Atmospheric aldol self-reactions of octanal, heptanal and hexanal in a range of aqueous H2SO4 w/v% concentrations as a catalyst were studied in both bulk liquid-liquid experiments and gas-liquid experiments. Initially, a new practical methodology was developed and enhanced to monitor aldol reactions in aqueous acidic media. The evaluation of a quenching and extracting method were performed, confirming the suitability, reliability and reproducibility of the extraction method. In bulk studies, aldol products of the three aldehydes were separated and identified by preparative HPLC, GC-MS and NMR. The major aldol products observed at high acid concentrations were alpha,β-unsaturated aldehyde (dimer), trialkyl benzene (trimer) and tetraalkylcycloocta-tetraene (tetramer). The trimer of octanal was formed as trioxane in low sulfuric acid concentration and the possible mechanism accretion reaction pathways of high and low acid concentrations are proposed in this study. A systematic kinetic study of octanal, heptanal and hexanal in the bulk experiments at 65, 60 and 55 w/v% H2SO4 at 294 K were monitored using gas chromatographic equipped with a flame ionisation detector (GC-FID). The rate constants were generally estimated using second order kinetics and observed to increase as a function of sulfuric acid concentrations and also as the chain length of aliphatic aldehyde increased. The aldol self-reaction in the bulk experiment was too fast at room temperature to be easily measured using a quenching method therefore attempts were made to follow the reaction at low temperature (0 °C). The result at low temperature indicated that the rate constant of aldehyde was reduced but there was an issue of rapid rise in temperature as a result of mixing concentrated sulfuric acid with aqueous solution of the aldehyde. A gas bubbling system was developed which better simulates atmospheric reality, and which also resolves the issue of temperature rise on mixing. Two different methodologies were used: one in which the aldehyde was continually added, and one where a fixed amount was added from the gas phase and the reaction was then allowed to proceed, monitored at selected time intervals. The precision and accuracy of the fixed method was then further improved by the addition of an internal standard (IS). Using this, the concentrations of aliphatic aldehydes (C6-C8) were calibrated using an experimentally determined response factor and used to follow the loss of the reactant aldehydes. Similar methods were applied to the aldol dimers (C6-C8), which were purified and used to calibrate the chromatographic response. The rate constant for octanal, heptanal and hexanal at 76 wt% and 294 K were 0.0969 M-1 s-1, 0.1497 M-1 s-1 and 0.2622 M-1 s-1 respectively. There are some observations based upon the results presented in this thesis that may be of atmospheric significance: (i) phase separation between organic and aqueous layers in both the bulk experiment and in the bubbling system; (ii) the acid strength dependence and concentration-dependence of the various products; (iii) the faster rates than previously reported, and variation between bulk and bubbling; and (v) the time-dependent colour changes. Further work to explore these observations is proposed.

The extraction procedures for the determination of polycyclic aromatic hydrocarbons (PAH) concentrations in sediment samples had been developed by using GC-FID and GC-MS. The optimized methods were soxhlet extraction, ultrasonic bath extraction and solid phase micro extraction (SPME). In order to search out the main factors affecting extraction efficiencies of the methods, factorial design was used. The best extraction method was chosen and optimum values for main factors were selected for the development of the extraction method for PAH determination in sediment samples. The accuracy of the method was verified by analyzing NIST SRM 1597 (complex mixture of polycyclic aromatic hydrocarbons from coal tar). The selectivitiy and sensitivity obtained were quite adequate for the determination of PAHs in sediment sample. The best extraction and analysis methods were then applied to determine 16 PAHs in sea sediments from &Ouml / l&uuml / deniz Lagoon, Mugla, Turkey and 19 PAHs in Ikizcetepeler Dam Lake, Balikesir, Turkey sediments to illustrate the capability of the selected extraction and analysis method to detect PAHs and to determine the status of the contamination.

