988 resultados para ultra fast gas chromatography


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A contínua subida dos preços dos combustíveis fósseis tradicionais aliada à crescente pressão por parte de várias instituições mundiais para uma política “verde” no que diz respeito aos combustíveis, levam a um aumento da procura dos biocombustíveis e é neste contexto que surge o biodiesel como um dos principais intervenientes. O biodiesel pode ser definido como um derivado éster monoalquílico de ácidos gordos de cadeia longa proveniente de fontes renováveis como óleos vegetais ou gorduras animais e que apresenta características semelhantes ao diesel de petróleo, podendo ser utilizado sem qualquer problema em motores de ignição por compressão. Este trabalho apresenta como principal objetivo o estudo da aplicação da tecnologia de ultrassons na produção de biodiesel. Foi utilizado neste trabalho como matéria-prima um óleo doméstico usado. Este óleo foi previamente filtrado sendo depois analisado o seu índice de acidez para avaliar o seu teor em ácidos gordos livres. O valor obtido para o índice de acidez do óleo foi de 1,91 mg KOH/g, um valor relativamente baixo permitindo a sua utilização sem ser necessário um tratamento inicial via esterificação para diminuir a acidez do mesmo. Foram realizados três ensaios de reação independentes, o primeiro recorrendo ao método tradicional de produção de biodiesel através de transesterificação e recorrendo a agitação mecânica e aquecimento, o segundo utilizando uma sonda de ultrassons com a potência de 500 W e um terceiro ensaio de reação utilizando uma sonda de ultrassons de 2000 W. Em todas as reações foi utilizada uma proporção de 1:5 de óleo usado e metanol e 0,5 % (em relação á massa de óleo utilizada) de catalisador metilato de sódio. Todas as alíquotas recolhidas durante os ensaios foram analisadas através de cromatografia gasosa de modo a determinar o conteúdo em ésteres presente em cada uma delas. A reação convencional teve uma duração total de 150 minutos e decorreu a uma temperatura de 65ºC e a agitação constante de 500 rpm. Ao longo da reação foram retiradas alíquotas de cerca de 25 ml, que foram tratadas de imediato e posteriormente analisadas de modo a estudar-se o comportamento da reação ao longo do tempo. A percentagem de ésteres metílicos no biodiesel obtida ao fim de 90 minutos foi de 81,3%. Em seguida realizou-se uma reação utilizando uma sonda de ultrassons de 500 W de potência mergulhada num recipiente reacional devidamente isolado com uma rolha de cortiça de modo a minimizar as perdas de metanol por evaporação. O tempo total de reação foi de 90 minutos e foram-se retirando alíquotas de cerca de 25 ml para acompanhar o desenrolar da reação, tendo-se obtido uma percentagem de ésteres metílicos de 85,9% ao fim dos 90 minutos. Foi realizada por fim um terceiro ensaio de reação utilizando uma sonda de 2000 W com uma duração total de 90 minutos, tendo-se obtido resultados pouco satisfatórios (77,7%), provavelmente devido a algum problema operacional relacionado com a sonda de ultrassons utilizada ou devido a uma geometria do reator pouco eficiente. Os produtos resultantes da reação convencional e da reação utilizando a sonda de ultrassons de 500 W, assim como o óleo utilizado como matéria-prima foram caracterizados em termos de índice de acidez, densidade a 15ºC e viscosidade a 40ºC.

