O estudo fitoquímico dos extratos de plantas adultas e plântulas da espécie Piper reticulatum, coletada na Floresta Nacional de Carajás, levou ao isolamento de quatro amidas, incluindo diidrowisanidina, descrita previamente nesta espécie, wisanidina, (2E,4E)-N-isobutileicosa-2,4-dienamida, (3E,5E,14E)-N-pirrolidileicosa-3,5,14-trienamida (inédita em função da posição das insaturações da cadeia alquílica), uma lignana (siringaresinol) e uma nitrila (benzoato de cianobenzila), além de terem sido propostas as estruturas de oito amidas contendo longa cadeia alquílica, com base nos dados de cromatografia gasosa e líquida acoplada a espectrometria de massas. Os extratos e produtos naturais isolados foram avaliados quanto aos seus potenciais antifúngicos frente aos fitopatógenos Cladosporium cladosporioides e C. sphaerospermum e atividade inibidora da enzima acetilcolinesterase, sendo constatada forte atividade para as amidas em ambos ensaios, além de forte atividade para a nitrila contra C. sphaerospermum. Além disso, os extratos de plantas adultas e plântulas de P. reticulatum foram analisados através de EM (ESI+) e os dados analisados por PCA (análise dos componentes principais) e através de HCA (análise por agrupamento hierárquico) juntamente com a espécie P. amalago, filogeneticamente relacionada com P. reticulatum, P. crassinervium, P. solmsianum, P. fuligineum, P. gaudichaudianum, P. aduncum e P. tuberculatum, afim de uma distinção ou classificação de grupos seguindo parâmetros metabólicos. / The phytochemical study of extracts from adult plants and seedlings of the species Piper reticulatum, collected in the Carajás National Forest, afforded the isolation of four amides, including dihydrowisanidine, previously described from this species, wisanidine, (2E,4E)-N-2-isobutyleicosa-2,4-dienamide, (3E,5E,14E)-N-3,5,14-pyrrolidyleicosa-trienamide (novel based on the unsaturations position at the alkyl chain), a lignan (syringaresinol) and a nitrile (cianobenzyl benzoate) and, additionaly eigh amides containing long alkyl chain had their structures proposed based on gas and liquid chromatography coupled to mass spectrometry data. The extracts and the isolated natural products were evaluated for their potential antifungal activity against the phytopathogens Cladosporium cladosporioides and C. sphaerospermum and acetylcholinesterase inhibitory activity, being found strong activity for amides for both two tests, and strong activity for nitrile against C. sphaerospermum. In addition, extracts of adult plants and seedlings of P. reticulatum were analyzed by MS (ESI +) and by PCA (principal component analysis) and HCA (hierarchical cluster analysis) together with the species P. amalago, phylogenetically related to P. reticulatum, P. crassinervium, P. solmsianum, P. fuligineum, P. gaudichaudianum, P. aduncum and P. tuberculatum in order to distinguish or classify them according to the metabolic profile.

N-Acylethanolamines (NAEs) are a class of fatty acid amides that act as important mammalian signaling molecules. N-Arachidonoylethanolamine is the best-studied representative and is one of the endogenous ligands for endocannabinoid receptors. NAEs play a role in the regulation of appetite, act as anti-inflammatory and analgesic agents, and are thought to have a neuroprotective function as well. They have been proposed to also serve as precursors to N-acylglycines (NAGs). N-Acylglycinals are likely to be intermediates between the NAEs and the NAGs. The sequential actions of a putative fatty alcohol dehydrogenase and a putative fatty aldehyde dehydrogenase are thought to affect the NAD+-dependent oxidation of the NAEs to the NAGs. NAGs, in turn, serve as precursor in the biosynthesis of primary fatty acid amides (PFAMs), another class of mammalian regulatory molecules. Alcohol dehydrogenase 3 (ADH3), an enzyme known to oxidize mid- and long-chain alcohols to aldehydes, was evaluated for its potential in oxidation of NAEs to N-acylglycinals. In order to evaluate the possibility of ADH3 involvement in NAE metabolism, variable chain length NAEs were synthesized and evaluated as substrates for bovine liver ADH3. NAEs were oxidized by ADH3 in the presence of NAD+, yielding the corresponding N-acylglycinals. VMax/KM values for assayed NAEs were low relative to cinnamyl alcohol, one of the preferred substrates for ADH3. Our data suggest that the ADH-mediated oxidation of NAEs could occur in vivo, but that ADH3 is unlikely to be the in vivo catalyst.