The hip-flask defence is a common claim in drunkdrinking cases. In Sweden and Norway two different models are used to determinethese cases. In Sweden one blood and two urine samples taken 60 minutes apartare used for analysis. In Norway two blood samples taken 30 minutes apart areused. Sweden focuses on the rise or fall of alcohol concentration in urine(UAC), and the ratio between UAC and blood alcohol concentrations (BAC). Norwayfocuses on the rise or fall of the alcohol metabolite ethylglucuronide (EtG) and the ratio between BAC and EtG. The aim of this study wasto test the models for multiple intakes and with different alcoholic beverages.Thirtyfive participants ingested two doses, first0.51 g/kg of beer and later either 0.25, 0.51 or 0.85 g/kg of beer, wine orvodka. Blood and urine samples were obtained before and after alcoholingestion. Alcohol was measured by GC-HS, and the alcohol metabolite byUPLC-MS/MS. The results showed that there are kineticdifferences between single and repeated intakes, that there are no significantdifferences in kinetics from different alcoholic beverages and thatthe Norwegian model appears to be the stronger one in hip-flask determination.

Dissertação(mestrado) - Universidade Federal do Rio Grande, Programa de Pós Graduação em Química Tecnológica e Ambiental, Escola de Química e Alimentos, 2010. / Submitted by Cristiane Silva (cristiane_gomides@hotmail.com) on 2013-03-26T16:43:15Z No. of bitstreams: 1 015 Adriana Neves Dias.pdf: 1206374 bytes, checksum: 1cbb9efe79ebbed837d737c5d8605fd1 (MD5) / Approved for entry into archive by Bruna Vieira(bruninha_vieira@ibest.com.br) on 2013-07-15T17:03:59Z (GMT) No. of bitstreams: 1 015 Adriana Neves Dias.pdf: 1206374 bytes, checksum: 1cbb9efe79ebbed837d737c5d8605fd1 (MD5) / Made available in DSpace on 2013-07-15T17:03:59Z (GMT). No. of bitstreams: 1 015 Adriana Neves Dias.pdf: 1206374 bytes, checksum: 1cbb9efe79ebbed837d737c5d8605fd1 (MD5) Previous issue date: 2010 / O biodiesel produzido para ser comercializado no Brasil deve estar de acordo aos padrões de qualidade estabelecidos pela resolução de 4 de fevereiro de 2010 da Agência Nacional do Petróleo, Gás Natural e do Biocombustível (ANP, 04/2010). Neste trabalho, foi estudada a aplicação dos métodos ASTM D 6584 e EN 14105 para o biodiesel de mamona e biodiesel oriundo de rota etílica. Ambos os métodos empregam GC (Cromatografia Gasosa, do inglês Gas Chromatography) com FID (Detecção por Ionização em Chama, do inglês Flame Ionization Detection) e reação de sililação com N-metil N(trimetilsilil)trifluoracetamida (MSTFA). Os compostos foram identificados para quantificação pelos tempos de retenção, para os diglicerídeos e triglicerídeos foram utilizadas bandas de tempo de retenção. Os parâmetros de validação considerados foram: curva analítica, linearidade, sensibilidade, robustez, precisão e exatidão. Os métodos ASTM D 6584 e EN 14105 apresentaram sensibilidade semelhante para todos os compostos. Foram escolhidas as condições cromatográficas estabelecidas pelo método ASTM D 6584 por ser mais rápido que o EN14105 e ter sensibilidade semelhante. O método apresentou boa linearidade com todas as curvas analíticas com r maiores que 0,999. A reação de sililação com MSTFA foi otimizada para o biodiesel etílico de mamona em virtude da sua composição química. Um volume de 500 μL de MSTFA foi escolhido para realização dos ensaios de exatidão e precisão. Os valores de exatidão ficaram entre 67 e 145,9% com valores de precisão menores que 11%. Foi avaliada a ocorrência de efeito matriz para biodiesel etílico de mamona, sendo que esse efeito foi considerado baixo para glicerol, monooleína e dioleína e médio para trioleína. Mesmo havendo efeito de matriz o preparo das curvas analíticas em solvente conforme sugerido pelos métodos de referência foi mantido. O método foi robusto frente às variações da composição química da matriz. Na aplicação do método, esse se mostrou adequado para amostras de biodiesel etílico de mamona, de girassol e da mistura de sebo e soja. / The biodiesel produced to be marketed in Brazil should be according to the quality standards established by the Resolution of February 4, 2010 of the Agência Nacional do Petróleo, Gás Natural e do Biocombustível (ANP, 04/2010). In this work, the application of the methods ASTM D 6584 e EN 14105 for castor oil biodiesel and biodiesel from ethylic routes was studied. Both the methods use Gas Chromatography with Flame Ionization Detection and silylation reaction with N-Methyl N-(trimethylsilyl)trifluoroacetamide (MSTFA). The compounds were identified by the retention times, and for di- and triglycerides were used bands of retention time. The validation parameters were: analytical curve, linearity, sensibility, robustness, precision and accuracy. The methods ASTM D 6584 e EN 14105 showed similar sensitivity for all the compounds. The chromatographic conditions established by the method ASTM D 6584 were chosen because it is faster than the method EN14105. The method presented good linearity with r greater than 0,999 for all analytical curves. The silylation reaction was optimized for the ethylic castor biodiesel because of its different chemical composition. A volume of 500 μL of MSTFA was chosen for the realization of the precision and accuracy assays. The accuracy values were between 67.0 and 145.9% with precision values lower than 11%. The matrix effect occurrence for ethylic castor oil biodiesel was evaluated. The effect was considered low for glycerol, mono- and diolein and it was considered media for triolein. But, the analytical curves were prepared in solvent even though the matrix effect. The method was robust regarding variations of the matrix chemical composition. In the application of the method, this proved to be suitable to the samplesof ethylic biodiesel of castor oil, sunflower and tallow/soybean mixture.

