Une nouvelle technique de dépôt de phases stationnaires solides pour la fabrication de micro colonnes de chromatographie en phase gazeuse a été proposée : pour dépasser les limites des phases stationnaires liquides conventionnelles (ou occasionnellement solides) en termes de rétention des composés très volatiles et/ou de fabrication par lots en salle blanche, une approche consistant en le dépôt direct de l'adsorbant sur le substrat par pulvérisation cathodique a été mise en œuvre. La méthode est par nature compatible avec le procédé de fabrication en salle blanche et industrialisable, et a montré de bons résultats en termes de précision. La séparation d'hydrocarbures volatiles a été rendue possible sur silice, alumine, graphite et magnésie. Différents types de colonnes (structure, phase stationnaire) ont été fabriquées sous la forme de puces en silicium de 2x2 cm², et leurs caractérisations thermodynamique et cinétique ont été réalisées. Des efficacités très satisfaisantes ont été obtenues (plus de 5700 plateaux, des hauteurs de plateau de 250 µm). La possibilité d'utiliser des colonnes à phase stationnaire déposée par pulvérisation cathodique pour l'analyse automatisée en temps réel d'hydrocarbures légers sur site pétrolier a été démontrée par l'implémentation d'un système de programmation en température de la puce et divers tests d'adaptabilité (haute température, gaz vecteur, humidité) : une séparation complète des alcanes linéaires C1-C9 en moins de 15 secondes a été obtenue, ainsi que des séparations de mélanges plus complexes (isomères, insaturés). Une application industrielle confidentielle a été brevetée et développée. / A totally new solid stationary phase deposition technique for micro machined gas chromatography (GC) columns fabrication was proposed: to overcome the limitations of conventional liquid (or occasionally solid) stationary phases in terms of very volatile compounds retention and/or clean room batch production, an approach consisting of the collective direct deposition of the adsorbent in micro columns channels by sputtering was performed. The process was fully compatible with clean room fabrication flow and industry-ready, with very good precision results. Silica, alumina, graphite and magnesia were proven able to separate volatile hydrocarbons. Various types of columns (structure, stationary phase) were fabricated in the form of 2x2 cm² silicon-Pyrex chips, and their thermodynamic and kinetic evaluations were reported. Retentions were observed to increase from magnesia to graphite through alumina and silica and with phase ratio decrease, as expected; very satisfying efficiencies were obtained: more than 5700 plates, and 250 µm-high plates. The possibility to use such columns for fast in-situ and autonomous monitoring of light hydrocarbons in oilfield environments was demonstrated by the implementation of a chip temperature-programming system and various versatility tests (high temperatures, carrier gas, humidity): a complete C1-C9 linear alkanes separation was performed in less than 15 seconds, as well as complex mixtures fast separations (isomers, unsaturated), and an industrial confidential application was developed and patented. Therefore, sputter-deposited stationary phase micro columns opened numerous perspectives for the developments of miniaturized GC apparatuses.

By virtue of their fragrance and therapeutic nature, essential oils have gained great application in the cosmetic and pharmaceutical industries. These oils, as products consumed by the public for the general health and cosmetics, should be of high quality and unadulterated. In this project comprehensive two-dimensional gas chromatography (GCxGC) was used for the qualitative analysis of some South African essential oils. The main purpose of the project was to evaluate GCxGC for identification of essential oil constituents and for fingerprinting the different essential oils for quality control purposes. Essential oils of the same kind but of different origin were compared and the quantitative variation between their components was studied. Gas chromatography-time-of flight mass spectrometry (GC-TOFMS) as well as comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GCxGC-TOFMS) was used to help identify component peaks separated in the GCxGC instrument. Once certain precautions are taken and the delicate modulator is correctly optimized, the GCxGC results are reproducible and easy to interpret. Overall, the GCxGC technique utilized showed good promise for quality control of essential oils. / Dissertation (MSc)--University of Pretoria, 2006. / Chemistry / unrestricted