The thesis entitled “Synthetic and Mechanistic Studies in Oxime and Amide Chemistry” consists of two chapters. Chapter 1 contains 3 parts, dealing with the Beckmann rearrangement under solvent free conditions, Mitsunobu conditions, and with catalytic succinic anhydride-ZnCl2. Chapter 2 deals with bond length and reactivity studies with several oxime esters. CHAPTER 1 Part 1: This describes studies aimed at the development of the Beckmann rearrangement in the solid state using phenylboronic acid. The adsorption of ketoximes on a mixture of phenylboronic acid and neutral alumina followed by heating >120 °C, afforded the expected amides, although with competing hydrolysis to corresponding ketones. It appeared that phenylboronic acid was being converted under the reaction conditions to triphenyl boroxine, which was presumably the active species effecting the Beckmann rearrangement. This was experimentally confirmed when the amide products were obtained in good yields when the reaction was performed with triphenyl boroxine. Part 2: This describes the Beckmann rearrangement under Mitsunobu conditions. Triphenyl phosphine and diethyl azodicarboxylate can react with various oximes to produce corresponding amides. Part 3: This describes the Beckmann rearrangement of oximes to amides by a combination of succinic anhydride and zinc chloride as catalyst. Zinc chloride can activate succinic anhydride, the activated succinic anhydride then reacting with the oximes. This forms the oxime ester of succinic acid, which undergoes the Beckmann rearrangement as shown. CHAPTER 2: This describes bond length and reactivity studies with several oxime esters. It was of interest to obtain a correlation between bond length and reactivity in ketoxime derivatives which are known to undergo the Beckmann rearrangement. Towards this end the crystal structures of a variety of oxime esters have been determined. The results indicate that the alkyl group anti to the oxime hydroxyl group is pre-disposed towards migration onto the nitrogen center. (pl refer the thesis for structural formula)

Thesis (Ph.D. in Pharmaceutical Sciences) -- University of Colorado at Denver and Health Sciences Center, 2006. / Typescript. Includes bibliographical references (leaves 203-215). Free to UCDHSC affiliates. Online version available via ProQuest Digital Dissertations;

Thesis (Ph.D.)--Duquesne University, 2005. / Title from document title page. Abstract included in electronic submission form. Includes bibliographical references (p. ) and index.

Made available in DSpace on 2015-05-14T12:59:38Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4924015 bytes, checksum: b58a10396c3699de03f34eaec912196b (MD5) Previous issue date: 2012-02-12 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The genus Piper considered the largest in the family Piperaceae, with at least 1000 species found mainly in Asia and the New World. Yours species have several representative commercial and medical applications, being subject of several studies related to the discovery of new sources of natural active substances. Based on data described in the literature regarding the pharmacological potential of the metabolites isolated from the genus Piper, as well as the occurrence of species not yet fully exploited in terms of chemical and pharmacological, then was decided to perform the phytochemical study of the species Piper mollicomum (Kunth) aiming at the isolation and identification of chemical constituents of this species, as well as the availability of its extracts, fractions and isolated compounds for pharmacological studies. From the phytochemical study of phase dichloromethane Piper mollicomum Kunth was possible to isolate, by chromatographic methods such as column chromatography on silica and Preparative Thin Layer Chromatography, five substances, among them two isobutyl amides: 2-Propenamide, 3-(6-methoxy-1,3-benzodioxol-5-yl)-N-(2-methylpropyl)-(2E) and 2- Propenamide,3-(6- methoxy -1,3-benzodioxol-5-yl)-N-(2-methylpropyl)-(2Z) and two pyrrolidines amides: Pirrolidine, 1-[3-(6- methoxy -1,3-benzodioxol-5-yl)-1-oxo-2-propenyl-(E) and Pirrolidine, 1-[3-(6- methoxy -1,3-benzodioxol-5-yl)-1-oxo-2-propenyl-(Z) and a phenylpropanoid called a 2-Methoxy-4,5-methylenedioxypropilphenone. For