O objetivo deste estudo foi sintetizar nanopartículas de ouro (AuNPs) em meio aquoso, transferí-las para diferentes meios orgânicos, e avaliar sua estabilidade (não-agregação) nesses meios, com o intuito de otimizar a exploração de suas propriedades ópticas. Foi utilizado o ácido tetracloroáurico (HAuCl4) como precursor de ouro metálico em meio aquoso e fez-se a transferência para clorofórmio (CHCl3) e diclorometano (CH2Cl2). Como agente de transferência, utilizou-se o polietilenoglicol tiolado (PEGSH) junto com o dodecanotiol (DDT). O PEG-SH foi adicionado na fase aquosa para evitar a agregação das AuNPs, assim como em fase orgânica, o DDT foi adicionado como agente estabilizador, pois sua cadeia alifática promove interações hidrofóbicas entre as partículas. Avaliou-se dois diâmetros médios de nanopartículas. A eficiência de transferência e a distribuição de tamanho das AuNPs foram estudadas utilizando a espectroscopia UV-Vis, espalhamento dinâmica de luz e microscopia eletrônica de transmissão. As nanopartículas denominadas AuNPs1 apresentaram AbsRPLS média de 0,8314 em ʎmédio = 521 nm e as AuNPs2 AbsRPLS média de 1,2643 em ʎmédio = 526 nm. Quando as AuNPs foram transferidas para solventes orgânicos, os espectros de absorção obtidos por UV-Vis apresentaram deslocamento da banda RPLS para o vermelho, em CHCl3, ʎAuNPs1 = 531 nm e ʎAuNPs2 = 534 nm; em CH2Cl2, ambas as soluções apresentaram ʎ = 530 nm. Este deslocamento é um dos fatores que indicaram a não-agregação das AuNPs. Em DLS, foi confirmada a nãoagregação. Em CHCl3, as AuNPs1 apresentaram eficiência de transferência de 97,27% e as AuNPs 98,88%, enquanto, em diclorometano, apenas 80,21% das AuNPs foram transferidas. As AuNPs apresentaram ao longo do tempo maior estabilidade em CHCl3 do que em CH2Cl2. Após a transferência para o CHCl3, as AuNPs foram separadas deste solvente e redissolvidas em outros solventes orgânicos com diferentes índices de refração: álcool benzílico, etanol e dimetilsulfóxido (DMSO). As AuNPS permaneceram visivelmente estáveis somente em álcool benzílico, pois nos outros solventes foi observado que a solução coloidal apresentou perda da coloração e por UV-Vis foi verificada a diminuição da banda da RPLS em DMSO e a ausência em etanol. / The objective of this study was to synthesize gold nanoparticles (AuNPs) in aqueous media, transfer them to different organic media, and evaluate their stability (non-aggregation) in these media, in order to optimize the exploration of their optical properties. Tetrachlorouric acid was used as the gold precursor in aqueous medium and transferred to chloroform (CHCl3) and dichloromethane (CH2Cl2). As the transfer agent, thiolated polyethylene glycol (PEG-SH) was used along with dodecanethiol (DDT). PEG-SH was added in the aqueous phase to prevent AuNPs from aggregating, as well as in the organic phase, DDT was added as a stabilizing agent because its aliphatic chain promotes hydrophobic interactions between the particles. Two average nanoparticle diameters were evaluated. The transfer efficiency and size distribution of the AuNPs were studied using UV-Vis spectroscopy, dynamic light scattering and transmission electron microscopy. The nanoparticles named AuNPs1 presented mean AbsRPLS of 0,8314 in ʎmedium = 521 nm and the AuNPs2 AbsLSPR mean of 1,2643 in ʎmedium = 526 nm. When the AuNPs were transferred to organic solvents, the absorption spectra obtained by UV-Vis showed red band shift in CHCl3, ʎAuNPs1 = 531 nm and ʎAuNPs2 = 534 nm; in CH2Cl2, both solutions showed ʎ = 530 nm. This displacement is one of the factors that indicated the non-aggregation of AuNPs. In DLS, non-aggregation was confirmed. In CHCl3, AuNPs1 showed transfer efficiency of 97,27% and AuNPs 98.88%, while in dichloromethane only 80,21% of AuNPs were transferred. AuNPs showed greater stability over time in CHCl3 than in CH2Cl2. After transfer to CHCl3, the AuNPs were separated from this solvent and redissolved in other organic solvents with different refractive indexes: benzyl alcohol, ethanol and dimethylsulfoxide (DMSO). The AuNPS remained visibly stable only in benzyl alcohol, because in the other solvents it was observed that the colloidal solution showed a loss of coloration and, by UV-Vis, the reduction of the LSPR band in DMSO and absence in ethanol was verified.

