Made available in DSpace on 2014-06-11T19:29:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-02-18Bitstream added on 2014-06-13T20:18:58Z : No. of bitstreams: 1 ferreira_rb_me_araiq.pdf: 771766 bytes, checksum: b69fe2b81286a33e730050f8930f9fab (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Foi desenvolvido um método para a determinação espectrométrica de fósforo em insumos agroindustriais. O método está baseado na determinação por Espectrometria de Absorção atômica com Fonte Contínua de Alta Resolução (HR-CS AAS) utilizando a linha atômica 213,618 nm e bandas de 246,400 nm e 324,616 nm. Foram estudadas as melhores condições para a análise via absorção pelas bandas de PO e da linha de P atômica. Para a primeira, a melhor forma de análise foi utilizar a chama oxidante ar / acetileno, já para a última situação a atomização foi pela utilização de uma chama oxidante de acetileno / óxido nitroso. As melhores condições de funcionamento, tais como altura do queimador, fluxo de gases e taxa de aspiração da amostra foram definidas, sendo seus valores ideais para cada comprimento de onda respectivamente: 246,400 nm (9 mm – 0,186 – 5 mL min-1), para 324,616 nm (8 mm – 0,170 – 5 mL min-1) e de 213,618 nm (4 mm – 0,450 – 5 mL min-1). Boa linearidade foinobtida para o intervalo de concentração 250 – 4000 mg L-1 P usando o modo de integração do sinal de absorbância CP ± 2 (5 pixels), utilizando-se os sais Na2HPO3.5H2O, NaH2PO4, NH4H2PO4 e H3PO4. Os resultados mostraram que era irrelevante a natureza dos compostos para obter um padrão de P. Quatro diferentes modos de integração de absorbância foram avaliados: CP ± 1 (3 pixels), CP ± 2 (5 pixels), CP ± 3 (7 pixels) e CP ± 4 (9 pixels). Foi observado que a sensibilidade (inclinação da curva e massa característica) melhoraram com o aumento do número de pixels. O método de determinação de P pelo HR-CS FAAS em insumos agroindustriais foi comparada com a titulação. A exatidão e precisão foram de acordo com 95% de confiança, o desvio padrão relativo (RSD) obtido foi de 2,0%. Boas recuperações, cerca de 98%, foi obtida a partir de testes de adição e recuperação. / It was developed a method for spectrometry determination of phosphorus in agroindustrial products. The method is based on the determination by high-resolution continuum source flame atomic absorption spectrometry technique (HR-CS FAAS) using the atomic line 213,618 nm and bands of 246,400 nm and 324,616 nm. It was studied the best conditions for the analysis, for the absorption by bands of PO and the line of P atomic. To the first the best form of analysis would be using an oxidizing air/acetylene flame for analyte atomization and the last an oxidizing acetylene/nitrous oxide flame. The best operating conditions was defined as the burner high, the gas flow rate and aspiration rate of the sample. The values for these operations conditions are respectively: to 246,400 nm ( 9 mm – 0,186 – 5 mL min-1), to 324,616 nm ( 8 mm – 0,170 - 5 mL min-1) and to 213,618 nm ( 4 mm – 0,450 - 5 mL min-1). Good linearity was obtained for the concentration range 250 – 4000 mg L-1 P using the wavelength integrate absorbance in CP ± 2 (5 pixels), using the salts Na2HPO3.5H2O, NaH2PO4, NH4H2PO4 e H3PO4. The results showed that the was irrelevant to the nature of the compound to obtain a standard of P. Four different wavelength integrated absorbance were evaluated: CP ± 1 (3 pixels), CP ± 2 (5 pixels), CP ± 3 (7 pixels) and CP ± 4 (9 pixels). It was observed that the sensitivity (slope and characteristic mass) improved with increased number of pixels. The method of analysis of P by HR-CS FAAS in agroindustrial products was compared with the titration. The accuracy and precision was agreement at 95% confidence level, the relative standard deviation (RSD) obtaneid was 2,0%. Good recoveries, about 98%, was obtained using test of addition and recovery.