structural identification of these substances were used spectroscopic methods such as IV and NMR 1H and 13C uni and two-dimensional techniques and the comparison with models data in the literature. / O gênero Piper considerado o maior da família Piperaceae, com pelo menos 1000 espécies encontradas especialmente na Ásia e no Novo Mundo. Suas espécies tem boa representatividade comercial e diversas aplicações medicinais, sendo objeto de vários estudos relacionados à descoberta de novas fontes de substâncias naturais ativas. Com base nos dados apresentados na literatura referentes ao potencial farmacológico dos metabólitos isolados do gênero Piper, bem como a ocorrência de espécies ainda não devidamente exploradas do ponto de vista químico e farmacológico, decidiu-se, então, realizar o estudo fitoquímico da espécie Piper mollicomum (Kunth) visando o isolamento e identificação de constituintes químicos desta espécie, bem como a disponibilização de seus extratos, frações e substâncias isoladas para realização de estudos farmacológicos. A partir do estudo fitoquímico da fase diclorometânica de Piper mollicomum Kunth foi possível isolar, através de métodos cromatográficos como Cromatografia em Coluna em sílica e Cromatografia em Camada Delgada Preparativa, cinco substâncias, dentre estas duas amidas isobutílicas: 2-Propenamida, 3-(6-metoxi-1,3-benzodioxol-5-il)-N-(2-metilpropil)-(2E) e 2-Propenamida, 3-(6-metoxi-1,3-benzodioxol-5-il)-N-(2-metilpropil)-(2Z) e duas amidas pirrolidínicas: Pirrolidina, 1-[3-(6-metoxi-1,3-benzodioxol-5-il)-1-oxo-2-propenil-(E) e Pirrolidina, 1-[3-(6-metoxi-1,3-benzodioxol-5-il)-1-oxo-2-propenil-(Z), além de um fenilpropanóide denominado 2-Metoxi-4,5-metilenodioxipropilfenona isolado nas espécies Piper marginatum, Piper barbatum e Piper aleyreanum. Para identificação estrutural destas substâncias utilizou-se métodos espectroscópicos como Infravermelho e Ressonância Magnética Nuclear de 1H e 13C uni e bidimensionais, bem como as comparações com dados de modelos da literatura.

Made available in DSpace on 2014-06-11T19:31:34Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-05-24Bitstream added on 2014-06-13T20:02:20Z : No. of bitstreams: 1 salata_cc_dr_botfca.pdf: 1371462 bytes, checksum: 6b53655dc286e55274fee57af09c38b1 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Universidade Estadual Paulista (UNESP) / Este trabalho teve como objetivo purificar bioetanol originário de amido de mandioca utilizando processos de adsorção e troca iônica, avaliar a influência da temperatura, tempo de contato, concentração de adsorvente, vazão, tempo de residência nos processos de adsorção e troca iônica, analisar como os diferentes parâmetros desses processos afetam importantes características físico-químicas do bioetanol, tais como: condutividade, acidez e teste de Barbet, visando propor inovações nos sistemas de purificação, substituindo os processos clássicos de redestilação que são consumidores de energia. O estudo ainda propõe novas metodologias para aplicação na melhoria da qualidade de etanol produzido em pequenas unidades utilizando a mandioca como matéria-prima. Para a realização deste trabalho foram utilizados: a) etanol adquirido e comercializado no mercado, tais como, etanol neutro, etanol de primeira, etanol de segunda; b) etanol produzido em escala piloto no CERAT/UNESP; e c) etanol preparado em laboratório denominado neste trabalho de solução e etanol fortificado. Para a preparação da solução e do etanol fortificado foram adicionadas ao etanol padrão algumas das substâncias orgânicas provenientes da fermentação do amido de mandioca, todas com alto grau de pureza para observar o desempenho das metodologias propostas. Para a purificação das diferentes amostras e das soluções etanólicas foram empregados: a) processo de adsorção; b) processo de troca iônica; e c) processo combinando adsorção e troca iônica. No processo de purificação por adsorção foram testados, como adsorventes... / The objective of present work was to purify bioethanol from cassava starch using adsorption and ion exchange processes, to evaluate the influence of the temperature, contact time, adsorbent concentration, flow rate, residence time in these adsorption and ion exchange processes, to