Fingerprint profiles generated through GC analysis, are powerful tools for quality control in the food and beverage industry. Beer aroma profiles can be used for the fingerprinting of specific beer brands or for trouble shooting purposes such as the identification of off-flavours. The multichannel silicone rubber trap (MCT) lends itself perfectly to this task. The simplicity and robustness of the MCT makes it ideal for concentrating the volatile compounds that constitute the aroma of an alcoholic beverage such as beer. The retention of these substances by the silicone is based on dissolution into the polymer. This gives more intrinsic stability to the concentrated aroma compounds than traditionally used, adsorption based methods, so transport of the trap and contents should not be a problem. Thermal desorption is used to introduce the trapped aroma compounds to the chromatographic instrument. This eliminates the need for high purity solvents and greatly reduces the sample preparation time. The easily identifiable and stable background peaks from the silicone matrix makes the MCT ideal for repeated use with a thermal desorber. During this study the performance of the MCT as concentration device was investigated for its ability to concentrate aroma volatiles representing a wide range of volatilities. The sampling and desorption procedures were optimised in order to attain the required detection levels and repeatability of the analytical method based on this purge-and-trap sampling scheme / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / MSc / unrestricted

The slow yet steady expansion of the global economies, has led to an increased demand for energy and fuel, which would eventually lead to shortage of fossil fuel resources in the near future. Consequently, researchers have been investigating other fuels like biodiesel. Biodiesel refers to the monoalkyl esters which can be derived from a wide range of sources like vegetable oils, animal fats, algae lipids and waste greases. Currently, biodiesel is largely produced by the conventional route, using an acid, a base or an enzyme catalyst. Drawbacks associated with this route result in higher production costs and longer processing times. Conversely, supercritical transesterification presents several advantages over conventional transesterification, such as, faster reaction rates, catalyst free reaction, less product purification steps and higher yields. This work focused on the supercritical transesterification of cooking oil, soybean in particular. The experimental investigation was conducted using methanol at supercritical conditions. These conditions were milder in terms of pressure than those reported in literature. A batch setup was designed, built and used to carry out the supercritical transesterification reactions. The biodiesel content was analyzed using gas chromatography-mass spectrometry to calculate reaction yields. Methyl ester yield of 90% was achieved within 10 minutes of reaction time using supercritical transesterification. A maximum yield of 97% was achieved with this process in 50 minutes of reaction time. Two key factors, temperature and molar ratio were studied using variance analysis and linear regression and their significance on the biodiesel yield was determined. The kinetic tendency of the reaction was investigated and the values of rate constants, activation energy and the pre-exponential factor were estimated.

The essential amino acid tryptophan is an important substrate for the synthesis of serotonin, melatonin, tryptamine, proteins and the kynurenines. The aim of this study was to investigate tryptophan metabolism along the kynurenine pathway in a low income sub- Saharan HIV/AIDS patient population from the Gauteng Province of South Africa. The first objective was to develop and validate a novel gas chromatography mass spectrometry method to enable reliable quantification of tryptophan and metabolites of the kynurenine pathway in plasma. Validation parameters for the detection of tryptophan, kynurenine, quinolinic acid and nicotinamide conformed to international criteria for newly developed methods. The next objective of the study was to find an appropriate biomarker against which to express the results. Several substances previously described as indicators were assessed and compared, including plasma neopterin, procalcitonin, C-reactive protein, the cytokines IL-2, IL-4, IL-6, IL-10, TNF, and IFN-gamma, as well as factors routinely measured and elsewhere described as biomarkers in HIV, i.e., albumin, the albumin/globulin ratio, haemoglobin and red cell distribution width. Neopterin was shown to be superior as indicator of pro-inflammatory status, as indicator of the degree of immune deficiency, to predict disease progression, to distinguish between patients with and without tuberculosis co-infection and to reflect the success of highly active antiretroviral treatment (HAART). In the analyses of the kynurenine pathway metabolites, tryptophan levels were seen to be significantly lower (24.36 ± 4.14 vs. 43.57 ± 11.85 μmol/l; p<0.0001), while the activity of the enzyme, indoleamine 2,3 dioxygenase (IDO), (K/T:136.03 vs. 52.18; p<0.001), as well as kynurenine (3.21 ± 1.33 vs. 2.14 ± 0.45 μmol/l; p<0.001) and quinolinic acid (4.46 ± 2.32 vs. 0.25 ± 0.058 μmol/l; p<0.001) levels were significantly higher in the total patient group (n=105) than in the control group (n=60). Patients on HAART showed not only significantly higher CD4 counts (296.21 ± 195.50 vs. 170.05 ± 167.26 cells/μl; p=0.003), but also lower inflammatory activity (neopterin: 35.51 ± 35.70 vs. 66.63 ± 40.73 nmol/l; p<0.001 and IL-6: 9.56 ± 12.54 vs. 15.04 ± 19.34 pg/ml; p<0.05), lower IFN-γ (41.43 ± 14.14 vs. 53.68±34.39 pg/ml; p<0.05), higher tryptophan levels (25.13 ± 3.80 vs. 22.04 ± 4.32 μmol/l; p=0.033), lower kynurenine levels (3.08 ± 1.28 vs. 3.58 ± 1.42 μmol/l; p=0.144) and lower quinolinic acid levels (4.03 ± 2.04 vs. 5.77 ± 2.65μmol/l; p=0.072) than patients not on HAART. Tryptophan depletion and IDO activity, as well as the levels of kynurenine and quinolinic acid, were generally greater than in populations from developed countries. Indications are that this can be ascribed to higher levels of inflammatory activity at comparable levels of immune deficiency in the disadvantaged population of this study. The degree of tryptophan depletion and quinolinic acid accumulation found could negatively impact on the physical and neuropsychiatric wellness of the population. Correlations between quinolinic acid, and nicotinamide levels showed a significant contribution of kynurenine pathway metabolism to the plasma levels of nicotinamide. This de novo synthesis of nicotinamide could offer protection against niacin deficiency and NAD depletion in populations with inadequate dietary intake. This is the first study to assess plasma tryptophan, kynurenine, quinolinic acid and nicotinamide levels, as well as IDO activity, pro-inflammatory status and IFN-γ levels, simultaneously in one population and to compare it to that of HIV/AIDS patients in developed countries. / Thesis (PhD)--University of Pretoria, 2015. / tm2015 / Physiology / PhD / Unrestricted