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Os ácidos gordos desempenham um papel fisiológico importante como componentes indispensáveis na estrutura celular, bem como fontes de energia. Nas últimas décadas, tem havido um aumento notável do interesse público nos ácidos gordos polinsaturados ómegas 3 e 6 e no seu impacto sobre a saúde humana, especialmente em doenças metabólicas e cardiovasculares. Estes ácidos gordos específicos podem prevenir e/ou tratar várias patologias metabólicas, atuando nomeadamente como compostos anti-inflamatórios. A menopausa é um fator de risco para doença cardiovascular, a diminuição de estrogénio, que ocorre neste estado fisiológico, provoca disfunção endotelial e stresse oxidativo. Consequentemente há uma redução dos níveis de ácidos gordos polinsaturados ómegas 3, o que contribui para o aparecimento de aterosclerose e doença cardiovascular. Neste contexto, o objetivo deste estudo foi avaliar e caracterizar o perfil lipídico de ácidos gordos de uma amostra de mulheres pós-menopausa e com este, estudar as associações entre o perfil lipídico determinado e parâmetros metabólicos de risco (parâmetros clínicos e bioquímicos). Inicialmente, os ácidos gordos foram extraídos da matriz plasmática através da derivatização destes e a sua composição percentual no plasma foi determinada com recurso a cromatografia gasosa com deteção de ionização de chama. De seguida, através do software IBM SPSS Statistics 21, foram estabelecidas associações entre os parâmetros clínicos e bioquímicos e o perfil lipídico determinado. A população em estudo foi divida em dois grupos consoante o período de entrada na menopausa (há menos de 7 anos e há 7 anos ou mais). Não há conhecimento de estudos semelhantes ao apresentado, que relacionem todo o perfil de ácidos gordos com parâmetros metabólicos de risco considerando o estado menopausal. Os resultados obtidos mostram que o perfil lipídico influencia vários marcadores metabólicos / endócrinos com relevância clínica que devem ser explorados em futuros ensaios clínicos. Para as mulheres na menopausa há menos de 7 anos foram estabelecidas as seguintes relações: i) entre os ácidos gordos saturados e insaturados cis e os níveis de ALP; ii) entre os ácidos gordos mono e polinsaturados cis e os níveis de GGT, IL10 e estradiol; iii) entre os ácidos gordos polinsaturados trans e o IMC e os níveis de IL6; iv) entre os ómegas 3 e os níveis de IL10 e ácido úrico; v) entre os ómegas 6 e os níveis de estradiol, ALP e GGT; vi) entre os ómegas 9 e os níveis de estradiol e GGT; vi) entre os ácidos gordos de curta cadeia e os níveis de colesterol total, LDL, triglicerídeos e IL10; vii) entre os ácidos gordos saturados de cadeia longa e o ΣÁcido láurico, mirístico, palmítico e esteárico e os níveis de triglicerídeos, ALP e GGT; viii) os níveis de IL10 podem ser simultaneamente associados com os ácidos gordos de curta cadeia e os ómegas 3. Para as mulheres na menopausa há 7 anos ou mais foram estabelecidas relações: i) entre os ómegas 3 e o IMC e os níveis de triglicerídeos; ii) entre os ácidos gordos monoinsaturados cis e os ómegas 9 com os níveis de ALT. Relações independentes do estado menopausal também foram estabelecidas, nomeadamente: i) entre os ácidos gordos polinsaturados cis e ómegas 6 e os níveis de ALT, triglicerídeos e AST; ii) entre os níveis de ácidos gordos monoinsaturados cis e ómegas 9 e os níveis de AST e triglicerídeos. O perfil lipídico de ácidos gordos pode ser considerado um biomarcador para a condição de saúde da mulher na menopausa.

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Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

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Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

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Dissertation for the obtention of the Master Degree in Biotechnology

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Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente Perfil de Gestão de Sistemas Ambientais

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Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

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New emerging contaminants could represent a danger to the environment and Humanity with repercussions not yet known. One of the major worldwide pharmaceutical and personal care productions are antimicrobials products, triclosan, is an antimicrobial agent present in most products. Despite the high removal rate of triclosan present in wastewater treatments, triclosan levels are on the rise in the environment through disposal of wastewater effluent and use of sewage sludge in land application. Regulated in the EC/1272/2008 (annex VI, table 3.1), this compound is considered very toxic to aquatic life and it has been reported that photochemical transformation of triclosan produces dioxins. In the current work it was defined three objectives; determination of the most efficient process in triclosan degradation, recurring to photochemical degradation methods comparing different sources of light; identification of the main by-products formed during the degradation and the study of the influence of the Fenton and photo-Fenton reaction. Photochemical degradation methods such as: photocatalysis under florescent light (UV), photocatalysis under visible light (sunlight), photocatalysis under LEDs, photo-Fenton and Fenton reaction have been compared in this work. The degradation of triclosan was visualized through gas chromatography/mass spectrometry (GC/MS). In this study photo-Fenton reaction has successfully oxidized triclosan to H2O and CO2 without any by-products within 2 hours. Photocatalysis by titanium dioxide (TiO2) under LEDs was possible, having a degradation rate of 53% in an 8 hours essay. The degradation rate of the Fenton reaction, UV light and sunlight showed degradation between 90% and 95%. The results are reported to the data observed without statistic support, since this was not possible during the work period. Hydroquinone specie and 2,4-dichlorophenol by-products were identified in the first hour of photocatalysis by UV. A common compound, possibly identified has C7O4H , was present at the degradation by UV, sunlight and LEDs and was concluded to be a contaminant. In the future more studies in the use of LEDs should be undertaken given the advantages of long durability and low consumption of energy of these lamps and that due to their negative impact on the environment fluorescent lamps are being progressively made unavailable by governments, requiring new solutions to be found. Fenton and photo-Fenton reactions can also be costly processes given the expensive reagents used.