Os extratos vegetais amazônicos para uso em beneficiamento têxtil podem ser uma alternativa sustentável e ecológica em relação às atuais matérias-primas utilizadas pelo mercado. Este estudo teve como objetivo efetuar a caracterização físicoquímica de extratos vegetais amazônicos (óleo-resina de copaíba, óleo de castanha do Brasil, óleo de buriti, manteiga de cacau, manteiga de tucumã e manteiga de cupuaçu), preparar emulsões e realizar aplicações preliminares destas em têxteis. A caracterização físico-química foi realizada através das técnicas instrumentais analíticas de espectroscopia de infravermelho por transformada de Fourrier (FTIR) e cromatografia a gás com detecção por ionização de chama (CG-FID). Além disso, foi realizada a determinação do Equilíbrio Hidrófilo-Lipófilo (EHL) das emulsões preparadas a partir dos extratos estudados; seleção da emulsão mais estável por extrato para aplicação por foulardagem; avaliação da oxidação das emulsões aplicadas sobre o material têxtil em diferentes temperaturas (120 a 200ºC); e avaliação sensorial de toque proporcionado pelas emulsões em comparação a um amaciante de uso industrial. Os principais resultados foram que o óleo de castanha do Brasil e as manteigas de cacau, tucumã e cupuaçu apresentaram resultados próximos nas análises por FTIR; a distribuição graxa por cromatografia a gás mostrou-se útil para a caracterização destes extratos vegetais; os valores de referência de EHL para os extratos analisados foram de 7,51 a 10,72 e estão de acordo com a literatura científica (de 6 a 12); os extratos estudados emulsionados nas condições do estudo não possuem tendência à oxidação por temperatura; as médias globais das análises sensoriais de toque indicam um resultado inferior ao padrão comercial, porém, as manteigas de cacau, cupuaçu e o óleo de castanha do Brasil apresentaram os melhores resultados, com notas entre 2,8 e 2,9 (numa escala de 1 a 5). Assim, nota-se que, os resultados obtidos podem ser utilizados como base para pesquisas futuras no sentido de melhorar as formulações das emulsões para a produção de amaciantes ou outros produtos / The Amazonian plant extracts for use in textile processing can be a sustainable and environmentally friendly alternative to the current raw materials used by the market. This study aimed to make the physicochemical characterization of Amazonian plant extracts (copaiba oleoresin, Brazil nut oil, buriti oil, cocoa butter, tucumã butter and cupuaçu butter), prepare emulsions and perform preliminary applications in textile. The physicochemical characterization was performed by analytical instrumental techniques, such as FTIR spectroscopy and gas chromatography with FID detection (GC-FID). Furthermore, the determination of the Hydrophile-Lipophile Balance (HLB) was performed of the emulsions prepared from the extracts studied; the emulsion more stable for selection extract for application by padding; evaluation of the oxidation of emulsions applied to the textile material at different temperatures (120 to 200C); and sensory evaluation provided by the touch emulsions compared to a industrial softener. The main results were that the Brazil nut oil and cocoa, tucumã and cupuaçu butters showed similar results in the analysis by FTIR; grease distribution by gas chromatography proved to be useful for the characterization of plant extracts; the HLB values for the reference analyzed the extracts were 7.51 to 10.72 are consistent with the literature (6 to 12); the extracts studied emulsified in the study conditions have no tendency to oxidation temperature; the global average of sensory analysis touch indicate somewhat lower than the commercial standard, however, cocoa and cupuaçu butter and Brazil nut oil showed the best results, with grades between 2.8 and 2.9 (on a scale of 1 to 5). Thus, it is noted that the results obtained can be used as the basis for further research in order to improve the formulations of emulsions for the production of fabric softeners or other products

