In part one, betulinic acid (1) was isolated from the American Sycamore (Platanus occidentalis) in 1.6% yield, while ursolic acid (3) was isolated from Fuji and McIntosh apple peels in 1.0% and 0.8% crude yields, respectively. Oleanolic (4) and dehydrocanophyllic (6) acids were previously available, along with several analogs. Additional analogs of 1, 3 and 4 were prepared, including 9 new compounds, for a total of 51 compounds. Compounds were initially screened for cortisol lowering properties in vitro using a fish head kidney cell assay. Platanic acid (43) was selected for in vivo study in rats, along with 1 and a blend of Platanus occidentalis and Souroubea sympetela. No significant cortisol lowering was observed in vivo. In part two, β-ionone-d6 (75) was synthesized in 6.5% yield from ethyl 2-oxo-cyclohexane carboxylate (77). Total deuterium incorporation was 99.85%, with 0.03% d0 analog. 75 was converted to retinoic acid-d6 (93) in 2.2% yield.

This is my thesis research on the preparation of borylazadipyrromethene (azaBODIPY) dyes bearing an anchoring group, such as a carboxylic acid group, at the β-pyrrolic position of the azadipyrromethene scaffold. Carboxylate groups form covalent bonds to oxide semiconductors such as TiO2 (n-type) or Cu2O (p-type) in dye-sensitized solar cells (DSCs) or photogalvanic dye-sensitized solar cells (P-DSCs). Oxide-binding azaBODIPY dyes can be used to investigate the rate and mechanism of electron injection from the dyes to the semiconductors. Two different types of azaBODIPY (difluoroboryl and dialkynylboryl) were prepared by following previously developed methods. To convert difluoroborylazaBODIPY to the final dyes having a carboxylic acid in the β-pyrrolic position, several distinct synthetic routes were designed, adopting various reactions, such as halogenation, Sonogashira coupling, Knoevenagel condensation, Grignard reagents, Vilsmeir-Haack, and Steglich esterification. Some of these reactions were successful, but the overall synthesis to the targeted final molecule couldn’t be accomplished. Even though further studies on the synthesis of oxide-binding azaBODIPYs are needed, at least my thesis research suggests what reactions can be implemented to complete this synthesis in the future. Proton NMR (nuclear magnetic resonance) and carbon NMR were commonly used to confirm the synthesized compounds, and sometimes crystallographic information was obtained by XRD (X-ray diffraction) whenever crystals of sufficient size and quality were grown. NMR spectra, interpreted by SpinWorks 3 software, and crystal structures will be introduced in each chapter.

Crystal Engineering is the design of crystalline material using non-covalent synthesis. Co-crystals are multi-component crystals which are constructed from complementary intermolecular interactions, they are also known as supramolecular complexes. Design of such materials utilises the synthon approach, this involves the understanding of common intermolecular interactions which occur in the crystal packing and is used to design new solids with desired physical properties and chemical properties. Primary amides form supramolecular heterosynthons, these synthons represent an opportunity for a design of multi-component crystals in which one molecule contains a primary amide and a second molecule which is complimentary to the primary amide, usually carboxylic acids. The progress with regards to the screening process for the determination of co-crystals is evident in the literature, In particular, high throughput solution growth methods and solvent drop grinding. The comparison of Isonicotinamide and Benzamide as a co-crystal component has been presented. This study was motivated by the observation that the CSD contains 24 Isonicotinamide and 1 Benzamide co-crystal. The interaction with carboxylic acids is the focus of the work, in particular those which form Isonicotinamide co-crystal are being screened with Benzamide. Our work utilises a ReactArray Microvate to carry out the low throughput solution growth on a matrix of carboxylic acid with Benzamide, this study has been coupled with the Kofler hot stage microscope method which visually aids to screen and view co-crystal phase formation. Crystallisation screens have resulted in the identification of known co-crystal phases of Isonicotinamide and Benzamide, additionally new co-crystal phases have also been identified with Fumaric, 3-hydroxybenzoic acid, Mandelic Acid, 4-Nitrobenzoic Acid and Tartaric Acid. Single crystal structures of the Fumaric and 4-Nitrobenzoic acid have been obtained. In order to develop an understanding of co-crystal formation in Isonicotinamide and Benzamide with our supramolecular library, packing landscape analysis is being undertaken using both the CSD and crystal structures we have obtained. This is undertaken as collaboration with Dr Andy Parkin and Professor Gilmore (University of Glasgow), we have identified that the dSNAP analysis is a way forward for the analysis of how co-crystals pack. The analysis highlighted the subtleties that were present in the packing motifs of the Isonicotinamide co-crystals. In particular the cis and trans orientation of the amide and acid carbonyl to each other and the planar and off planar layer assemblies. All of which are required to maximise the hydrogen bond usage of the components comprising the co-crystals. Further investigations have led to the collaborative project with Syngenta Ltd in the design of a co-crystal screen using a high through-put robot, Crissy® -Automation Platform by Zinsser Analytical, using an extended screen of 16 acid coformers with Isonicotinamide, Benzamide and Nicotinamide the sample have been characterised using a reflectance diffraction method, GADDS. Further analysis of this data involves the use of polySNAP, which has led to further collaboration with Professor Gilmore¿s group. / Syngenta