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Introduction There are few studies reporting the antifungal activities of Lippia alba extracts. Methods A broth microdilution assay was used to evaluate the antifungal effects of Lippia alba extracts against seven yeast species of Candida and Cryptococcus. The butanol fraction was investigated by gas chromatography-mass spectrometry. Results The butanol fraction showed the highest activity against Candida glabrata. The fraction also acted synergistically with itraconazole and fluconazole against C. glabrata. The dominant compounds in the butanol fraction were 2,2,5-trimethyl-3,4-hexanedione, 3,5-dimethyl-4-octanone and hexadecane. Conclusions The butanol fraction may be a good candidate in the search for new drugs from natural products with antifungal activity.

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Abstract INTRODUCTION: The aim of this study was to determine whether an herbal extract containing monoterpene exhibited activity against multidrug-resistant Staphylococcus aureus and Pseudomonas aeruginosa isolated from clinical infection samples. METHODS: The essential oil of Trachyspermum ammi (L.) Sprague ex Turrill (Apiaceae) fruit was extracted by hydrodistillation. Fruit residues were treated with hydrochloric acid and re-hydrodistilled to obtain volatile compounds. Compounds in the distilled oil were identified using gas-chromatography (GC) and GC-mass spectrometry (MS). The antibiotic susceptibility of all bacterial isolates was analyzed using both the disc diffusion method and determination of the minimum inhibitory concentration (MIC). The sensitivity of antibiotic-resistant isolates to essential oil was also determined by using the disc diffusion method and MIC determination. RESULTS: Of 26 clinical isolates, 92% were multidrug-resistant (MDR). Aromatic monoterpenes (thymol, paracymene, and gamma-terpinene) were the major (90%) components of the oil. Growth of S. aureus strains was successfully inhibited by the oil, with an inhibitory zone diameter (IZD) between 30-60mm and MIC <0.02μL/mL. The oil had no antimicrobial activity against clinical isolates of P. aeruginosa; rather, it prevented pigment production in these isolates. CONCLUSIONS: This study revealed that the essential oil of Trachyspermum ammi, which contains monoterpene, has good antibacterial potency. Monoterpenes could thus be incorporated into antimicrobial ointment formulas in order to treat highly drug-resistant S. aureus infections. Our findings also underscore the utility of research on natural products in order to combat bacterial multidrug resistance.

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Tese de Doutoramento em Ciências - Especialidade em Biologia

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The use of chemical analysis of microbial components, including proteins, became an important achievement in the 80’s of the last century to the microbial identification. This led a more objective microbial identification scheme, called chemotaxonomy, and the analytical tools used in the field are mainly 1D/2D gel electrophoresis, spectrophotometry, high-performance liquid chromatography, gas chromatography, and combined gas chromatography-mass spectrometry. The Edman degradation reaction was also applied to peptides sequence giving important insights to the microbial identification. The rapid development of these techniques, in association with knowledge generated by DNA sequencing and phylogeny based on rRNA gene and housekeeping genes sequences, boosted the microbial identification to an unparalleled scale. The recent results of mass spectrometry (MS), like Matrix-Assisted Laser Desorption/Ionisation Time-of-Flight (MALDI-TOF), for rapid and reliable microbial identification showed considerable promise. In addition, the technique is rapid, reliable and inexpensive in terms of labour and consumables when compared with other biological techniques. At present, MALDI-TOF MS adds an additional step for polyphasic identification which is essential when there is a paucity of characters or high DNA homologies for delimiting very close related species. The full impact of this approach is now being appreciated when more diverse species are studied in detail and successfully identified. However, even with the best polyphasic system, identification of some taxa remains time-consuming and determining what represents a species remains subjective. The possibilities opened with new and even more robust mass spectrometers combined with sound and reliable databases allow not only the microbial identification based on the proteome fingerprinting but also include de novo specific proteins sequencing as additional step. These approaches are pushing the boundaries in the microbial identification field.

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The use of chemical analysis of microbial components, including proteins, became an important achievement in the 80’s of the last century to the microbial identification. This led a more objective microbial identification scheme, called chemotaxonomy, and the analytical tools used in the field are mainly 1D/2D gel electrophoresis, spectrophotometry, high-performance liquid chromatography, gas chromatography, and combined gas chromatography-mass spectrometry. The Edman degradation reaction was also applied to peptides sequence giving important insights to the microbial identification. The rapid development of these techniques, in association with knowledge generated by DNA sequencing and phylogeny based on rRNA gene and housekeeping genes sequences, boosted the microbial identification to an unparalleled scale. The recent results of mass spectrometry (MS), like Matrix-Assisted Laser Desorption/Ionisation Time-of-Flight (MALDI-TOF), for rapid and reliable microbial identification showed considerable promise. In addition, the technique is rapid, reliable and inexpensive in terms of labour and consumables when compared with other biological techniques. At present, MALDI-TOF MS adds an additional step for polyphasic identification which is essential when there is a paucity of characters or high DNA homologies for delimiting very close related species. The full impact of this approach is now being appreciated when more diverse species are studied in detail and successfully identified. However, even with the best polyphasic system, identification of some taxa remains time-consuming and determining what represents a species remains subjective. The possibilities opened with new and even more robust mass spectrometers combined with sound and reliable databases allow not only the microbial identification based on the proteome fingerprinting but also include de novo specific proteins sequencing as additional step. These approaches are pushing the boundaries in the microbial identification field.

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Long pepper (Piper hispidinervum) is an Amazonian species of commercial interest due to the production of safrole. Drying long pepper biomass to extract safrole is a time consuming and costly process that can also result in the contamination of the material by microorganisms. The objective of this study was to analyze the yield of essential oil and safrole content of fresh and dried biomass of long pepper accessions maintained in the Active Germoplasm Bank of Embrapa Acre, in the state of Acre, Brazil, aiming at selecting genotypes with best performance on fresh biomass to recommend to the breeding program of the species. Yield of essential oil and safrole content were assessed in 15 long pepper accessions. The essential oil extraction was performed by hydrodistillation and analyzed by gas chromatography. A joint analysis of experiments was performed and the means of essential oil yield and safrole content for each biomass were compared by Student's t-test. There was variability in the essential oil yield and safrole content. There was no difference between the types of biomass for oil yield; however to the safrole content there was difference. Populations 9, 10, 12 and 15 had values of oil yield between 4.1 and 5.3%, and safrole content between 87.2 and 94.3%. The drying process does not interfere in oil productivity. These populations have potential for selection to the long pepper breeding program using oil extraction in the fresh biomass

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Aromatic amines are widely used industrial chemicals as their major sources in the environment include several chemical industry sectors such as oil refining, synthetic polymers, dyes, adhesives, rubbers, perfume, pharmaceuticals, pesticides and explosives. They result also from diesel exhaust, combustion of wood chips and rubber and tobacco smoke. Some types of aromatic amines are generated during cooking, special grilled meat and fish, as well. The intensive use and production of these compounds explains its occurrence in the environment such as in air, water and soil, thereby creating a potential for human exposure. Since aromatic amines are potential carcinogenic and toxic agents, they constitute an important class of environmental pollutants of enormous concern, which efficient removal is a crucial task for researchers, so several methods have been investigated and applied. In this chapter the types and general properties of aromatic amine compounds are reviewed. As aromatic amines are continuously entering the environment from various sources and have been designated as high priority pollutants, their presence in the environment must be monitored at concentration levels lower than 30 mg L1, compatible with the limits allowed by the regulations. Consequently, most relevant analytical methods to detect the aromatic amines composition in environmental matrices, and for monitoring their degradation, are essential and will be presented. Those include Spectroscopy, namely UV/visible and Fourier Transform Infrared Spectroscopy (FTIR); Chromatography, in particular Thin Layer (TLC), High Performance Liquid (HPLC) and Gas chromatography (GC); Capillary electrophoresis (CE); Mass spectrometry (MS) and combination of different methods including GC-MS, HPLC-MS and CE-MS. Choosing the best methods depend on their availability, costs, detection limit and sample concentration, which sometimes need to be concentrate or pretreated. However, combined methods may give more complete results based on the complementary information. The environmental impact, toxicity and carcinogenicity of many aromatic amines have been reported and are emphasized in this chapter too. Lately, the conventional aromatic amines degradation and the alternative biodegradation processes are highlighted. Parameters affecting biodegradation, role of different electron acceptors in aerobic and anaerobic biodegradation and kinetics are discussed. Conventional processes including extraction, adsorption onto activated carbon, chemical oxidation, advanced oxidation, electrochemical techniques and irradiation suffer from drawbacks including high costs, formation of hazardous by-products and low efficiency. Biological processes, taking advantage of the naturally processes occurring in environment, have been developed and tested, proved as an economic, energy efficient and environmentally feasible alternative. Aerobic biodegradation is one of the most promising techniques for aromatic amines remediation, but has the drawback of aromatic amines autooxidation once they are exposed to oxygen, instead of their degradation. Higher costs, especially due to power consumption for aeration, can also limit its application. Anaerobic degradation technology is the novel path for treatment of a wide variety of aromatic amines, including industrial wastewater, and will be discussed. However, some are difficult to degrade under anaerobic conditions and, thus, other electron acceptors such as nitrate, iron, sulphate, manganese and carbonate have, alternatively, been tested.