analyze as the parameters different of those processes affect important physico-chemical properties of the bioethanol such as conductivity, acidity and Barbet, to propose innovations in the purification systems, replacing the classic processes of redistillation that are consumers of energy. The study still propose new methodologies for application in the improvement of the quality of ethanol produced in small units using cassava as raw material. For the accomplishment of this work were used: a) purchased and sold ethanol in the market, such as, neutral ethanol, first ethanol, second ethanol; b) ethanol produced in scale pilot in the CERAT/UNESP; and c) ethanol prepared in the laboratory named as solution and contaminated ethanol. For the preparation of the solutions and of the contaminated ethanol, were added to the standard ethanol some organic substances from the fermentation of the cassava starch, all with a high degree of purity to observe the performance of the proposed methodologies. For the purification of samples different and of ethanolics solutions were employed: a) adsorption process; b) ion exchange process; and c) process combining adsorption and ion exchange. In the purification process by adsorption were tested, as adsorbents, different types of activated charcoal and diatomaceous earth. In the ion exchange... (Complete abstract click electronic access below)

Made available in DSpace on 2014-06-11T19:31:34Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-05-08Bitstream added on 2014-06-13T21:02:51Z : No. of bitstreams: 1 cerqueira_vc_dr_botfca.pdf: 1017835 bytes, checksum: f5e403927b163c750f9e0cca2acae31a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Universidade Estadual Paulista (UNESP) / Os produtos das hidrólises de amido são glicose, maltose e uma série de oligossacarídeos e polissacarídeos que encontram utilização principalmente na indústria de alimentos. Neste grupo enquadram-se os adoçantes que aditam sabores a produtos que são demandados por consumidores específicos. Atualmente o açúcar mais utilizado no Brasil é a sacarose, produto extraído da cana-de-açúcar, e o mais utilizado mundialmente é a frutose obtida a partir da hidrólise do milho e posterior isomerização da glicose para frutose. A frutose apresenta capacidade edulcorante 30% maior que a sacarose, 2,5 vezes maior que a glicose e 2 vezes mais solúvel que a glicose, com isso, pode ser utilizada em menor quantidade, diminuindo o poder calórico do alimento e viabilizando sua utilização no tratamento da obesidade. Levando em consideração a importância dos adoçantes para o mercado de alimentos, o presente trabalho teve como objetivo realizar estudos sobre o processo de obtenção da frutose a partir de amido de mandioca. Para a execução dos ensaios utilizou-se fontes comerciais de α– amilase e amiloglucosidase, Liquozyme Supra 2.2X e Saczyme 750 AGUg-1, respectivamente, aplicadas em substrato de amido de mandioca em reator agitado com temperatura controlada. Após o processo de hidrólise enzimática, o hidrolisado passou por um processo de purificação utilizando terra diatomácea e carvão ativado em quatro temperaturas (30, 40, 50 e 60°C), com a finalidade de remoção de contaminantes originários da matéria prima, que levam a odor, cor e sabores indesejáveis. Após o tratamento com carvão ativo e terra diatomácea foram realizados ensaios para estabelecer os melhores parâmetros para a realização do processo de isomerização, buscando a conversão de parte da glicose à frutose, utilizando a enzima... / The products of starch hydrolyses are glucose, maltose and a series of oligosaccharides and polysaccharides which have their main utilization in food industry. This group comprises sweeteners that add flavor to products demanded by specific consumers. Currently the most used sugar in Brazil is sucrose, a product extracted from sugarcane, while the most used sugar worldwide is fructose obtained from maize hydrolysis and subsequent glucose isomerization to fructose. The sweetening capacity of fructose is 30% higher than that of sucrose and 2.5-fold higher than that of glucose; in addition, fructose is 2-fold more soluble than glucose and thus can be used in smaller quantities, decreasing the food’s caloric potential and making its use viable in obesity treatment. Considering the importance of sweeteners for the food market, the present study aimed to investigate the process of fructose production from cassava starch. The assays were performed by using commercial sources of α–amylase and amyloglucosidase, Liquozyme Supra 2.2X and Saczyme 750 AGUg-1, respectively, applied to cassava starch substrate in an agitated reactor at controlled temperature. Following the process of enzymatic hydrolysis, the hydrolysate underwent a purification process using diatomaceous earth and activated charcoal at four temperatures (30, 40, 50 and 60°C), in order to remove contaminants originated from the raw material, which lead to undesirable smell, color and flavor. After the treatment with activated charcoal and diatomaceous earth, assays were carried out to establish the best parameters for the isomerization process, aiming at the conversion of part of glucose into fructose, using the enzyme isomerase. The process selected for the studies was in a continuous system where the glucose syrup, previously purified, was continuously pumped... (Complete abstract click electronic access below)

Nos últimos anos, questões ambientais têm merecido destaque na mídia nacional e internacional. A química tem uma grande participação nos dias atuais com os inúmeros produtos fundamentais à humanidade. A sua presença pode ser destacada desde diversos combustíveis aos mais complexos medicamentos. As reações de síntese orgânica devem ser guiadas por novas práticas mais sustentáveis. Nesse campo, tem-se o conceito da Green Chemistry ou Química Verde, que consiste na estratégia em desenvolver metodologias e processos que usem e gerem a menor quantidade de materiais tóxicos e/ou inflamáveis ou reaproveitáveis. Com o intuito de contribuir com a Química Verde, estudou-se a síntese de iminas que consistiu da primeira etapa do processo de aminação livre de solventes orgânicos e apresentaram rendimentos superiores a 95,0 %; gem-dicloroaziridinas foram preparadas a partir de inserção de diclorocarbeno em iminas em condições mínimas de solvente orgânico, utilizando como catalisador o KF/Al2O3 e com rendimentos superiores a 98,0%. As gem-dicloroaziridinas foram convertidas em amidas por hidrolise, na ausência de solvente e com rendimentos superiores a 98,0%. Dentro do conceito de Química Verde foram preparadas as seis iminas: N-benzilfenilmetanoimina, N-fenil-furilmetanoimina, N-fenilfenilmetanoimina, N-fenil-(4-metoxifenil)-metanoimina, N-benzil-(4-metoxifenil)metanoimina e N-furfurilfurilmetanoimina; duas gem-dicloroaziridinas: 2,2-dicloro-1,3-difenilaziridina e 1-benzil-2,2-dicloro-3-fenilaziridina e duas amidas: cloro-fenilacetanilida e N-benzil-cloro-fenilacetamida. / For the last years Environmental issues have deserved featured in the National and International media. Chemistry has had great participation on currently days with countless products which are fundamental to humanity. Its presence can be detached from various fuels to the most complex drugs.The organic synthesis reactions should be guided by more sustainable new practices. In this field, the Green Chemistry concept or (Química Verde) strategy which aims to develop methodology and and/or processes which use and generate the minimum quality of toxic inflammable material. With the purpose of contribute to green chemistry, we studied the synthesis of imines which consisted of the first stage of the process of amination, free of organic solvents and have yields higher than 95%; gem-dichloroaziridine were prepared from the imines insertion dichlorocarbene in a minimum of organic solvent conditions, using as catalyst KF/Al2O3 and yields higher than 98%. The gem-dichloroaziridines were converted to amides by hydrolysis in absence of solvent and yields higher than 98.0%. Within the concept of Green Chemistry were prepared six imines: N-benzyl- phenylmethanimine, N-phenyl-2- furylmethanimine, N-phenyl- phenylmethanimine, N-phenyl-(4-methoxyphenyl)methanimine, N-benzyl-(4-methoxyphenyl)metha-nimine,N-(2-furylmethyl)-2-furylmethanimine; two gem-dichloroaziridinas: 2,2-dichloro-1,3-diphenyla-ziridine and 1-benzyl-2,2-dichloro-3-phenylaziridine and two amides: chlorophenylacetanilide and N-benzyl-chloro-phenylacetamide.