Denna studie undersöker effektiviteten hos Calamos nyligen utvecklade elektrolyt. Det är av stor betydelse att förstå hur denna nya elektrolyt, som är fosforfri och baserad på organiska syror, fungerar för att minska beroendet av ändliga resurser och därigenom främja en mer hållbar produktion. Projektets mål var att utveckla en enkel kvantitativ analysmetod för myrsyra, mjölksyra, glykolsyra och oxalsyra i den nya elektrolyten. Tekniken som användes för detektion och kvantifiering var gaskromatografi (GC) kopplad till en flamjoniseringsdetektor (FID). GC är begränsad till analyter som kan överföras till gasfasen utan att brytas ned termiskt. Ett sätt för att öka en förenings flyktighet, termiska stabilitet och kromatografiska beteende är genom en derivatiseringsreaktion. För bättre kromatografisk beteende derivatiserades karboxylsyror före GC-analys med N,O-bis-(trimetylsilyl)trifluoracetamid (BSTFA) som silyleringsreagens och dimetylformamid (DMF) som derivatiseringsmedium. Efter optimering validerades metoden och dess linjäriteten. Metoden har tillämpats för kvantitativ bestämning av karboxylsyror i elektrolyten, följt av lösningsmedelsextraktion med dietyleter. I detta arbete undersöktes även extraktionen av en karboxylsyra genom derivatisering med hjälp av dimetylkarbonat och natriummetoxid, vilket resulterade i bildandet av metylestrar som är relativt opolära och underlättar överföringen av karboxylsyror till den organiska fasen. Resultaten visade att båda teknikerna totalt sett inte verkar lämpliga för analys av karboxylsyror i elektrolyten. Dessutom utsaltningsextraktion av de karboxylsyrorna studerades också med användning av ett system bestående av butanon och ammoniumhydroxid. Resultaten indikerade att denna extraktionsmetod inte var effektiv för karboxylsyrorna. / This study examines the effectiveness of Calamo's newly developed electrolyte. It is of great importance to understand how this new electrolyte, which is phosphorus-free and based on organic acids, works to reduce dependence on finite resources and thereby promote more sustainable production. The project's goal was to develop a simple quantitative analysis method for formic acid, lactic acid, glycolic acid and oxalic acid in the new electrolyte. The technique used for detection and quantification was gas chromatography (GC) coupled to a flame ionization detector (FID). GC is limited to analytes that can be transferred to the gas phase without thermal degradation. One way to increase a compound's volatility, thermal stability and chromatographic behaviour is through a derivatization reaction. For better chromatographic behaviour, carboxylic acids were derivatized prior to GC analysis with N,O-bis-(trimethylsilyl) trifluoroacetamide (BSTFA) as the silylation reagent and dimethylformamide (DMF) as the derivatization medium. After optimization, the method and its linearity were validated. The method was applied for quantitative determination of carboxylic acids in the electrolyte, followed by solvent extraction with diethyl ether. In this work, the extraction of a carboxylic acid by derivatization with dimethyl carbonate and sodium methoxide was also investigated, which resulted in the formation of methyl esters that are relatively non-polar and facilitate the transfer of carboxylic acids to the organic phase. The results showed that both techniques overall did not seem suitable for the analysis of carboxylic acids in the electrolyte. In addition, salting-out extraction of the carboxylic acids was also studied using a system consisting of butanone and ammonium hydroxide. The results indicated that this extraction method was not effective for the carboxylic acids.