Made available in DSpace on 2014-06-11T19:29:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-07-13Bitstream added on 2014-06-13T19:17:24Z : No. of bitstreams: 1 sousa_wr_me_araiq.pdf: 1471121 bytes, checksum: 02a8f19f5f1305b98fe374ef6264bb94 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho consiste na avaliação dos parâmetros cinéticos (E, A, f(a)) relativo à decomposição térmica do nitrato de níquel hexahidratado isolado e em presença de carbeto de tungstênio, de grafite, e de carbeto de tungstênio mais grafite, a partir da utilização de métodos não isotérmicos na avaliação de dados obtidos por análise termogravimétrica (TG). Identificação dos resíduos de decomposição térmica de nitrato de níquel e de suas misturas com ligantes orgânicos (ácido oxálico, ácido cítrico, ácido etileno diaminotetraacético (EDTA), ácido ascórbico e sacarose) em suporte de alumina e em presença de carbeto de tungstênio, de grafite, e de carbeto de tungstênio mais grafite, através de cálculos com dados e comportamento térmico obtidos das curvas TG sob atmosfera inerte e por análise de difração de raios - X (método do pó). Os resultados mostram que para a decomposição do nitrato de níquel puro e em presença de WC (carbeto de tungstênio), grafite, WC e grafite o modelo cinético que melhor se aplica em toda extensão é o modelo ESTÁK - BERGGREN ou autocalitico (SB), porém até aproximadamente 50% o processo pode ser governado por nucleação/crescimento, modelo Johnson - Mehl - Avrami - Erofeev - Kolgomorov (JMAEK). A presença de ligantes orgânicos influência de forma diferente na decomposição térmica no nitrato de níquel com formação de resíduos favorecendo ou não a formação de Ni0, NiO ou NiWO4; em complemento podem proteger ou favorecer a oxidação de WC por oxigênio residual. / Not available.

Made available in DSpace on 2014-06-11T19:29:09Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-12-21Bitstream added on 2014-06-13T19:58:47Z : No. of bitstreams: 1 carvalho_gc_me_araiq.pdf: 2780066 bytes, checksum: 373166ff1df7c9a7a4eec770d434e0a1 (MD5) / Este trabalho teve como objetivos a validação do método analítico para determinação do pH em águas, o levantamento das fontes prováveis de incerteza e a estimativa da incerteza associada ao resultado da medição. A abordagem foi desenvolvida com vistas à melhoria do processo analítico e à adoção de medidas preventivas, buscando-se, ao final desta etapa, repassar o conhecimento obtido, para o corpo técnico da empresa OIKOS: Controle Ambiental Ltda., e atender aos requisitos da norma ABNT NBR ISO/IEC 17025: 2005. Durante os experimentos o sistema de medição foi calibrado / ajustado utilizando-se: pH 7,00 e pH 4,00 (para leitura na faixa ácida) ou pH 7,00 e pH 10,00 (para leitura na faixa alcalina); e utilizou-se padrões rastreáveis ao NIST para a comparação. Foram obtidos os parâmetros: 1- precisão por repetitividade; precisão intermediária variando-se dias, equipamento e analista; a reprodutibilidade foi avaliada a partir da participação em ensaios de proficiência (EP) promovidos pelo INMETRO: pH 4,00 e pH 6,86. O laboratório apresentou desempenho satisfatório nestes ensaios, apresentando bom índice z em ambos, sendo que no segundo EP a precisão pôde ser melhorada. O método em estudo também apresentou 2- exatidão, obtida por meio da comparação entre o valor médio determinado e o valor aceito como verdadeiro, neste caso, o pHnominal disponibilizado no certificado do material de referência (MRC); 3- linearidade (Y-Yo); e 4- sensibilidade, em função da pendente de Nerst, considerando a temperatura média no dia de trabalho. Para a estimativa da incerteza foram consideradas as fontes de incerteza: i- precisão por repetitividade (maior valor de sr); ii- determinação do pH, obtida da regressão linear; iii- do potenciômetro; e iv- dos materiais de referência certificados utilizados... / This work aims the validation, the survey of likely sources of uncertainty, its estimate, the calculation of uncertainty and expanded uncertainty of quantitative analytical methods related to measures of pH in waters. This approach was developed to improve the analytical process, seeking the fitness of methods for use, recognizing the possible adoption of preventive measures, as well as the adequacy of the laboratory and analytical methods in compliance with the requirements of ABNT ISO/IEC 17025:2005. This work was undertaken in partnership with the company OIKOS Environmental Control Ltda. seeking, at the end of this step, pass on the knowledge obtained for the company's technical team. During the experiments, the calibration / adjustment of the measuring system were done using: pH 7.00 and pH 4.00 (for reading in the acid range) or pH 7.00 and pH 10.00 (for reading in the alkaline range); and traceable to NIST standards were used for comparison. The performance parameters obtained were: the: 1- repeatability; intermediate precision varying the conditions: day, equipment and analyst; and finally, reproducibility was evaluated from the participation in proficiency testing (EP) pH 4.00 and pH 6.86 promoted by INMETRO. The laboratory showed satisfactory performance in these trials, showing good z-index in both tests, but in the second EP, the “precision” was improved... (Complete abstract click electronic access below)

Volatile organic compounds (VOCs) are the key aroma producers in fruits and sensory quality of fruits is widely determined by qualitative and quantitative composition of VOCs. The aroma of grape is a complex of hundreds of VOCs belonging to different chemical classes like alcohols, esters, acids, terpenes, aldehydes, furanones, pyrazines, isoprenoids and many more. VOCs play important role as they determine the flavor of grapes and wine made from it. The objective of this thesis is to study of VOCs through development of different mass spectrometry based analytical methodologies and its applications for the comprehensive investigation and construction of database of the VOCs in grapes. First part of the study was dedicated to generation of the comprehensive database of grape VOCs through the screening of multiple grape varieties (n=124) representing different species, color and origin. The experiment was carried out using headspace solid-phase microextraction (HS-SPME) and gas chromatography mass spectrometry (GC-MS) based approach and according to metabolomics protocols. A customized dataset of reference standards (>350) was generated and, an automated pipeline for data analysis was created in collaboration with data management group of the institute. The results showed annotation of “level 1†of 117 VOCs in grape. The established database in this experiment will represent the significant portion of the future Grape Metabolome database. The second part of the study was dedicated to study the differential behavior of volatile organic compounds and their glycosylated precursors qualitatively and semi quantitatively. Volatile secondary metabolites also exist in the form of nonvolatile and odorless glycosylated precursors in grape and studies have confirmed that concentration of these precursors can be much higher than its free counterparts. The elevated concentrations of volatiles in glycosylated forms can significantly affect the wine aroma because of possible chemical modifications throughout the process of fermentation and wine ageing. In addition, the investigation of the biosynthesis and accumulation of VOCs in the fruit tissues requires the consideration of both the free and bound forms. To study the phenomenon an experiment was carried using solid phase extraction (SPE) of the free and glycosylated precursors; with enzymatic hydrolysis aglycone part of the precursors was released followed by subsequent GC-MS analysis. Over 10 different selected grape varieties were analyzed. Sixty-six significant different aroma compounds in grapes (pre and post hydrolysis) were identified. Identification was done based on several parameters like retention time, retention index and MS spectral database. The multivariate statistical analysis by two-way hierarchical clustering with heat map visualization showed distribution of the compounds within different varieties before and after hydrolysis. In the third part of the study, we performed experiments dedicated to training and applications of atmospheric pressure gas chromatography mass spectrometry (APGC-MS). The experiment was carried out at the Department of Biological Sciences, University of North Texas, under the supervision of Prof. Vladimir Shulaev. We have established the metabolomics protocol for the analysis of fruit volatiles using APGC-MS with an optimized GC and MS conditions and created novel library of the fruit volatile compounds using APGC-MS system. Six different grape varieties were analyzed as a case study and experimental results showed APGC-MS as a valuable solution for metabolomics analysis. The data processing and statistical evaluation was done using XCMS and progenesis QI© software. Moreover, observations based on injections of pure reference standards showed high abundance of molecular ions with minimal fragmentation at low collision energy that is typically missing in traditional vacuum source GC-MS. Moreover, the use of elevated collision energy data resulted in a spectrum similar to the traditional EI data.

Cell membrane is the biological barrier serving as both territorial defense and the communication hinge for the interior of cell from its surroundings. As building blocks of cellular membranes and also precursor for second messengers, a variety of lipids play essential roles in cellular membrane dynamics as well as important functions such as cell proliferation, apoptosis, signal transduction and membrane trafficking modulation. Lipidomics, representing the systematic and integrative studies of diversified lipids (lipidome) in a biological system, is an emerging yet rapid developing field and hence requires advanced and complementary analytical techniques as well as multiple statistical tools. Our development of reliable analytical methodology (the advanced Mass Spectrometric and high-resolution NMR techniques) and application of multiple statitistical approaches (multivariate data analysis and univariate t-test) enable us to achieve these comprehensive understandings. We have investigated, first of all, the effects induced by hypoxia on cervical cancer derived cells (HeLa cells) to see how and how much the changes in phospholipids profile are able to get light into the targeted biological problem (hypoxia) and provide a preliminary insight into the underlying mechanisms. We found that hypoxia stimulation dramatically reduced the total amount of cellular phosphoinositols (PI) but prominently increased the amount of lyso phosphocholines (lyso-PC) and lyso phosphoethanolamines (lyso-PE). Moreover, our studies suggested the polyunsaturated phospholipids species as stronger biomarkers upon hypoxia treatment. The evaluation of changes in the average unsaturation index (UI) of the membrane lipids acyl chains revealed that UI slightly increased in several lipid classes, thus affecting membrane fluidity and further membrane-dependent functions. The plausible mechanisms by HeLa cells to adapt to hypoxia conditions are briefly reported as well. We have also conducted the comparative lipidomic studies of urothelial cancer cell line RT4 (a model system of a benign tumor) and T24 (a model system of a metastatic tumor) aiming to reveal probable roles and relevant differential changes of membrane lipids with respect to urinary bladder metastasis progress. Significant changes of lipids metabolism were found to correlate with urothelial nonmetastatic and metastatic cell models. The most remarkable finding was that the malignant cell type (T24) showed a strong decrease of ether PC species complemented by a sharp increase of the length and the average unsaturation number of lipids acyl chains. Ceramide-based sphinglipids also showed altered profiles in these two cell types. Such analyses suggest a certain significant re-organization of cellular membrane in malignant cell transformation, involving variations in compositional lipid structures and possible signaling transduction pathways. Observations of such reduction of the 1-alkyl PC species and the chain shortening of lipid species might serve as a tool in urinary bladder cancer intervention.

This PhD project arises from the growing awareness of food quality and safety on the part of citizens and institutions. The increase in the population to feed, the lengthening of the production and distribution chains and the socio-economic risks of a poor diet make it crucial to monitor the quality of food from the producer to the consumer. Traditional methods (sensory panels and laboratory analytical techniques) are too expensive and above all slow to evaluate the quality of fresh foods that deteriorate over the course of a few hours. In this context, it is crucial to develop monitoring devices that are cheap, rapid and non-invasive, in order to be able to evaluate the quality of food products extensively and constantly. Solid-state gas sensors are an ideal candidate, as they are inherently non-invasive and inexpensive. In this context, the project focused on chemoresistive sensors based on semiconductor metal oxides, which are among the simplest and most performing, and have the advantage of being sensitive to almost all gases and VOCs. Initially, nanostructures of different materials (n- and p-type semiconductors) and of different morphologies (nanowires and nanosheets) were studied in order to investigate the performance of individual sensors. In this way, some devices have been optimized with respect to the detection of possible biomarkers of the degradation of specific foods. The sensors have demonstrated a rapid response (from a few seconds to a minute), an intense response and above all a very low detection limit (less than 1ppmv, in some cases a few tens of ppbv), important for agri-food applications. This approach is the simplest since it requires a single sensor that is selective towards a certain molecule (ammonia, ethylene...) which can be considered the only important information parameter in a certain application. In most cases, however, the gaseous emission of a food is composed of a large quantity of volatile compounds, and the low selectivity of resistive sensors makes it difficult to discriminate the molecules most informative regarding the degradation process. For this reason, in the second part of the PhD we used the sensors developed up to then to create electronic noses. Exploiting the dimensions of nanostructures, we have developed a new concept of thermal electronic nose, i.e. with sensors of the same material, but within a thermal gradient. In this way, by exploiting multivariate statistical analysis and machine learning techniques, the devices acquired a greater ability to discriminate and quantify the different gases. The electronic noses have shown that they can perfectly recognize the different gases tested (100%) and estimate their concentration with an error of a few ppmv. Measurements in the laboratory are very useful for testing the performance parameters of sensors and electronic noses, as they make it possible to evaluate the correctness of the classification and the error in estimating the concentration of any gas. On the other hand, measuring the emissions of fresh food is different, as the concentrations are not known, and therefore a different approach is needed. The final stage of the project involved using electronic noses to assess the freshness of certain agri-food products. As the developed sensors were particularly sensitive to ammonia, it was decided to study the degradation of meat and fish, where this gas is an important marker. The electronic noses have been able to accurately recognize the meat from the fish (> 95%), and evaluate the state of degradation by giving a very accurate estimate of the microbial count (>95%), responding in a very short time (tens of seconds). The miniaturized electronic noses developed during this PhD project have therefore successfully demonstrated to be a rapid and non-invasive cross-sectional tool for assessing the freshness of agri-food products.

Neste trabalho foi desenvolvido um sistema de pré-concentração em fase sólida de íons urânio acoplado ―on-line‖ à espectrofotometria. O método baseia-se na pré-concentração de urânio sobre nanotubo de carbono oxidado com ácido nítrico, com posterior eluição com ácido clorídrico 0,32 mol L-1 e reação com arsenazo III, sendo a absorbância do complexo monitorada em 650 nm. A triagem dos fatores pertinentes ao sistema foi efetuada por meio de planejamento fatorial de dois níveis, enquanto que a otimização foi realizada usando planejamento Doehlert. As condições otimizadas foram: pH da amostra (3,75); concentração do tampão (6,80x10 -3 mol L-1); concentração do arsenazo III (0,08% m/v); concentração do eluente (0,32 mol L-1); tipo de eluente (HCl) e vazão de pré-concentração (7,20 mL min-1). Para o estudo de interferentes realizou-se a determinação de urânio por meio de soluções binárias nas seguintes proporções, 1:1; 1:10; 1:100 (m/m), analito/interferente, respectivamente. Os íons de estudo foram: Th4+, Mn2+, Ni2+, Co2+, Cu2+, Fe3+, Cr3+, Cd2+, Zn2+, Pb2+, sendo que os dois últimos apresentaram interferência na proporção de 1:10. A precisão (n=10) foi avaliada para padrões de 10,0 e 100,0 μg L-1 rendendo desvios padrão relativos de 3,27 e 2,56%, respectivamente. O método apresentou fator de pré-concentração de 228 vezes e respectivos limites de detecção e quantificação de 0,21 e 0,7 μg L-1. A exatidão do método foi avaliada a partir da análise de amostras de água de diferentes fontes, bem como água do mar simulada. / In this work a solid phase preconcentration system of uranium on-line coupled to spectrophotometry was developed. The method is based on preconcentration of uranium on carbon nanotube oxidized with nitric acid, with further elution with 0.32 mol L-1 hydrochloric acid and reaction with Arsenazo III, being the absorbance of the complex monitored at 650 nm. The screening of the factors relevant to the system was carried out from two level factorial design while the optimization was performed using Doehlert design. The following conditions were optimized: sample pH (3.75), buffer concentration (6.8x10-3 mol L-1), Arsenazo III concentration (0.08% w/v) concentration eluent (0.32 mol L-1), type of eluent (HCl) and preconcentration flow rate (7.2 mL min-1). For the study of interfering held the determination of uranium by means of binary solutions in the following ratios, 1:1; 1:10; 1:100 (m/m) analyte/interferent, respectively. The ions study were: Th4+, Mn2+, Ni2+, Co2+, Cu2+, Fe3+, Cr3+, Cd2+, Zn2+, Pb2+, where the two latter showed interference in the 1:10 proportion. The precision (n=10) was evaluated for the standards 10.0 and 100.0 μg L-1 yielding relative standard deviations of 3.27 and 2.56%, respectively. The method presented preconcentration factor of 228 and respective detection and quantification limits of 0.21 and 0.7 μg L-1. The accuracy of the method was assessed from analysis of water samples from different sources as well as simulated seawater. / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq

Neste trabalho, propomos o estudo dos mecanismos de adsorção de um novo material adsorvente capaz de extrair íons metálicos, obtido através da modificação química de nanotubos de carbono (CNT) com o emprego de agente oxidante ácido, seguido do revestimento com uma camada externa de albumina de soro bovino (BSA), resultando em nanotubos de carbono de acesso restrito revestidos com BSA (RACNT-BSA). Os materiais foram caracterizados por: análise termogravimétrica (TG/DTG) a fim de avaliar a estabilidade térmica, espectroscopia no infravermelho (IR) para confirmação dos grupos funcionais envolvidos nos processos oxidação dos CNT e recobrimento dos mesmos com BSA, análise elementar (CHN), microscopia eletrônica de varredura (MEV) para avaliar a morfologia e difração de raio-X. Para facilitar a compreensão dos mecanismos de interações entre os RACNT-BSA com BSA em solução e com íons metálicos, determinaram-se os pontos isoelétricos de todos os materiais. Para o estudo dos possíveis mecanismos de interação entre os RACNT-BSA e proteínas em solução, percolou-se soluções de BSA com concentração 3 μg. mL-¹ em tampão fosfato com pH no intervalo de 2,2 a 7,0 nos RACNT-BSA. Dessa maneira, verificou-se uma relação entre o processo adsortivo nos RACNT-BSA e o pI (ponto isoelétrico) das proteínas, ou seja, propomos um mecanismo para o funcionamento dos RACNT-BSA dependente do pH da solução e das proteínas a serem percoladas. Quando uma solução de proteínas é percolada através de um cartucho de SPE contendo RACNT-BSA e o pH da solução é maior do que o ponto isoelétrico das proteínas, ambas as proteínas solubilizadas e a camada de BSA são ionizadas negativamente. Assim, uma repulsão eletrostática impede a interação entre as proteínas da amostra e a superfície do RACNT-BSA. Verificou-se que os íons metálicos podem ser adsorvidos nos RACNT-BSA, porém os processos adsortivos são afetados quanto a variação do pH da solução e a escolha do tampão adequado. Também se estudou a extração dos íons Fe das estruturas das proteínas da catalase. Quanto à aplicação para a catalase, verificamos que ao mesmo tempo em que não há adsorção desta proteína nos RACNT-BSA, os íons Fe, ligados covalentemente à ela, são atraídos e adsorvidos nos RACNT-BSA, sendo necessário, porém a desnaturação proteíca. Isto nos mostrou que o material RACNT-BSA se mostrou promissor para a formação de apoproteínas. / In this work, we proposed to study the adsorption mechanisms of a new adsorbent material capable of extracting metal ions, obtained by chemical modification of carbon nanotubes (CNT) with the use of oxidizing acidic agent, followed by coating with an outer layer of bovine serum albumin (BSA), resulting in restricted access of carbon nanotubes coated with BSA (RACNT-BSA). The materials were characterized by thermogravimetric analysis (TG) in order to evaluate thermal stability, infrared spectroscopy (IR) to confirm the functional groups involved in the oxidation processes of CNT and covering the same with BSA, elemental analysis (CHN), scanning electron microscopy (SEM) to evaluate the morphology and powder X-ray diffraction. To facilitate the understanding of the interaction mechanisms among RACNT-BSA and BSA in solution and metal ions, the isoelectric points (Ip) (isoelectric point) of all materials were determined. To study the possible interaction mechanisms between RACNT-BSA and solubilized proteins, the BSA solutions (3 μg. mL-¹) in phosphate buffer with a pH in the range 2.2 to 7.0 were percolated through the RACNT-BSA. Thus, there is a relationship between the adsorptive process in the RACNT-BSA and the protein Ip’s, i.e., we proposed a working mechanism for RACNT-BSA dependent on the pH solution and on the type of percolated protein. When a protein solution is percolated through a SPE cartridge containing RACNT-BSA and the pH solution is higher than the protein Ip, both solubilized protein and BSA layer (from RACNT-BSA) are negatively ionized. Therefore, an electrostatic repulsion prevents the interaction between the solubilized proteins and the surface of RACNT-BSA. It was found that metal ions can be adsorbed on RACNT-BSA, but the adsorptive processes can be affected according the changing of pH solution, and the choice of the appropriate buffer. The application to catalase protein, we found that while there is no adsorption of this protein on RACNT-BSA, the Fe ions, covalently linked to it, are attracted and adsorbed on RACNT-BSA, requiring, however, the denaturation of protein. These results showed us that the RACNT-BSA material is promising for the apoprotein’s formation. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES

Submitted by Jaqueline Silva (jtas29@gmail.com) on 2014-10-06T18:08:43Z No. of bitstreams: 2 Dissertação - Thaíza Carvalho da Rocha - 2012.pdf: 1513291 bytes, checksum: 5cdef676b716525fc5590bddb862c72f (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Jaqueline Silva (jtas29@gmail.com) on 2014-10-06T19:16:52Z (GMT) No. of bitstreams: 2 Dissertação - Thaíza Carvalho da Rocha - 2012.pdf: 1513291 bytes, checksum: 5cdef676b716525fc5590bddb862c72f (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2014-10-06T19:16:52Z (GMT). No. of bitstreams: 2 Dissertação - Thaíza Carvalho da Rocha - 2012.pdf: 1513291 bytes, checksum: 5cdef676b716525fc5590bddb862c72f (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2012-05-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Thermal analysis techniques have been very useful to study the pre-formulations since it consists in techniques that can provide quick and reliable results. This study evaluated the thermoanalytical profiles of psoralen and bergapten, compounds used in the treatment of vitiligo, and their interactions with excipients. We also evaluated the thermal profile of the plant extract Brosimum gaudichaudii Trécul (Moraceae) and a medicine containing the same extract. The results showed that psoralen and bergapten are substances with decomposition and have only one melting step at 162 ° C and 190 respectively. The compounds psoralen and bergapten interact with each other, but the results by XRD clearly show that the crystal structures of the compounds are not affected by these interactions. Furthermore, the results of thermal analysis showed that there was no interaction with the excipients of these compounds under study. All results were confirmed by FT-IR, used as a complementary technique. The plant extract showed an endothermic event which can be attributed to the fusion of these assets. The DSC curve profile of the drug trade allowed the detection of lactose in their composition, whose presence is not included in the package leaflet. / As técnicas de análise térmica tem se mostrado muito úteis no estudo de pré-formulações visto que consiste em técnicas que apresentam resultados rápidos e seguros. Neste trabalho foram avaliados os perfis termoanalíticos do psoraleno e bergapteno, compostos utilizados no tratamento de vitiligo, e suas interações com excipientes. Avaliou-se também o perfil térmico do extrato da planta Brosimum gaudichaudii Trécul (Moraceae) e de um medicamento contendo o mesmo extrato. Os resultados mostraram que psoraleno e bergapteno são substâncias que possuem decomposição em apenas uma etapa e apresentam fusão em 162 e 190 °C, respectivamente. Os compostos psoraleno e bergapteno interagem entre si, mas os resultados através de DRX deixam claro que as estruturas cristalinas dos compostos não são afetadas por essas interações. Além disso, os resultados obtidos com a análise térmica evidenciam que não ocorreu nenhuma interação destes compostos com os excipientes em estudo. Todos os resultados foram confirmados por FT-IR, utilizada como técnica complementar. O extrato da planta mostrou um evento endotérmico que pode ser atribuído à fusão dos ativos presentes. O perfil da curva DSC do medicamento comercial possibilitou a detecção da lactose em sua composição, cuja presença não consta na bula do medicamento.

Made available in DSpace on 2014-08-13T14:50:39Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-03-01Bitstream added on 2014-08-13T18:01:29Z : No. of bitstreams: 1 000747100_20150301.pdf: 781780 bytes, checksum: 17a6575811150f77e56c55b45e901e6b (MD5) Bitstreams deleted on 2015-03-03T12:45:17Z: 000747100_20150301.pdf,Bitstream added on 2015-03-03T12:45:54Z : No. of bitstreams: 1 000747100.pdf: 1832373 bytes, checksum: e90900cd2fd8776fe0cd6e6e2e7b06a4 (MD5) / As tinturas de cabelo representam uma importante área da indústria cosmética e são usadas por 50% da população feminina mundial. Nos anos mais recentes houve uma crescente preocupação com as regulamentações do uso e do limite permitido para estes compostos devido a efeitos dermatológicos, mutagênicos e cancerígenos e associados ao seu uso. Como consequência as demandas por métodos analíticos confiáveis para o controle do nível estabelecido dos corantes em meio aquoso são extremamente importantes. Diante disso, o presente trabalho descreve a construção e caracterização de dois eletrodos desenvolvidos pela modificação com materiais nanoestruturados (TiO2 e NTC). No caso dos eletrodos modificados com nanotubos de TiO2, estes foram crescidos sobre placas de Ti como substrato e sua aplicação na identificação e quantificação do corante de cabelo Marrom Básico 17 em águas de torneira usando a técnica de voltametria de varredura linear. Já os Nanotubos de Carbono de Parede Múltiplas foram usados na modificação de um eletrodo de carbono vítreo e aplicados na determinação do corante de cabelo Verde Ácido 25 em meio aquoso. Para o corante Marrom Básico 17, foi obtida uma curva analítica no intervalo de concentração de 1,0 x 10-6 a 1,0 x 10-4 mol L-1, seguindo a equação: Ip (mA) = 47,7 mA/mol L-1 [MB - 17] – 2,8 x 10-6 mA, r= 0.9952, n=7. O limite de detecção (LOD) e quantificação (LOQ) foi de 1,3x10-7 mol L-1 e 4,4x10-7 mol L-1, respectivamente. O método foi aplicado em água de torneira contaminada fortificada com 12 mg L-1 do corante e submetida á análise usando o método de adição de padrão. A média de recuperação (n=5) foi 99,4 ± 1,4%. Para o corante Verde Ácido 25 uma curva analítica foi construída usando voltametria de onda quadrada no intervalo de 1,0x10-7 a 2,0x10-6 mol L-1 e pré-acúmulo de 10 min, seguindo a equação: Ip = 42,7 μA/mol L-1 [VA - 25] – 5,1 x 10-6 μA, r = 0,9998... / The hair dyes represent an important area of the cosmetic industry and are used by 50% of the female population worldwide. In recent years there has been a growing concern with the use regulations and the permitted limit for these compounds due to dermatological effects, mutagenic and carcinogenic and associated with its use. As a result the demand for reliable analytical methods for the control of the level of dyes in aqueous media are extremely important. Thus, the present work describes the construction and characterization of two electrodes developed by modification with nanostructured materials (TiO2 and CNT). In the case of electrodes modified with TiO2 nanotubes, these were grown on plates as Ti substrate and its application in the identification and quantification of hair dye Basic Brown 17 in tap water using the technique of linear sweep voltammetry. Already the Multi Wall Carbon Nanotubes were used in the modification of a glassy carbon electrode and applied in determining the hair dye Acid Green 25 in aqueous medium. For Basic Brown 17 dye, an analytical curve was obtained over the concentration range 1.0 x 10-6 to 1.0 x 10-4 mol L-1, the following equation: Ip (mA) = 47.7 mA / mol-1 [MB - 17] - 2.8 x 10-6 mA, r = 0.9952, n = 7. The limit of detection (LOD) and quantitation (LOQ) was 1.3 x10-7 mol L-1 and 4.4 x10-7 mol L-1, respectively. The method was applied to contaminated tap water fortified with 12 mg L-1 dye and will undergo analysis using the method of standard addition. The mean recovery (n = 5) was 99.4 ± 1.4%. For the dye Acid Green 25 a calibration curve was constructed using square wave voltammetry in the range 1.0 x10-7 to 2.0 x 10-6 mol L-1 and pre-accumulation of 10 min following equation: Ip = 42.7 μA/mol L-1 [VA - 25] - 5.1 x 10-6 μA, r = 0.9998, reaching limits of detection and quantification of 2.7 x10-9 mol L-1 and 8.9 x10-9 mol L-1, respectively. The method was applied in tap water spiked...