Orientadores: Lauro Euclides Soares Barata, Fabio Augusto / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-18T13:25:10Z (GMT). No. of bitstreams: 1 Souza_RitadeCassiaZacardide_M.pdf: 1828503 bytes, checksum: c564b2bcd8fc2c55c0690d12a6c9dc53 (MD5) Previous issue date: 2011 / Resumo: O presente trabalho é apresentado em dois capítulos: o primeiro compreende o desenvolvimento de uma metodologia de diferenciação entre duas espécies de Aniba frequentemente confundidas, Aniba parviflora e Aniba rosaeodora e o segundo compreende o estudo da composição química dos óleos essenciais de Aniba parviflora através de cromatografia gasosa acoplada a espectrometria de massas (CG-EM), cromatografia gasosa com detector de ionização de chama (CG-DIC) e cromatografia gasosa bidimensional abrangente acoplada à espectrometria de massas (CG × CGEM). Para a diferenciação das espécies foi utilizada a avaliação das suas frações voláteis (headspace) através da SPME-CG (Microextração em Fase Sólida acoplada a Cromatografia Gasosa). Foram analisadas um total de 100 amostras de folhas das duas espécies e a diferenciação foi feita através do tratamento quimiométrico dos dados obtidos. Foram analisados ainda óleos essenciais das folhas e da madeira de A. parviflora obtidos por arraste a vapor. O estudo destes forneceu além da composição química, a análise quantitativa dos seus componentes. Por fim foi realizada a comparação da técnica de CG-EM com a inovadora técnica de CGxCG-EM que possibilitou um aumento de 50% na identificação dos componentes e aproximadamente de 80% na separação e detecção. Os resultados obtidos permitem dizer que e possível diferenciar duas espécies botanicamente vizinhas através de técnicas analíticas de maneira objetiva com respaldo estatístico / Abstract: This work consists of two main parts: The first part involves the development of a differentiation methodology between two Aniba species that are often confused with one another, they are Aniba parviflora and Aniba rosaeodora. The second part involves the chemical composition study of Aniba parviflora essential oils through gas chromatography coupled to mass spectrometry (GC-MS), gas chromatography with flame ionization detection (GC-FID) and comprehensive two-dimensional gas chromatography (GC × GC- MS). In the first part, the species differentiation was performed using SPME-GC and chemometric tools for the assessment of their volatile fraction (headspace). A total of 100 different leaf samples coming from distinct individuals of these two species were examined and the differentiation was made based on the SPME-GC chromatograms data that were treated using chemometric tools. In the second part the essential oils of A. parviflora coming both from leaves and wood were also analyzed and its study resulted in the oils chemical composition and in the quantitative analyses of its components. This work provided also a comparison between two techniques, GC-MS and the innovative GCxGC-MS. The later technique allowed an increase of at least 80 % of total components separation and detection and an increase of more than 50 % of the total identified components / Mestrado / Quimica Organica / Mestre em Química