Orientador: Odair Correa Bueno / Banca: Marcos Roberto Potenza / Banca: Fabiana Elaine Casarin / Resumo: O cupim subterrâneo Coptotermes gestroi (WASMANN, 1896) é uma das principais pragas responsável por danos econômicos em estruturas de madeira nas áreas urbanas do litoral e interior do sudeste brasileiro. A metodologia mais empregada no controle de cupins subterrâneos é a aplicação direta de inseticidas no solo, porém esse tipo de tratamento não é destinado à eliminação da colônia e sim a formar uma barreira química entre a fonte de alimento que está sendo consumida e a colônia dos cupins. Essa barreira química também não evita que alados infestem prédios na época da revoada, pois eles não terão contato com os inseticidas. Essas infestações podem continuar sendo subterrâneas em porões de edificações ou podem ser aéreas, onde os cupins nidificam em espaços entre os andares dos edifícios, pois estes locais oferecem o ambiente ideal para os cupins com água, abrigo e alimento. Uma estratégia alternativa que visa à eliminação da colônia dos cupins subterrâneos é a utilização da metodologia de isca. Nas iscas o ingrediente ativo é incorporado a substratos que contenham celulose, sendo assim, a quantidade de inseticida usado é mínima, pois ele não pode ser repelente e precisa ter ação lenta e as partes não consumidas das iscas podem ser removidas depois do tratamento. No presente estudo foram realizados bioensaios laboratoriais com C. gestroi para avaliar a toxicidade de cinco substâncias que foram sintetizadas tendo como modelo a molécula da sesamina, sendo duas amidas e três compostos piperonílicos. Adicionalmente, foi analisado um inibidor de síntese de quitina, representado pelo bistrifluron. Os resultados revelaram que para as duas amidas e composto piperonílico 1, apesar de serem tóxicos, seriam necessários novos bioensaios com concentrações acima de 10 000 ppm para verificar se ocorre o aumento da dose ingerida pelos cupins. / Abstract: The subterranean termite Coptotermes gestroi (WASMANN, 1896) is a major urban pest that attacks wooden structures throughout southeastern Brazil. The most widely employed method to control subterranean termites is the direct application of insecticides on soil, however this method does not eliminate the colonies, but creates a chemical barrier between termites and their food. Moreover, this chemical barrier does not preclude infestation of buildings by alate reproductives during the reproductive season as they don't come in contact with the insecticides. The infestation may remain underground at basements or in the spaces between the stories of the buildings, as these sites offer the ideal habitat for termites with water, protection and food. An alternative strategy eliminating subterranean termite's colonies is the use of baits. In baits the insecticide is embedded in cellulose substrates, thus minimizing, the amount of insecticide used, which can't be repellent and has to have slow mode of action, generating easily removable unconsumed wastes. In this study, we performed laboratory bioassays with C. gestroi to evaluate the toxicity of five substances that were synthesized with a model of the molecule of sesamine, being two amides and three piperonyl compounds. Additionally, was analyzed a chitin synthesis inhibitor, represented by bistrifluron. The results showed that the two amides and piperonyl compound 1, although toxic, would have to be tested at concentrations above 10 000 ppm to verify if there is an increase in the uptake of insecticide. Piperonyl compounds 3 and 5 shown to be effective at the concentration of 10 000 ppm, but new bioassays would be needed to confirm this results. Bistrifluron proved efficient to be used in baits, although causing a reduction in the intake of food by termites, but didn't influence the effect of the insecticide... (Complete abstract click electronic access below) / Mestre