La production de l'hydrogène à partir de biomasse est actuellement à l'étude mais la méthode de valorisation du biogaz (mélange H2/CO2) par réactions catalytiques, autres que la simple combustion, n'a pas encore été retenue. Par conséquent, le principal objectif de ce travail est d'explorer les autres voies. L'effet du CO2 sur le système catalytique est mal connu et seulement un effet négatif sur la dissociation de l'hydrogène a été mentionné. L'hydrogénation du toluène sur un catalyseur Pt a d'abord été étudiée sans CO2 pour suivre son comportement et éventuellement sa perte d'activité. En présence de CO2, l'inactivité complète du catalyseur pour l'hydrogénation du toluène a été mis en évidence. La modification de la surface du catalyseur par le CO2 est quantifiée par DRIFT et un mécanisme à deux sites a été montré. La réaction de Reverse Water Gas Shift produisant du CO se trouve être la principale cause de la désactivation de la surface de catalyseur avec le CO2. Donc la compétition d'adsorption entre le CO et des acides carboxyliques a été mise à profit pour favoriser sélectivement la conversion des acides. Pour l'alumine, elle est polluée par des carbonates complexes venant du CO2. La silice étant aussi connue pour promouvoir la décomposition, ces supports ont été rejetés. L'oxyde de titane a été utilisé pour catalyser une autre gamme de produits. Sur ce catalyseur, le changement de sélectivité entre le RWGS et la conversion de l'acide a été observé. Quant à l'oxyde de fer (catalyseur moins actif), il n’est pas capable de produire du CO à partir du CO2. La chimie de surface de l'oxyde de fer joue un rôle important sur la sélectivité du produit parmi les cétones et les aldéhydes. Un mécanisme à deux sites peut réutiliser pour l'oxyde de fer, montrant qu'un fonctionnement stable peut être trouvé si la réduction par l'hydrogène est continue. Si l'oxyde de fer est totalement oxydé par le CO2, produit de réaction, la production des cétones cesse. Énergiquement, le procédé de production d'acétone peut être autosuffisant et l'acétone peut être utilisée comme une molécule de stockage d'énergie. Le procédé va aussi compenser le nouveau procédé de production de phénol qui ne produit pas l'acétone / Hydrogen potential from biomass is currently being studied but ways of valorization of such biogas (H2/CO2 mix) via catalytic reaction, other than simply burning has not yet been considered. Thus the main objective of this work is the exploration of such methods. Effect of CO2 over catalytic system was not well known and only hydrogen dissociation inhibition is reported. Toluene hydrogenation over Pt catalyst is studied and activity loss transition behavior is observed with no CO2 where as complete catalyst inactivity for toluene hydrogenation is found in presence of CO2. Catalyst surface change by CO2 is quantified by DRIFT analysis and two-site mechanism is found to prevail. Reverse water gas shift reaction producing CO is found to be the main cause behind such catalyst surface response to CO2. Adsorption competition between CO and carboxylic acids is exploited for selectivity shift in favor of acids conversion. Alumina support is fouled by carbonates complexes with CO2 while silica is reported to promote decomposition, thus both were rejected and titanium oxide is used instead with a range of products produced. The required selectivity shift between reverse water gas shift and acid conversion is thus observed. Less active iron oxide catalyst further suppresses CO2 conversion. Iron oxide surface chemistry plays an important role over product selectivity among ketones and aldehydes. Two sites mechanism still prevails over iron and stable continuous operation requires simultaneous iron reduction via hydrogen, if totally oxidized by CO2–a reaction product, will cease to produce ketones. Energetically the process devised for acetone production is self sufficient and acetone not only act as an energy storage molecule but can also compensate new phenol production process producing no acetone

No description available.

<p>Diss. (sammanfattning) Umeå : Umeå universitet, 1990, härtill 5 uppsatser.</p> / digitalisering@umu.se