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Made available in DSpace on 2016-01-26T18:55:45Z (GMT). No. of bitstreams: 1 Dissertacao Cleidemar.pdf: 291699 bytes, checksum: 46535cd36bde0f3bcd3e5d22ca0f3899 (MD5) Previous issue date: 2008-03-28 / The objective was to validate a sensitive, single, rapid and low cost analytical method is presented for determination of amitraz concentration in cat plasma samples using gas chromatography with capillary column and thermionic specific detector (GC-TSD). The method was linear between 20 to 400 ng ml-1 with regression coefficients corresponding to 0.9987 and the coefficient of variation of the points of the calibration curve lower than 20%. The detection limits and quantification were 10 and 20 ng ml-1 respectively. The proposed method was useful and efficient for detection of the amitraz in the plasma of cats intoxicated with this product in a dipping bath. / O objetivo foi validar um método analítico simples, rápido e de baixo custo para determinação da concentração de amitraz no plasma de gatos intoxicados experimentalmente através de banho, empregando-se a cromatografia gasosa com coluna capilar e detector termiônico específico (CG-DTE). O método mostrou-se linear na faixa entre 20 a 400 ng/mL com coeficiente de correlação igual a 0,9987 e o coeficiente de variação dos pontos da curva de calibração abaixo de 15%. Os limites de detecção e quantificação foram 10 ng/mL e 20 ng/mL respectivamente. A metodologia empregada se mostrou útil e eficiente para detecção do amitraz no plasma de gatos intoxicados com este produto.

Made available in DSpace on 2016-07-18T17:53:18Z (GMT). No. of bitstreams: 1 Dissertacao Cleidemar.pdf: 291699 bytes, checksum: 46535cd36bde0f3bcd3e5d22ca0f3899 (MD5) Previous issue date: 2008-03-28 / The objective was to validate a sensitive, single, rapid and low cost analytical method is presented for determination of amitraz concentration in cat plasma samples using gas chromatography with capillary column and thermionic specific detector (GC-TSD). The method was linear between 20 to 400 ng ml-1 with regression coefficients corresponding to 0.9987 and the coefficient of variation of the points of the calibration curve lower than 20%. The detection limits and quantification were 10 and 20 ng ml-1 respectively. The proposed method was useful and efficient for detection of the amitraz in the plasma of cats intoxicated with this product in a dipping bath. / O objetivo foi validar um método analítico simples, rápido e de baixo custo para determinação da concentração de amitraz no plasma de gatos intoxicados experimentalmente através de banho, empregando-se a cromatografia gasosa com coluna capilar e detector termiônico específico (CG-DTE). O método mostrou-se linear na faixa entre 20 a 400 ng/mL com coeficiente de correlação igual a 0,9987 e o coeficiente de variação dos pontos da curva de calibração abaixo de 15%. Os limites de detecção e quantificação foram 10 ng/mL e 20 ng/mL respectivamente. A metodologia empregada se mostrou útil e eficiente para detecção do amitraz no plasma de gatos intoxicados com este produto.

Bis(1,3,7,9-tetramethyl-5-mesityldipyrrinato)zinc(II) (ZnDPY) was synthesized in the lab by the McCusker group and a procedure was created to analyze its ability as a photosensitizer, a molecule that provides the energy for the reaction to occur by capturing light energy and turning it into a form that can be used by the photocatalyst. While more work is needed, preliminary steps have been made to create a process that can analyze the amount of carbon monoxide produced by a photocatalytic CO2 reduction reaction with ZnDPY as the photosensitizer. Progress has been made via the setup of a reaction apparatus, targeted gas chromatography (GC) peak separation, and GC calibration. More work will need to be done in order to determine the optimal reaction mix to showcase the sensitizer’s potential.