations are involved in many biological processes. Such structural phenomena can be the source of remarkable properties in flexible or disordered proteins, properties hardly accessible by conventional structural techniques. Site-directed spin labeling combined with electron paramagnetic resonance spectroscopy (EPR) is a technique well suited for the study of these structural transitions. The insertion of a nitroxide reagent on a cysteine, natural or introduced by site-directed mutagenesis, located in a key position of a protein provides local information on possible structural changes induced by the addition of a partner. This technique was applied on two biological systems with a different degree of flexibility. The flexibility of NarJ, a chaperon protein involved in the biogenesis of the complex nitrate reductase of Escherichia coli was studied in the presence of its peptide partner. These studies enabled us to determine the interaction site and to show that the association of the two partners induced a locked conformation of NarJ. The second system is the CP12 protein of Chlamydomonas reinhardtii, involved in the regulation of a supramolecular complex of the Calvin cycle. CP12 shares some similarities with the intrinsically disordered protein but having natural and functional cysteines. The conventional labeling allowed us to highlight a new role of its partner and to demonstrate that CP12 remains disordered in the complex. Moreover, this protein was used as a model system to develop a new labeling strategy on tyrosine and to demonstrate its feasibility.

Luminescent lanthanide containing coordination polymers and metal-organic frameworks hold great potential in many applications due to their distinctive spectroscopic properties. While the ability to design coordination polymers for specific functions is often mentioned as a major benefit bestowed upon these compounds, the lack of a meaningful understanding of the crystal engineering and luminescence in lanthanide coordination polymers remains a significant challenge toward functional design. Currently, the study of luminescence attributed to these compounds is based on the antenna effect as derived from molecular systems, where organic antennae are used to facilitate lanthanide-centered luminescence. This molecular based approach does not take into account the unique features of extended network solids, particularly the formation of band structure. By comparing molecular and band-based approaches, it was determined that the band structure of the organic sensitizing linker needs to be considered when evaluating the luminescence of lanthanide coordination polymers. This new model, as well as work on the crystal engineering and sensor applications of these materials will be presented. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2017. / FAU Electronic Theses and Dissertations Collection

Este trabalho tem como meta o estudo comparativo de duas rotas de síntese do megazol, tomando como base estudos feitos na Faculdade de Ciências Farmacêuticas da USP. Nestes foram observados que a obtenção do megazol pode ser feita por diferentes caminhos sintéticos, modificando processos e reagentes envolvidos na química de heterocíclicos, em particular os imidazóis. Foram avaliadas condições experimentais, rendimentos parciais e globais bem como as características de reagentes envolvidos nos processos indicados. / The scope of the present work is the analogy study over the two main routes on megazol synthesis, based on studies previously accomplished at the College of Pharmaceutical Sciences of USP. In the results of the above referred studies, it was observed that the obtaining of the megazol can be achieved by different synthetic ways, by modifying processes and reagents related to the chemical properties of heterocyclic compounds, particularly with the imidazoles. Experimental conditions, both partial and final yields as well as the characteristics of the reagents evolved in the indicated processes were evaluated.

Este trabalho tem como meta o estudo comparativo de duas rotas de síntese do megazol, tomando como base estudos feitos na Faculdade de Ciências Farmacêuticas da USP. Nestes foram observados que a obtenção do megazol pode ser feita por diferentes caminhos sintéticos, modificando processos e reagentes envolvidos na química de heterocíclicos, em particular os imidazóis. Foram avaliadas condições experimentais, rendimentos parciais e globais bem como as características de reagentes envolvidos nos processos indicados. / The scope of the present work is the analogy study over the two main routes on megazol synthesis, based on studies previously accomplished at the College of Pharmaceutical Sciences of USP. In the results of the above referred studies, it was observed that the obtaining of the megazol can be achieved by different synthetic ways, by modifying processes and reagents related to the chemical properties of heterocyclic compounds, particularly with the imidazoles. Experimental conditions, both partial and final yields as well as the characteristics of the reagents evolved in the indicated processes were evaluated.

Na primeira parte deste trabalho, desenvolvemos duas metodologias para a preparação de α-dicloroteluro cetonas. A primeira utiliza a reação direta de tricloretos de ariltelúrio com cetonas e a segunda envolve a reação do mesmo reagente com éteres enólicos de silício de cetonas. As dicloroteluro cetonas preparadas foram transformadas em α-halo cetonas pela reação com cloro ou bromo, ou utilizando condições de termólise sob pressão reduzida. Dados de ressonância magnética nuclear de 1H e de 13C, de difração de raios-X e de espectros no infra-vermelho foram utilizados na determinação estrutural dos compostos preparados. Numa segunda arte foram preparados α-halo-α-seleno alcanos através da adição de HBr a selenetos vinílicos obtidos por reação de acetilenos aromáticos com selenofenol. Os α-halo-α-seleno alcanos foram transformados em α-selenofenil acetaldeídos por reação de solvólise em DMSO. / In the first parto of this work two methodologies for the synthesis of α-dichlorotelluroketones were developed. The first one employs the reaction of aryltellurium tricholorides with ketones and the second one involves the reaction of the same reagent with silylenol ethers of ketones. The α-dichlorotelluroketones prepared were transformed into α-halo ketones by means of the reaction with chlorine or bromine or by pyrolysis at reduced pressure. 1H and 13C nuclear magnetic ressonance, x-ray difraction and infrared data were used in the structure elucidations of the compounds prepared. In the second part of the work α-halo- α-seleno-alkanes were prepared by addition of hydrogen bromide to vinylic selenides which were prepared by reacting aromatic acetylenes with selenophenol. The α-halo-α-seleno-alkanes were transformed into α-selenophenyl acetaldehydes by solvolysis in DMSO.

A di-2-piridil cetona benzoilhidrazona (DPKBH) é um reagente solúvel em uma série de solventes orgânicos mas pouco solúvel em água. Vem sendo utilizado para a determinação de metais, (principalmente do grupo de transição) como Fe(II), Fe(III), Ni(II), Cu(II), entre outros e como ligante de referência para estudar o comportamento dos íons Fe(II) e Fe(III) em presença de espécies orgânicos encontrados em águas naturais. Com o objetivo de entender melhor as propriedades do DPKBH em meio de etanol, foi necessário determinar as constantes de dissociaçãolionização em diferentes porcentagens desse solvente orgânico (10, 19, 29 e 48 %). Nestas porcentagens de etanol, através de medidas absolutas de pH determinaram-se os pKs do DPKBH utilizando-se a técnica potenciométrica e em 10 e 48 % de etanol através de medidas absolutas de pH associadas às absorbâncias das espécies presentes nos equilíbrios, utilizando-se a técnica espectrofotométrica. Nas devidas porcentagens de etanol, o comportamento do eletrodo foi previamente determinado. Os valores de pK1 3,210; 3,342; 3,398 e 3,360 e de pK2 10,834; 11,013; 11,793 e 11,382 foram obtidos respectivamente para 10, 19, 29 e 48 % de etanol, utilizando-se a técnica potenciométrica. Através da técnica espectrofotométrica os valores de pK1 foram 3,257 e 3,322 e pK2 10,880 e 11,820, em 10 e 48 % de etanol, respectivamente. / The di-2-pyridyl ketone benzoylhydrazone (DPKBH) is a soluble reagent in different organic solvents but slightly soluble in water. It has been used for metal determinations, (mainly transition metals) such as for Fe (II), Fe(III), Ni(II), Cu(II) and also like a reference ligand to study the behavior of Fe(II) and Fe(III) ions in the presence of organic species found in natural waters. So as to better understand the DPKBH properties In ethanol, it was necessary to determine the dissociation/ionization constant in different percentages of ethanol (l0, 19, 29 and 48%). In these ethanol percentages, through absolute pH measurements, pKs of DPKBH could be the found by using the potentiometric technique, and in 10 and 48% of ethanol the pKs of DPKBH were determined with pH measurements associated to absorbance of the species present in the equilibria by using the spectrophotometric technique. In appropiate percentage of ethanol the behavior of the glass electrode was previously determined. The pK1 values 3.210; 3.342; 3.398 and 3.362, and pK2 10.834; 11.013; 11.793 and 11.382 were found for 10,19,29,48 % of ethanol, by using the potentiometric technique. The spectrophotometric technique led to pK1 values 3.257 and 3.322, and the pK2 ones 10.880 and 11. 820 in 10 and 48 % of ethanol respectively.