This thesis deals with the production and characterization of cheese analogues, ie products in which some of the dairy components are mutually or completely replaced by a non-dairy component. Model samples of fresh cheese and analogues of fresh cheese (standard) with the addition of linseed and rapeseed oil were produced by a standard technological procedure in MENDELU Brno. The content of bound and free fatty acids, volatile (aroma) substances and sensory quality was monitored in the samples. The main focus was to evaluate the effect of added vegetable oil on the monitored parameters. The fats from the sample were extracted with a mixture of diethyl ether and petroleum ether. Fatty acids were converted to methyl esters by boron trifluoride-catalyzed acid esterification and subsequently identified by GC-FID. The analysis found a higher content of fatty acids in cheese analogues in comparison with the control sample, also the content of unsaturated fatty acids increased. The HS-SPME-GC-MS method was used for the identification and semi-quantification of volatile substances (aromatic substances). 56 volatile compounds were identified in the samples; The percentage of individual chemical groups differed significantly, the highest content was found in the control sample. Sensory evaluation was performed using a scale and a serial test. In all of monitored indicators (apparence, color, consistency, smell and taste) the control sample was evaluated as best. As for the analogues the taste and smell of used oils were detected, which was unpleasant for the evaluators. The obtained results show that the addition of vegetable oils increases the nutritional value of cheeses (higher content of unsaturated fatty acids), but reduces their sensory quality and overall consumer acceptability.

The diploma thesis is focused on the study of chemical reaction products in prebiotic atmospheres. The theoretical part deals with the main theories of composing the atmosphere of the early Earth, hypotheses of the origin of life and genetic code in the form of RNA, the atmosphere of the moon Titan and the basic characteristics of the gliding arc discharge, and the analytical techniques used in the diploma thesis. In the experimental part, study of products was carried out by experimental atmospheric simulations in a special stainless steel reactor in various mixtures of gases N2, CH4, CO2 and O2. The electrical discharge for atmospheric simulation was generated by an electrode configuration for the gliding arc discharge and glow discharge. Detection and identification of chemical reaction products was performed by Gas Chromatography with Mass Spectrometry (GC-MS) and Flame Ionization Detector (GC-FID), Testo 350 M/XL and Proton Transfer Reaction Mass Spectrometry (PTR-MS). A theoretical kinetic model was created to predict and confirm the detected products. During the experiments, the dependence of the product intensity on changes in the composition of the gaseous mixture and the applied value of the electric current was also observed.