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-11-11T11:16:35Z No. of bitstreams: 0 / Made available in DSpace on 2016-11-11T11:16:35Z (GMT). No. of bitstreams: 0 / Neste trabalho serão apresentados novos métodos baseados na geração e controle de comprimento de onda em lasers aleatórios e lasers de diodo. Na primeira parte do trabalho será demonstrado um laser aleatório com realimentação localizada em filmes em biopolímeros dopado com corante. O filme é constituído por um ácido desoxirribonucleico e cloreto de cetiltrimetilamônio (DNA-CTMA) dopado com DCM. No dispositivo proposto, a realimentação óptica para o laser aleatório é dada por centros de dispersão posicionados aleatoriamente ao longo das bordas da área ativa. Os elementos de dispersão são nanopartículas de dióxido de titânio (TiO2) ou defeitos aleatórios na interface entre o polímero ativo e ar. Diferentes espectros de emissão são observados, dependendo da geometria da área excitada. Um único ressonador aleatório com dimensões de 2.6 x 0.65 mm2 foi fabricado com emissão aleatória com realimentação obtida pela excitação do dispositivo por completo. A segunda parte deste trabalho apresenta um novo método para a geração e manipulação de franjas de contorno por meio de interferometria speckle com comprimento de onda sintética, usando um único laser de diodo com cavidade externa. A cavidade externa permite sintonizar duas emissões simultaneamente, o que por sua vez muda o intervalo entre as franjas de contorno do interferômetro, além de aumentar a estabilidade do laser. Uma análise de Fourier é proposta como alternativa para medir o comprimento de onda sintético resultante das duas emissões do laser. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-12-22T12:14:15Z No. of bitstreams: 0 / Made available in DSpace on 2016-12-22T12:14:15Z (GMT). No. of bitstreams: 0 / A irradiação de alimentos é um meio de preservação de alimentos onde se utiliza uma técnica de processamento que expõe os alimentos a uma radiação ionizante controlada de alta energia. O tratamento realizado com o uso das radiações ionizantes em alimentos tem muitas aplicações tecnologicamente e tecnicamente viáveis incluindo a capacidade de melhorar a segurança microbiológica, reduzir os níveis de bactérias patogénicas, inibir a germinação de tubérculos, aplicação fitossanitária, conservar alimentos armazenados ou a estabilidade de armazenamento e também é utilizada para aumentar a vida de prateleira de determinados produtos devido à redução da contaminação por microrganismos. Em função do aumento do comércio internacional de alimentos e das crescentes exigências regulatórias dos mercados consumidores, cada vez mais países importadores e exportadores têm demonstrando interesse na irradiação de alimentos e desenvolvido pesquisas na aplicação prática desta tecnologia e de métodos de detecção do tratamento. Inúmeras pesquisas foram realizadas mundialmente, resultando em eficientes protocolos para identificar quais alimentos foram ou não irradiados. Até então, o \"mito\" que alimentos irradiados não poderiam ser detectados e que não eram formados quaisquer produtos únicos da radiação foi substituído pelo conhecimento que muitas mudanças podem ocorrer nos alimentos irradiados e essas mudanças poderiam ser utilizadas como ferramentas para identificar essa tecnologia. O processamento por radiação resulta em formações de padrões característicos de hidrocarbonetos saturados, aldeídos, metil e etil ésteres e 2-alcilciclobutanonas, dependendo da composição do ácido graxo do lipídio que compõe o alimento. Com isso a proposta do trabalho foi levantar dados para comparar os efeitos das diferentes doses de radiação gama e de elétrons em alimentos que possuem gordura para verificar as possíveis alterações decorrentes do uso da irradiação, como a presença de 2-Alcilciclobutanonas e também, mostrar os principais equipamentos utilizados para a irradiação de alimentos e suas categorias, com o objetivo de informar o publico em geral. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-10-09T19:13:18Z No. of bitstreams: 0 / Made available in DSpace on 2017-10-09T19:13:18Z (GMT). No. of bitstreams: 0 / Estudos têm demonstrado o potencial da terapia fotodinâmica antimicrobiana (aPDT) na inativação de diferentes células microbianas. No geral, são três as fases de crescimento dos microrganismos: fase lag, exponencial e estacionária. Os objetivos deste estudo foram avaliar a susceptibilidade de células de Candida albicans em diferentes fases de crescimento, submetidas à aPDT, associando azul de metileno (50 &mu;M) e luz de emissão vermelha (&lambda;= 660 nm) e investigar alterações morfológicas, mecânicas e bioquímicas, antes e depois da aPDT, por microscopia eletrônica de varredura, de força atômica e por espectroscopia no infravermelho por transformada de Fourier. Os resultados obtidos sugerem que, em parâmetros letais, células em fase estacionária de crescimento (48 h) são menos susceptíveis à aPDT, quando comparadas àquelas em fases lag (6 h) e ex-ponencial (24 h) de crescimento. Entretanto, em parâmetros subletais, células de 6 h e 48 h mostraram a mesma susceptibilidade à aPDT. Em sequência, os experimentos foram realizados em parâmetros considerados subletais para células crescidas por 6 e 48 h. A avaliação morfológica mostrou menor quantidade de matriz extracelular em células de 6 h comparada àquelas de 48 h. A espectroscopia de força atômica mostrou que células em fase lag perderam a rigidez após a aPDT, enquanto que células em fase estacionária mostraram comportamento in-verso. Ainda, células de 48 h diminuíram sua adesividade após a aPDT, enquanto que células de 6 h e 24 h tornaram-se mais adesivas. Os resultados bioquímicos revelaram que as diferenças mais significativas entre as células fúngicas de 6 h e 48 h ocorreram na região de DNA e carboidratos. A aPDT promoveu mais alterações bioquímicas na região de DNA e carboidratos em células de 6 h e em lipídios e ácidos graxos em células de 48 h. Nossos resultados indicam que a fase de crescimento celular desempenha papel importante no sítio de ação da aPDT em células de C. albicans. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP