Pervaporation is a selective membrane technique in which a liquid feed mixture is separated by means of partial vaporization through a non-porous perm-selective membrane. This method can be used for the recovery of heat sensitive aroma compounds to avoid them from thermal damage in beverage industries. The main objective of this study was to determine the effects of feed temperature (30, 40, 50&deg / C), composition (different model solutions, strawberry essence), concentration (50, 100, 150 ppm) and permeate pressure (4, 8 mbar) on the recovery of aroma compounds of strawberry by pervaporation in terms of mass flux and selectivity. In addition, it was aimed to optimize the extraction conditions (extraction time, temperature, agitation speed, strawberry matrix) of Solid-phase microextraction (SPME), which is used for the analysis of strawberry aroma compounds. Optimum results for SPME were obtained at 40&deg / C, 700 rpm for 30 min and no matrix effect was observed. Pervaporation experiments were performed using a hydrophobic membrane, PERVAP 1070 (PDMS). As the feed temperature increased, the mass flux and selectivity increased and the total mass flux followed an Arrhenius type relation. Decreasing downstream pressure increased both total flux and selectivity, while increase in feed concentration led to higher organic fluxes but lower selectivities. In general, PERVAP 1070 showed a higher selectivity towards Methyl butyrate (MTB) than Ethyl butyrate (ETB) and MTB flux was affected negatively by the presence of ETB in the feed solution. Pervaporation experiments were also performed with a strawberry essence and strawberry model solution. The selectivities of MTB and ETB were negatively affected by the presence of other aroma compounds.

ABSTRACT PRECONCENTRATION OF SOME PRECIOUS METALS USING DEBT IMPREGNATED RESIN Refiker, H&uuml / rm&uuml / s M. Sc., Department of Chemistry Supervisor: Prof. Dr. R. Sezer Ayg&uuml / n Co-supervisor: Assoc. Prof. Dr. Melek Merdivan August 2005, 107 pages In this thesis, trace amounts of gold and silver have been determined by flame absorption spectrometry (FAAS) after preconcentration by N,N-diethyl-N&#039 / -benzoylthiourea (DEBT) impregnated resin (Amberlite XAD-16). In the first part of the thesis, sorption behaviours of gold and silver with DEBT impregnated resin under optimized conditions / stirring time, pH, desorption of metals and metal ion capacities of the resin have been studied in batch process. Metal ion capacity of resin is calculated as 0.17 mmol/g resin and 0.104 mmol/g resin for silver and for gold, respectively. In the second part of the thesis, preconcentration of gold and silver was tried by DEBT impregnated resin using column process under optimized conditions / pH, flow rate and volume of sample solution, nature of eluent, flow rate and volume of eluent However, due to partial leaching of DEBT by time, no satisfactory and reproducible results could be obtained. In the final part of the study, metal chelates prepared in aqueous solutions were passed through the column under optimized conditions and satisfactory sorption-desorption and selective preconcentration could be achieved. Under optimized conditions, silver and gold ions at the concentrations of 0.05 &amp / #61549 / g/mL and 0.015 &amp / #61549 / g/mL with preconcentration factors of 7.7 and 6.7, respectively could be determined by FAAS. The proposed method is highly selective without the need for any interference elimination process. Keywords: Precious metals, Solid-phase extraction, DEBT, Amberlite XAD-16

The detection and quantification of biomolecules, and proteins in particular, are of great interest since these molecules are of fundamental importance to our well-being. Body fluids, as for instance human blood, are well suited for sampling of protein levels. However, the complexity of the fluids and the low abundance of many of the interesting biomolecules makes detection and quantification difficult. This has spurred an interest into the development of many protein detection methods, and of these, ligand assays have proven particularly suitable. In this thesis, different types of ligand assays for protein detection have been developed using affibody molecules as ligands. In a first study, a homogeneous competitive detection assay was investigated, based on antiidiotypic affibody molecule pairs and fluorescence resonance energy transfer (FRET) as reporting system. The individual members of two anti-idiotypic affibody pairs, each consisting of a target binding (idiotypic) and an anti-idiotypic affibody ligand, were labeled with a donor fluorophore and an acceptor fluorophore, respectively. Incubation with the two target proteins IgA and Taq DNA polymerase resulted in a concentration dependent decrease in the FRET signal, allowing for target protein detection and quantification. For Taq DNA polymerase, detection in 25% human plasma was also possible in the same concentration span as in buffer. In a second study, a homogeneous, non-competitive detection system was described. Affibody molecules of 58 amino acids directed against IgA and IgG were produced with chemical synthesis, and two fluorophores capable of FRET were site-specifically introduced. Binding of target protein induced a concentration-dependent change in the relative emission of the two fluorophores, which formed the basis for the detection system. In two studies, affibody molecules were evaluated and shown to function well as capture ligands on microarrays. Synthetic affibody molecules directed against Taq DNA polymerase and IgA were modified by the introduction of immobilization tags. Specific immobilization via a C-terminal cysteine or a biotin moiety, or random immobilization via amino groups, were studied in protein microarray experiments and SPR-based biosensor studies. The experiments showed that all immobilization chemistries resulted in functional capture molecules. A short spacer was also introduced, situated between the affibody and the cysteine and biotin moieties, which was shown to improve binding for all constructs. Multidomain affibody constructs of up to four N- to C-terminally linked domains were shown to increase the amount of bound target, compared to monomeric affibody ligands. Six dimeric affibody constructs directed against IgA, IgG, IgE, Taq DNA polymerase, TNF-α and insulin, respectively, showed low limits of detections for their targets and little or no cross-reactivity with the other target proteins. Dimeric affibody molecules directed against IgA and TNF-α were also shown to function in a sandwich format with antibodies for detection of targets in buffer and in human serum and plasma. Successful discrimination between normal and IgA-deficient sera showed that affibody molecules could be used for specific detection of protein in highly complex backgrounds on microarrays. / QC 20100916

One of the poly-Si thin-film cells developed at the University of New South Wales (UNSW) is the EVA cell. In this work, SiN films for EVA cells as an antireflection/barrier coating were investigated. In addition, the effect of hydrogenation pre-treatment of solid phase crystallisation (SPC) on grain size and open-circuit voltage (Voc) was investigated. The SiN films deposited by PECVD were examined for uniformity of the thickness and the refractive index of the films across the position of the samples in the PECVD deposition system. A spectrophotometric analysis was used to determine these film properties. It was found that these properties were very uniform over the deposition area. Good repeatability of the depositions was also observed. A series of SiN film depositions by reactive sputtering were also performed to optimize the deposition process. Parameters adjusted during the deposition were nitrogen flow rate, substrate bias, and substrate temperature. By investigating the deposition rate, refractive index, and surface roughness of the films, the three deposition parameters were optimised. The effects of post SiN deposition treatments (a-Si deposition, SPC, RTA, and hydrogenation) on thickness and refractive index of both SiN films deposited by PECVD and reactive sputtering were investigated by using samples which have the same structure as the EVA cells. The thickness of the PECVD SiN films decreased about 6 % after all the treatments. On the other hand, the thickness reductions of the reactively sputtered SiN films were very small. The refractive index of the PECVD SiN films increased about 0.6 % after the treatments, whereas that of the reactively sputtered SiN films decreased 1.3 % after the treatments. As a possible method to improve the performance of EVA cells, hydrogenation of a-Si was investigated as a pre-treatment of SPC process. There were no obvious differences in the grainsize and the Voc of the EVA cells with and without the hydrogenation. Therefore it is likely that the hydrogenation pre-treatment of SPC does not have a beneficial effect on the performance of EVA cells.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 151-159). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 151-159). Also available on the Internet.

The ability to locate human remains, specifically in a forensic setting, is crucial to investigations. Research in the past two decades has identified volatile organic compounds (VOCs) as the source of the decomposition odor. The study examined the headspace (area directly above) of decomposing remains, Sigma-Aldrich (St. Louis, MO) Pseudo Corpse Scents (formulations one and two), cadaveric blood, and decompositional fluid for target VOCs to which human remains detection (HRD) dogs could indicate. These samples were tested using solid-phase microextraction (SPME) and a gas chromatograph-mass spectrometer (GC/MS) for the exact odor profile and compared to literature about VOCs present in decomposition. The author hypothesized that a series of seven target chemical compounds (carbon disulfide, hexanal, nonanal, dimethyl sulfide, dimethyl disulfide, styrene, and benzoic acid methyl ester) would be present when the headspace of all samples tested. Ideally, a synthetic compound that will better mimic human decomposition odor profile can be created to aid in the training of HRD dogs. There are some disadvantages to using dogs in the field, and the lack of standardization when training HRD dogs is a major one. By examining VOC profiles of different sources of decomposition, a core set of VOCs of human decomposition may be identified to aid in the standardization of training. Of the eight target compounds chosen from the literature, only two were found in any samples tested for this experiment, hexanal and nonanal found in pig heart, deer liver, as well as human muscle and epidermis. Acetic acid was identified in every sample with the exception of the control. Also, in accordance with the literature, putrescine and cadaverine were not found in any of the samples.

104f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-10T12:46:40Z No. of bitstreams: 1 Dissertação.pdf: 828536 bytes, checksum: 3694e4a12f58240a1aaa95041bf6ed2f (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-09T17:35:10Z (GMT) No. of bitstreams: 1 Dissertação.pdf: 828536 bytes, checksum: 3694e4a12f58240a1aaa95041bf6ed2f (MD5) / Made available in DSpace on 2013-05-09T17:35:10Z (GMT). No. of bitstreams: 1 Dissertação.pdf: 828536 bytes, checksum: 3694e4a12f58240a1aaa95041bf6ed2f (MD5) Previous issue date: 2009 / CAPES / O vinho é um produto da fermentação de açúcares naturais presente em suco de uva. É uma bebida amplamente consumida em muitas partes do mundo por milhares de anos, com elevado valor comercial e importância social. Esta dissertação apresenta o desenvolvimento de dois métodos para determinação de metais em vinho. O primeiro descreve a otimização e validação de um método para determinação direta de cádmio em amostras de vinho por espectrometria de absorção atômica com atomização eletrotérmica (ET AAS). A otimização foi realizada empregando um planejamento fatorial completo de dois níveis, incluindo os fatores: tempo (10 s) e temperatura de pirólise (600 oC), temperatura de atomização (1300 oC) e massa de modificador (15 mg). Sob as condições otimizadas, foi encontrada uma massa característica de 0,7 pg, limite de detecção e quantificação de 0,030 e 0,100 mg L-1, respectivamente, para um volume de amostra de 20 mL. A precisão foi de 0,30, 0,37 e 0,49% (RSD) para amostras de vinho com concentrações de cádmio 1,286, 0,266 e 0,356 mg L-1, respectivamente. A exatidão do método de determinação direta empregando ET AAS foi avaliada por comparação usando um método de digestão ácida e determinação também por ET AAS para cinco amostras de vinho. O método foi aplicado para determinação de cádmio em 30 amostras de vinhos Brasileiros. A concentração de cádmio variou de 0,146 a 1,563 mg L-1, cujos valores estão abaixo do nível máximo permitido pela Organização Internacional de vinha e vinho (OIV) e pela legislação Brasileira, 10 mg L-1. No segundo método foram avaliados processos de extração em fase sólida de Cu, Fe, Zn, e Mn em amostras de vinhos, utilizando carvão ativo e resina de troca iônica como adsorventes. As quantificações foram realizadas por