The presented work was focused on the comparison between the production of selected metabolites by carotenogenic yeasts and microalgae cultivated under conditions of external stress. The main metabolites of interest were carotenoids, further lipophilic substances and lipids. Biotechnological overproduction of these metabolites could serve as a source of potentially beneficial substances not only for the pharmaceutical, cosmetic and food industries, but also for the production of third generation biofuels. Recently, there has been a growing interest in biofuels primarily from microalgae, which have a high potential in biofuel production and seem to be a promising source. The theoretical part deals with the description of individual genera of carotenogenic yeasts, microalgae, cyanobacteria, chemical composition of produced metabolites and brief biosynthesis. In addition, individual methods for analyzing the production of the metabolites of interest were described. The experimental part is focused on the comparison of production of carotenoids, coenzyme Q, ergosterols (phytosterols) and lipids by yeasts, microalgae and cyanobacteria. As a source of external stress, temperature, salt and light stress were chosen. The strains of Rhodotorula glutinis, Rhodotorula mucilaginosa, Sporidiobolus pararoseus and Cystofilobasidium macerans were studied from the yeast strains. Microalgae and cyanobacteria were Scenedesmus obliqus, Scenedesmus dimorphus, Chlorella sorokiniana, Chlorella saccharophila, Botryococcus brauni, Synechococcus nidulans and Arthrospira maxima. The yeast and algal strains were optimized for growth, carotenoid and lipid production. Applied salt stress showed a significant liquidation effect on algal and cyanobacterial strains. The thesis also monitored the biological stress, so-called co-cultivation of microalgae and yeasts. Further experiments will be the subject of future work.

This paper deals with the manufacture and characterisation of cheese analogues, which are products, where the milk components are totally or partially replaced by non-milk components. Model samples, edam type cheese and the analogue containing hazelnut oil, were manufactured using the standard way at Brno Mendelu. The main parameters chosen to describe the quality of samples were free and bound fatty acids, volatile compounds and sensory quality. The main aim was to judge the influence of added hazelnut oil on mentioned parameters. For the identification and semiquantification of volatile compounds HS-SPME-GC-MS method was used. Fat extraction from sample was made with a mixture of two solvents (diethylether, petrolether), fatty acids were identified and quantified by GC-FID, with their former acid transesterification using methanolic solution of BF3 as a catalyst. For sensory analysis of the appearance, colour, texture, aroma, taste and overall acceptance of the sample descriptive scales and comparison with standard were used, the structure was observed by electron microscopy. The results show that addition of hazelnut oil affects the sensory properties, ripening process (higher amount of volatile compounds, faster lipolysis), nutrition value (higher amount of unsaturated fatty acids), and the stability of the product.

The presented diploma thesis deals with the extraction and storage stability of lipophilic pigments produced by selected strains of yeasts and algae. In this thesis, there was studied the influence of the selected solvents on the efficiency of extraction, as well as the effect of ambient temperature on the stability of the pigments during storage. The work is divided into two main parts, theoretical and practical part. In the theoretical part knowledge about algae, yeasts and their cultivation parameters is summarized. Furthermore, some information regarding the selected lipid metabolites, their properties and possibilities of application in various branches of industry is mentioned. The practical part deals with the preparation of extracts and stability tests. Extracts were prepared from selected biomass samples in solvents suitable for applications in food industry or cosmetics (ethanol and hexane). Subsequently, the long-term stability tests lasting 4 months and short-term stability tests lasting a total of 28 days were performed on these extracts. The pigments were determined by HPLC and spectrophotometrically, the fatty acid content was determined by GC. For the extraction of pigments from biomass, in the most cases ethanol appears to be the optimal solvent. However, for lipid extraction from biomass, hexane appears to be the optimal solvent for a significant number of samples. In most samples, storage in the freezer showed the most favourable effect on pigment stability, but some samples showed comparable stability even when stored in the refrigerator.