This thesis presents the application and development of H-bond donor organocatalysts. Chapter 2 presents an intramolecular Michael addition of β-dicarbonyls onto α,β-unsaturated esters catalyzed by tertiary amine/H-bond donor bifunctional catalysts, achieving up to 88% ee. Chapter 3 outlines the design and synthesis of a new family of cinchona-derived H-bond donor/ammonium salt phase-transfer catalysts. The ability of these asymmetric phase-transfer catalysts to activate less reactive substrates than their tertiary amine analogues and to induce higher levels of enantiocontrol than commercially available phase-transfer catalysts was demonstrated in an intramolecular Michael addition. Chapter 4 details the highly successful application of these new H-bond donor/ammonium salt phase-transfer catalysts to the enantio- and diastereoselective nitro-Mannich reaction of α-amido sulfones with nitroalkanes. Preliminary investigations into a novel phase-transfer catalyzed asymmetric ketimine reduction demonstrate the ability of these catalysts to provide access to new methods.

O objetivo deste estudo foi sintetizar nanopartículas de ouro (AuNPs) em meio aquoso, transferí-las para diferentes meios orgânicos, e avaliar sua estabilidade (não-agregação) nesses meios, com o intuito de otimizar a exploração de suas propriedades ópticas. Foi utilizado o ácido tetracloroáurico (HAuCl4) como precursor de ouro metálico em meio aquoso e fez-se a transferência para clorofórmio (CHCl3) e diclorometano (CH2Cl2). Como agente de transferência, utilizou-se o polietilenoglicol tiolado (PEGSH) junto com o dodecanotiol (DDT). O PEG-SH foi adicionado na fase aquosa para evitar a agregação das AuNPs, assim como em fase orgânica, o DDT foi adicionado como agente estabilizador, pois sua cadeia alifática promove interações hidrofóbicas entre as partículas. Avaliou-se dois diâmetros médios de nanopartículas. A eficiência de transferência e a distribuição de tamanho das AuNPs foram estudadas utilizando a espectroscopia UV-Vis, espalhamento dinâmica de luz e microscopia eletrônica de transmissão. As nanopartículas denominadas AuNPs1 apresentaram AbsRPLS média de 0,8314 em ʎmédio = 521 nm e as AuNPs2 AbsRPLS média de 1,2643 em ʎmédio = 526 nm. Quando as AuNPs foram transferidas para solventes orgânicos, os espectros de absorção obtidos por UV-Vis apresentaram deslocamento da banda RPLS para o vermelho, em CHCl3, ʎAuNPs1 = 531 nm e ʎAuNPs2 = 534 nm; em CH2Cl2, ambas as soluções apresentaram ʎ = 530 nm. Este deslocamento é um dos fatores que indicaram a não-agregação das AuNPs. Em DLS, foi confirmada a nãoagregação. Em CHCl3, as AuNPs1 apresentaram eficiência de transferência de 97,27% e as AuNPs 98,88%, enquanto, em diclorometano, apenas 80,21% das AuNPs foram transferidas. As AuNPs apresentaram ao longo do tempo maior estabilidade em CHCl3 do que em CH2Cl2. Após a transferência para o CHCl3, as AuNPs foram separadas deste solvente e redissolvidas em outros solventes orgânicos com diferentes índices de refração: álcool benzílico, etanol e dimetilsulfóxido (DMSO). As AuNPS permaneceram visivelmente estáveis somente em álcool benzílico, pois nos outros solventes foi observado que a solução coloidal apresentou perda da coloração e por UV-Vis foi verificada a diminuição da banda da RPLS em DMSO e a ausência em etanol. / The objective of this study was to synthesize gold nanoparticles (AuNPs) in aqueous media, transfer them to different organic media, and evaluate their stability (non-aggregation) in these media, in order to optimize the exploration of their optical properties. Tetrachlorouric acid was used as the gold precursor in aqueous medium and transferred to chloroform (CHCl3) and dichloromethane (CH2Cl2). As the transfer agent, thiolated polyethylene glycol (PEG-SH) was used along with dodecanethiol (DDT). PEG-SH was added in the aqueous phase to prevent AuNPs from aggregating, as well as in the organic phase, DDT was added as a stabilizing agent because its aliphatic chain promotes hydrophobic interactions between the particles. Two average nanoparticle diameters were evaluated. The transfer efficiency and size distribution of the AuNPs were studied using UV-Vis spectroscopy, dynamic light scattering and transmission electron microscopy. The nanoparticles named AuNPs1 presented mean AbsRPLS of 0,8314 in ʎmedium = 521 nm and the AuNPs2 AbsLSPR mean of 1,2643 in ʎmedium = 526 nm. When the AuNPs were transferred to organic solvents, the absorption spectra obtained by UV-Vis showed red band shift in CHCl3, ʎAuNPs1 = 531 nm and ʎAuNPs2 = 534 nm; in CH2Cl2, both solutions showed ʎ = 530 nm. This displacement is one of the factors that indicated the non-aggregation of AuNPs. In DLS, non-aggregation was confirmed. In CHCl3, AuNPs1 showed transfer efficiency of 97,27% and AuNPs 98.88%, while in dichloromethane only 80,21% of AuNPs were transferred. AuNPs showed greater stability over time in CHCl3 than in CH2Cl2. After transfer to CHCl3, the AuNPs were separated from this solvent and redissolved in other organic solvents with different refractive indexes: benzyl alcohol, ethanol and dimethylsulfoxide (DMSO). The AuNPS remained visibly stable only in benzyl alcohol, because in the other solvents it was observed that the colloidal solution showed a loss of coloration and, by UV-Vis, the reduction of the LSPR band in DMSO and absence in ethanol was verified.

No description available.

O emprego da catálise de transferência de fase substituindo uma ou mais etapas da síntese de um fármaco, pode ser um recurso vantajoso sob o ponto de vista tecnológico. Empregado na síntese de importantes fármacos que são a dicicloverina, caramifeno eamiodarona, a catálise de transferência de fase revelou-se muito vantajosa na síntese dos dois primeiros. A dicicloverina e o caramifeno tiveram as suas rotas de obtenção verticalizadas, com bons resultados e custos bem mais baixos quando comparados com os atualmente adquiridos no exterior. Ficou evidente que a catálise de transferência de fase pode ser aplicada com sucesso na produção destes e outros fármacos em associação com técnicas já conhecidas com ótimos resultados. / The phase transfer catalysis application replacing one or more steps in the drug synthesis, can be of advantage in the technologycal approach. Applied to the synthesis of important drugs such as diciclomine, caramiphen,and amiodarone, the phase transfer catalysis resulted in a very advantageous method in the first two drugs. The diciclomine and the caramiphen, gets their obtention routes from raw materiaIs wi th good resul ts and low coasts, when compared wi th the drugs presently purchassed in foreign countries. It is clear that the phase transfer catalysis, can be applied succesfully in the manufacturing of these and other drugs, in conjuction with known techniques with good results.

O presente trabalho teve como objetivo central estudar, sob condições de Catálise de Transferência de Fase, as reações de C-alquilação de diversos compostos contendo em sua estrutura molecular os grupos α-fenil ou α-naftilacetila: (Ver arquivo PDF). Nas várias reações efetuadas, foram empregados o hidrogenossulfato de tetrabutilamônio (TBAH) e catalisadores quirais derivados de alcalóides da cinchona. Foram investigadas, para cada substrato, várias condições experimentais, tanto em sistema sólido-líquido como líquido-líquido. Nas reações dos ésteres (24), (25) e (26) foram observados produtos derivados da hidrólise do grupo éster. No entanto, para os ésteres (27), (28) e (29) a reação de C-alquilação era preponderante, o que permitiu a extrapolação ao uso de catalisadores quirais. Para estes substratos, apenas o produto de C-alquilação do éster (28) apresentou excesso enantiomérico (8-12%). Os resultados insatisfatórios obtidos para os 6 ésteres estudados foram atribuídos à baixa acidez dos prótons metilênicos, à enolização do produto ou a fatores estruturais. O produto da C-benzilação da amida (31) foi isolado em baixo rendimento e 30% de excesso enantiomérico. Uma comparação com os resultados obtidos para amida (30) permitiu inferir que a substituição de um grupo fenila por um grupo naftila produz um aumento de reatividade e uma melhor interação com o catalisador quiral. No caso da acil-imina (32) e das acil-hidrazonas (33) e (34) os produtos foram obtidos em rendimentos de médios a bons e apresentavam atividade óptica. No entanto, a dificuldade técnica de determinar seu excesso enantiomérico impossibilitou a avaliação da enantiosseletividade das reações de C-alquilação efetuadas com estes substratos. O conjunto dos resultados obtido foi analisado à luz dos modelos atualmente propostos para reações de CTF assimétrica. / The present work focussed on the alkylation reactions, via Phase Transfer Catalysis, of several acyl derivatives: (See files PDF). In order to evaluate the extension of the backgroud reaction, several blank experiments were performed, in the absence of catalyst. The efficiency of the catalitic process was determined using as catalyst an achiral ammonium salt (TBAH). Experimental conditions were optimized using liquid-liquid or solid-liquid systems. In reactions performed with the ester derivatives (24), (25) and (26), hydrolytic acyl cleavage could be observed. However, for compounds (27), (28) and (29), C-alkylated products could be isolated in reasonable yields. Reactions conducted under asymmetric PTC conditions led, in most cases, to racemic products. Esters were considered inadequate substrates for C-alkylation as a consequence of three main factors: (i) low reactivity under PTC conditions, (ii) product racemization or (iii) formation of loose ion-pairs, or diastereomeric intermediates of equal thermodynamic stability. Asymmetric PTC alkylation of amide (31) afforded a C-benzylated optically active product in low yield (ee= 30%). Improved reactivity could be observed for this substrate as compared to amide (30), as a result of increasing acidity and a more favorable interaction between the catalyst and the corresponding enolate. For compounds (32), (33) and (34), the enantiomeric excess of the corresponding C-benzylated products could not be determined, precluding a comparison of the efficiency of the stereoselective catalytic process. For each case, results were discussed in terms of currently accepted models for the enolate/catalyst interaction.

In this dissertation, we discuss the development of new phase transfer agents, which are capable of rapid fluorination of silicon. These are 18-C-6 derivatives containing a hydroxyl group in the side arm (podand), also known as C-pivot lariats. The syntheses of these lariats including several that have not been previously reported and their efficient purification are described. The synthesis route leads to a robust and generalized approach to obtain these lariats on the gram scale. These agents were initially designed for applications in positron emission tomography (PET). In this medical imaging modality, tracer agents containing silicon have found promising utility as fluoride receptors for more rapid radiolabeling. Phase transfer agents are generally required for 18F-labeling due to the low solubility in organic reaction media and reactivity of cyclotron-generated [18F]potassium fluoride. We envisioned that 18-C-6 derivatives may serve as both phase transfer agents as well as nucleophilic catalysts (CENCs). In this conception, CENCs were rapidly pre-complexed with KF followed by silicon fluorination, which takes advantage of a previously established silicon dianion mechanism. In collaboration with researchers at the NIH, we studied the effect of various linkers connecting the metal chelating unit to the nucleophilic hydroxyl group on the radiofluorination of silicon under mild condition. A hydrolysis resistant aryl silicon fragment has also been developed that contains various functional groups for convenient attachment to the potential PET radiotracer agents. In a second project, we demonstrate the unique reactivity of γ-silyl allenyl esters. Taking advantage of the silyl group as a fluoride acceptor, these allenoates readily underwent addition to a variety of carbon electrophiles, including aryl fluorides, to afford all-carbon quaternary centers bearing an ethynyl group. Surprisingly, in the presence of aldehydes, exclusive bis-substitution occurs at the γ-position to afford the dicarbinol. Details relating to reaction optimization and substrate scope for both the reactions are presented. Dicarbinol allenes were subsequently converted to highly substituted δ-lactones, a novel 6-hydro-2-pyrone as single diastereomers. / Includes bibliography. / Dissertation (Ph.D.)--Florida Atlantic University, 2018. / FAU Electronic Theses and Dissertations Collection

O emprego da catálise de transferência de fase substituindo uma ou mais etapas da síntese de um fármaco, pode ser um recurso vantajoso sob o ponto de vista tecnológico. Empregado na síntese de importantes fármacos que são a dicicloverina, caramifeno eamiodarona, a catálise de transferência de fase revelou-se muito vantajosa na síntese dos dois primeiros. A dicicloverina e o caramifeno tiveram as suas rotas de obtenção verticalizadas, com bons resultados e custos bem mais baixos quando comparados com os atualmente adquiridos no exterior. Ficou evidente que a catálise de transferência de fase pode ser aplicada com sucesso na produção destes e outros fármacos em associação com técnicas já conhecidas com ótimos resultados. / The phase transfer catalysis application replacing one or more steps in the drug synthesis, can be of advantage in the technologycal approach. Applied to the synthesis of important drugs such as diciclomine, caramiphen,and amiodarone, the phase transfer catalysis resulted in a very advantageous method in the first two drugs. The diciclomine and the caramiphen, gets their obtention routes from raw materiaIs wi th good resul ts and low coasts, when compared wi th the drugs presently purchassed in foreign countries. It is clear that the phase transfer catalysis, can be applied succesfully in the manufacturing of these and other drugs, in conjuction with known techniques with good results.

Nanoparticles (NPs) are often synthesized in organic solvents due to advantages of superior size and shape control obtainable in a non-polar environment. However, many applications featuring NPs require them to be in aqueous media. To transfer NPs from oil to water, surfactants with amphiphilic (hydrophobic and hydrophilic) groups have been widely used. A popular phase-transfer approach involves formation of oil-in-water emulsions upon which the oil storing the NPs is boiled off. In the process, surfactants form bilayers with hydrophobic groups on the NPs rendering them water-dispersible. This transfer route however is limited in that NPs aggregate to form clusters which results in poor colloidal stability and for the specific case of quantum dots (QDs), adversely impacts optical properties. It has ever since remained a challenge to devise approaches that transfer NPs from oil to water as single particles without compromising NP stability and properties. We have discovered that by simple addition of salt to water during the step of emulsion formation, NP transfer efficiency can be greatly enhanced in "salty-micelles" of surfactants. The strength of this approach lies in its simplicity and generic nature in that the transfer scheme is valid for different NP, surfactant and salt types. Using a model system with cadmium selenide (CdSe) QDs as NPs, Aerosol-OT (AOT) as the surfactant and NaCl as the salt in water, we found >90% of CdSe QDs transferred in salty-micelles of AOT which was significantly higher than the 45-55% QDs that transferred in deionized-water (DI-water) micelles of AOT. In the salty-micelle environment, QDs were found to exist predominantly as single NPs with narrow size distribution, as established by light scattering, analytical ultracentrifugation and electron microscopy. The effects of salt were in lowering aqueous solubility of AOT through "salting-out" action and in screening repulsions between like-charged head groups of AOT molecules. Electrophoresis, thermogravimetric analysis and photoluminescence measurements using a solvatochromic dye established higher surfactant coverage with greater lateral compaction for QDs in salty-micelles over the DI-micelle counterpart. Single NP characteristics along with a hydrophobic environment in laterally compact salty-micelles resulted in better retention of optical properties of QDs. Observations of a secondary effect by salt in inducing spontaneous emulsification of a hydrocarbon (octane)/AOT/brine system were systematically investigated by tracking time-variant octane droplet size and charge. Salinity levels that determine the spontaneous curvature and phase behavior of AOT were seen to influence the initial nucleation of octane droplets and their subsequent growth. The smallest octane drops (sub 50 nm) were nucleated at the optimum cross-over salinity and emergence of the liquid crystalline phase of AOT resulted in slowest growth rates. These factors contributed towards higher transfer efficiency of NPs in salty-micelles. Two applications from formulating aqueous NP suspensions by the new phase-transfer approach are described. In the first, QD and carbon-dot (C-Dot) "nanoreporters" were formulated for oil-field reservoir characterization using Neodol 91-7 (nonionic) and Avanel S150 CGN (hybrid nonionic and anionic) as surfactants. These NPs were stable to aggregation under reservoir-representative conditions (salinities: 1M NaCl, 1M KCl and 0.55M synthetic seawater; temperatures: 70-100 °C) and demonstrated flow and transport through crushed-calcite and quartz-sand columns with high breakthrough and recovery (> 90%). In the second application, tandem assembly of a cationic polymer, multivalent salt, and NPs was investigated in a microfluidic channel where charge ratio of the polymer/salt and shear from flow and device geometry determined their assembly into higher ordered structures such as gels and capsules.

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