FAAS. Com base nos resultados pode-se observar que o carvão ativo demonstrou ser bastante eficiente na extração de Cu, Fe, Zn e Mn em vinho, e que o Cu, Fe e Zn estão na forma de organocomplexos. Já, o Mn presente nas soluções residuais da extração apresentou-se predominantemente na forma iônica. A resina de troca catiônica apresentou uma alta capacidade de sorção para todos os metais avaliados. Entretanto, a resina aniônica apresentou certa afinidade de sorção pelos metais Cu, Fe e Zn. Os limites de detecção para Cu, Fe, Zn e Mn foram 0,02, 0,04, 0,02 e 0,02 mg L-1, respectivamente. Os limites de quantificação para Cu, Fe, Zn e Mn foram 0,08, 0,13, 0,06 e 0,06 mg L-1, respectivamente. A precisão foi expressa como desvio padrão relativo (%RSD), variando de 1,78 a 6,78%, para amostra de vinho com concentrações de 0,13, 3,33, 0,36 e 1,52 para Cu, Fe, Zn e Mn, respectivamente. Esta avaliação foi feita para seis amostras de vinhos brasileiros. / Salvador

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-22T14:14:47Z No. of bitstreams: 1 Alailson Dantas.pdf: 1207742 bytes, checksum: dd96111e79eb0488c462e0a90329ca1a (MD5) / Made available in DSpace on 2013-04-22T14:14:47Z (GMT). No. of bitstreams: 1 Alailson Dantas.pdf: 1207742 bytes, checksum: dd96111e79eb0488c462e0a90329ca1a (MD5) Previous issue date: 2004 / O presente trabalho propõe o estudo da utilização da cuproína na separação, preconcentração e determinação de cobre por espectrofotometria de absorção molecular em solução e espectrofotometria de absorção molecular em fase sólida. Em uma primeira etapa, estudou-se um sistema para espectrofotometria em solução, sendo que o cátion cobre (I) reage com a cuproína em pH 4,8 formando um complexo rosa, estável por cerca de 48 horas, com absorvância máxima em 545 nm e absortividade molar e = 6,25x103 L.mol-1.cm-1, contra um branco do reagente. A reação de complexação ocorre na presença de hidroxilamina, etanol, do tensoativo Triton-X100 e de EDTA. A determinação do cobre é possível numa faixa linear dinâmica que vai de 0,2 a até 5,0 mg.L-1, com um limite de detecção de 0,05 mg.L-1. A principal vantagem do procedimento sugerido é à eliminação da etapa de extração líquido ? líquido ou a eliminação da utilização de solventes orgânicos tóxicos, como dimetilformamida (DMF), para dissolução da cuproína. Em uma segunda etapa, estudaram-se três sistemas para separação, preconcentração e determinação de cobre por espectrofotometria em fase sólida, utilizando sílica funcionalizada C18 modificada com cuproína para retenção do quelato Cu(biq)2+, na presença de hidroxilamina e tampão acetato pH 4,8. As três metodologias propostas envolvem sistemas de análise por injeção em fluxo (FIA) com injetores e celas de fluxo artesanais, tornando os procedimentos rápidos, sensíveis, baratos e com baixo consumo de reagentes e baixa produção de resíduos. Estes estudos envolveram a comparação entre uma cela axial e uma cela plana, onde a primeira mostrou-se mais sensível, porém com muitos problemas de vazamento em função da alta impedância hidrodinâmica. Houve também a comparação das soluções de tiouréia/tampão acetato e Fe(III) / HCl como eluentes do Cu(I) retido na fase sólida modificada cuproína-C18 em uma cela plana. A solução ácida de Fe(III) mostrou-se mais eficiente que a tiouréia, pois não deixava resíduos e aumentava a vida útil da fase sólida modificada. / Salvador

Os contaminantes emergentes são considerados compostos onipresentes em águas, portanto investigar a degradação e comportamento dessas substâncias torna-se necessária, pois é reportado que estes compostos causam efeitos adversos em seres vivos. O composto 2-(tiocianometiltio) benzotiazol (TCMTB), considerado um contaminante emergente, é amplamente empregado na indústria do couro como biocida com a finalidade de inibir o desenvolvimento de microrganismos na pele. Sendo assim, o objetivo do presente trabalho foi estudar a degradação do contaminante emergente TCMTB, por meio das técnicas de fotólise direta com radiação UV, radiação solar e oxidação com ozônio. Experimentos de fotólise direta do TCMTB, em soluções aquosas com diferentes concentrações, em efluente do processo de remolho e efluente simulado do remolho, foram conduzidos em reator com lâmpada de vapor de mercúrio (250 W). O teste de hidrólise foi realizado protegido da luz, a temperatura ambiente com diferentes concentrações do TCMTB para observar o comportamento do contaminante na ausência de luz. O maior coeficiente de absorção molar foi medido e identificado em 220 e 280 nm como 20489 e 11317 M-1 cm-1, respectivamente, para pH 5,0. Os resultados experimentais da fotodegradação mostraram que TCMTB foi rapidamente degradado por fotólise direta em soluções aquosas em 30 min de tratamento fotolítico. Os resultados do estudo do pH, demonstraram que pH interfere no processo fotoquímico, uma vez que em condições alcalinas o composto é mais estável e a taxa de fotodegradação diminui. Os ensaios com o efluente do processo de remolho mostraram que a degradação do TCMTB tem comportamento semelhante às soluções aquosas. O efluente simulado do remolho mostrou que uma alta concentração do contaminante leva a um maior tempo de irradiação de luz para a degradação. A aplicação de luz natural evidenciou degradação mais lenta, mas ainda assim, foi possível observar degradação de até 96% para a concentração de 6 mg L-1 em 420 min. A utilização do oxidante ozônio como tratamento, alcançou 40% de remoção do contaminante em 30 min, assinalando a alta estabilidade do composto. Portanto, este trabalho aponta o potencial do uso de fotólise direta (luz v artificial), ou radiação solar (luz natural) para a degradação de contaminantes emergentes como o 2 (tiocianometiltio) benzotiazol (TCMTB). / Emerging contaminants are considered omnipresent compounds in water, thus investigate the degradation and behavior of these substances becomes necessary as it is reported that these compounds cause adverse effects on living beings. The 2- (thiocyanomethylthio) benzothiazole compound (TCMTB), considered an emerging contaminant, is widely used in the leather industry as a microbicide for the purpose of inhibiting the development of microorganisms in the skin and leather. In this context, the purpose of the present work was to study the degradation of the emerging contaminant TCMTB by direct photolysis with UV radiation, solar radiation and ozone. Experiments of direct photolysis of the TCMTB in aqueous solutions with different concentrations, in the effluent from the soaking process were conducted in a reactor with mercury vapor lamp (250 W). The hydrolysis test was performed protected from light at room temperature with different concentrations of TCMTB to observe the behavior of the contaminant in the absence of light. The highest molar absorption coefficient was measured and identified at 220 and 280 nm as 20489 and 11317 M-1 cm -1, respectively, at pH 5.0. The experimental results of photodegradation showed that TCMTB was rapidly degraded by direct photolysis in aqueous solutions in 30 min of photolytic treatment. The results of the pH study showed that pH interfered in the photochemical process, since under alkaline conditions the compound is more stable and the photodegradation rate decreases. Assays of the direct photolysis in effluent from the soaking process have shown that TCMTB degradation behaves similarly to aqueous solutions. The direct photolysis of the the simulated effluent from the soaking showed that a high concentration of the contaminant leads to a longer time of light irradiation for degradation. The application of natural light evidenced slower degradation, however, it was possible to observe degradation of up to 96% for the 6 mg L-1 concentration with 420 min. The use of the ozone oxidant as a treatment, achieved 40% removal of the contaminant for 30 min of treatment, indicating the high stability of the compound. Therefore, this work highlights the potential of the use of direct photolysis (artificial light), or solar radiation (natural light) for the vii degradation of emerging contaminants such as 2 (thiocyanomethylthio) benzothiazole (TCMTB).