Submitted by Renata Lopes (renatasil82@gmail.com) on 2016-06-28T12:37:36Z No. of bitstreams: 1 carlaalicetheodorobatista.pdf: 1563638 bytes, checksum: 1ab6a3b656a9e8afc9dccb7d96235060 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2016-06-28T12:51:20Z (GMT) No. of bitstreams: 1 carlaalicetheodorobatista.pdf: 1563638 bytes, checksum: 1ab6a3b656a9e8afc9dccb7d96235060 (MD5) / Made available in DSpace on 2016-06-28T12:51:20Z (GMT). No. of bitstreams: 1 carlaalicetheodorobatista.pdf: 1563638 bytes, checksum: 1ab6a3b656a9e8afc9dccb7d96235060 (MD5) Previous issue date: 2012-07-03 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho são apresentados resultados relacionados a estudos sobre o comportamento eletroquímico do lactato e do peróxido de hidrogênio em diversos eletrodos utilizando voltametria cíclica. O comportamento eletroquímico do peróxido de hidrogênio em eletrodos modificados com filme de Azul da Prússia utilizando eletrodos de ouro, compósito e carbono vítreo também foi investigado. Em uma segunda etapa desenvolveu-se um biossensor eletroquímico para determinar lactato por meio do monitoramento do peróxido de hidrogênio produzido na reação catalisada do lactato com oxigênio na presença da enzima lactato oxidase. Nessa etapa, o trabalho consistiu em imobilizar a enzima lactato oxidase na superfície do eletrodo, previamente, modificado com Azul da Prússia, com o auxílio de Nafion. Após a construção do biossensor e a otimização das condições de análise (vazão, potencial, volume de amostra, quantidade de enzima e volume de Nafion) para obtenção de maior sensibilidade no desenvolvimento do método para a determinação de lactato por análise em fluxo, averiguou-se a repetibilidade das medidas (Clactato = 0,20 mmol.L-1) obtendo-se um desvio padrão de 7,1% para 27 repetições. A frequência analítica foi estimada em 41 injeções por hora. Foi obtido um limite de detecção de 2,95 μmol.L-1 e um limite de quantificação igual a 9,84 μmol.L-1. O biossensor foi aplicado na quantificação de lactato em amostras biológicas (urina e saliva). Os resultados obtidos pelo método proposto foram comparados com aqueles oriundos do uso de método de referência. / This paper presents findings related to studies on the electrochemical behavior of lactate and hydrogen peroxide in various electrodes using cyclic voltammetry. The electrochemical behavior of hydrogen peroxide on modified electrodes with Prussian blue film using gold electrodes, composite and glassy carbon was also investigated. In a second step it was developed an electrochemical biosensor for determining lactate by monitoring the hydrogen peroxide produced in the reaction catalyzed lactate with oxygen in the presence of the enzyme lactate oxidase. At this stage, the work consisted of the enzyme lactate oxidase immobilized on the electrode surface, previously modified with Prussian Blue, with the aid of Nafion®. After the construction and optimization of the biosensor analysis conditions (flow rate, potential, sample volume, amount of enzyme and volume of Nafion) for obtaining greater sensitivity in development of the method for the determination of lactate by flow analysis, it was investigated whether the repeatability of measurements (Clactate = 0.20 mmol.L-1) obtaining a standard deviation of 7.1% to 27 repetitions. The analytical frequency was estimated to 41 injections per hour. It was obtained a detection limit of 2.95 μmol.L-1 and a limit of quantification equal to 9.84 μmol.L-1. The biosensor was applied to the quantification of lactate in biological samples (urine and saliva). The results obtained by the proposed method were compared with those from the use of the reference method.

This thesis was focused on a determination of nadroparin using sequential injection analysis and flow injection analysis with fluorimetric and spectrophotometric detection. The principle of determination was based on the interaction of nadroparin with phenothiazine dye. Methylene blue was used as phenothiazine dye. The determination was performed on a laboratory made FIA instrument and on the commercial SIA instrument. Optimal conditions for SIA were concentration of dye 6 ∙ 10-5 mol dm-3 , injected volume 100 µl, flowrate 1,5 ml min-1 , for FIA: concentration of dye 3 ∙10-5 mol dm-3 flowrate 2 ml ∙ min-1 , injected volume= 100 µl, for fluorimetric detection was sensivity of the detector 1000 V, Emission was measured by 2 nm and excitation wavelenght 621 nm. For spectrophotometric detection, absorbance was detected at the absorption maximum wavelength. Repeatability ranged from 2.01 to 2.85%. The limit of detection for FIA was 0.05-0.09 IU ml-1 , for SIA were limits of detection in range 0,25 - 1,63 IU ml-1 , limits of quantification in range 0,83 - 5,44 and linear range was from 0,5 - 20 IU ml-1 . The limits of detection, limits of determination and the linear range could be corrected for the SIA by the injected volume of phenothiazine dye.

This work focuses on optimization and application of voltammetric methods for determination of 5-nitroquinoline in model samples of drinking and river water using carbon film electrode (CFE). The advantages of carbon film electrode are primarily its wide potential window in both cathodic and anodic regions and also low environmental stress compared to mercury electrodes. In this contribution, CV and AdSV were used to observe electrochemical processes. For determination of 5-nitroquinoline DPV and FIA were used. Solid phase extraction was investigated as a method for preliminary separation and preconcentration for DPV. Determination of 5-nitroquinoline at CFE is based on cathodic reduction of nitrogroup. This work demonstrates the application of carbon film electrode for determination of 5-nitroquinoline in submicromolar concentrations in model samples of water.

Tellurium and bismuth are non-biogenous elements, which can be accumulated in human body. The aim of this work is focused on the determination of these elements by the electrochemical hydride generation with non-membrane electrolytic cell with quartz tube - atomic absorption spectrometry. The first step of the work was to optimize parameters for the continuous setup measurements and to obtain its figures of merit. After this, the arrangement with most suitable conditions for determination of these elements was converted to the flow injection setup (FIA) and all experimental parameters were again optimized and its figures of merit were obtained. The conditions of hydride generation were studied for platinum, lead and silver cathodes with hydrochloric and sulphuric acids and their sodium salts as electrolytes. The optimizations of the FIA setup were performed on platinum cathode in hydrochloric acid for bismuth and on lead cathode in sulphuric acid for tellurium. The limit of detection achieved for the generation of tellurium hydride was 1.1 ppm with a linear range up to 20 ppm; for the bismuth hydride the limit of detection was 9.5 ppm and limit of linearity 50 ppm. Keywords Bismuth, tellurium, electrochemical hydride generation, atomic absorption spectroscopy, flow injection analysis

This diploma thesis deals with the determination of creatinine using a combination of flow injection analysis (FIA) or high-performance liquid chromatography (HPLC) with pulse amperometry, an electrochemical technique based on the application of potential pulses on a gold working electrode. The determination was performed in a basic environment of borate buffer with creatinine concentration of 1∙10-4 mol∙l-1 . The lenght of the cleaning and activation pulse was optimized as well as the pH of the running buffer. A cleaning pulse of +1.8 V was first applied to the electrode for 100 ms, then an activation potential of -0.5 V was applied for 150 ms and then a measuring potential of +0.2 V for 300 ms. The optimal pH was selected as pH=9,4. Methanol and acetonitrile were added to the borate buffer to test whether creatinine could be determined in presence of these organic solvents and whether flow injection analysis could be transformed into HPLC. Methanol in the system caused peak deformation, acetonitrile did not cause the peak deformation in the system, at higher contents the baseline was destabilized. Furthermore, the calibration dependence in the range of concentrations from 2.5∙10-4 mol∙l-1 to 5∙10-6 mol ∙ l-1 was measured using PAD in combination with FIA. At higher concentrations, peaks splitted....

[pt] Uma sonda fotoluminescente do tipo turn-off foi avaliada para a detecção de Hg(2+) usando pontos quânticos de grafeno (GQDs). Diferentes nanopartículas de carbono fotoluminescentes foram preparadas usando a abordagem bottom-up, usando ácido cítrico ou ácido cítrico misturado com algum composto contendo enxofre (tioureia, tioacetamida ou glutationa). Dispersões desses GQDs foram comparadas em termos de comportamento fotofísico na presença de Hg(2+). Observou-se que as nanopartículas preparadas com ácido cítrico e tioureia (GQDs- TU) apresentaram melhor perfil de supressão fotoluminescente (resposta analítica) na presença de Hg(2+). As condições experimentais foram ajustadas para o melhor perfil de resposta e para obter os parâmetros analíticos de mérito. Um estudo para avaliar possíveis interferências na presença de outros íons de metais pesados além de íons alcalinos e alcalino-terrosos, comumente presentes em amostras de água natural. A curva analítica normalizada (concentração L0/L versus Hg(2+) foi linear (R(2) = 0,998) até 0,20 microgramas L(-1). O limite de quantificação (LOQ) foi de 10 microgramas L(-1) e o limite de detecção (LOD) foi de 3 microgramas L(-1) para o ensaio em batelada. Além disso, a estratégia proposta para a determinação indireta de Hg(2+) foi adaptada para um sistema de análise por injeção em fluxo (FIA). Após a otimização do ensaio, com a faixa linear cobrindo o intervalo até 900 microgramas L(-1) (R(2)= 0,999), os valores de LOD e LOQ foram 24 microgramas L(-1) e 80 microgramas L(-1), respectivamente. A recuperação na amostra simulada de água fortificada foi de 99,4 por cento mais ou menos 1,2. / [en] A photoluminescent turn-off probe was evaluated for the detection of Hg(2+) based on graphene quantum dots (GQDs). Different photoluminescent carbon nanoparticles were prepared using the bottom-up approach, with citric acid and with citric acid mixed with some sulfur compound (thiourea, thioacetamide or glutathione). Dispersions of these GQDs were compared in terms of photophysical behavoior in the presence of Hg(2+) . It was observed that the nanoparticles prepared with citric acid and thiourea (GQDs-TU) presented a better linear photoluminescent suppression (analytical response) in the presence of Hg(2+). Experimental conditions were adjusted to improve analytical response and to obtain analytical figures of merit. A study to evaluate potential interferences in the presence of other heavy metal ions and alkaline and alkaline-earth ions, commonly present in natural water samples. The normalized analytical curve (L0/L versus Hg(2+) concentration) was linear (R(2) = 0.998) up to 0.20 micrograms (L-1). The limit of quantification (LOQ) was 10 micrograms L(-1) and the limit of detection (LOD) was 3 micrograms L(-1) for the batch assay. In addition, the proposed strategy for indirect determination of Hg2+ was applied in a flow injection analysis system (FIA). After optimization of the assay, linear range covered a range up to 900 micrograms L(-1) (R(2) = 0.999) with LOD of 24 micrograms L(-1) and LOQ of 80 micrograms L(-1). The recovery in the fortified water sample was 99.4 percent.

[pt] Uma sonda fotoluminescente do tipo turn-on foi avaliada para a detecção de putrescina usando pontos quânticos de grafeno (GQDs). Diferentes nanopartículas de carbono fotoluminescentes foram preparadas usando a abordagem bottom-up, usando ácido cítrico como precursor, sozinho ou misturado com outros compostos contendo heteroátomos (N e/ou S) visando funcionalização da nanoestrutura. Observou- se que as nanopartículas preparadas com ácido cítrico e tioureia (GQDs-TU) apresentaram melhor perfil aumento da fotoluminescência (resposta analítica) na presença dessa amina biogênica. As condições experimentais foram ajustadas para o melhor perfil de resposta e para obter os parâmetros analíticos de mérito. No ensaio em batelada, a curva analítica normalizada (concentração L-L0 versus PUT) foi linear (R2 = 0,9498) até 90 mg L1 . O limite de quantificação (LOQ) foi de 15,1 mg L-1 e o limite de detecção (LOD) foi de 4,5 mg L-1 . Além disso, a estratégia proposta para a determinação indireta de putrescina foi adaptada para um sistema de análise por injeção em fluxo (FIA) a fim de aumentar a frequência analítica, diminuir os resíduos e automatizar a quantificação do analito. Após a otimização do ensaio, com a faixa linear cobrindo o intervalo até 50 mg L-1 (R2 = 0,9980), os valores de LOD e LOQ foram 3,0 mg L1 e 9,9 mg L-1 , respectivamente. / [en] A photoluminescent turn-on probe was evaluated for putrescine detection using graphene quantum dots (GQDs). Different photoluminescent carbon nanoparticles were prepared using a bottom-up approach, employing citric acid as a precursor, either alone or mixed with other compounds containing heteroatoms (N and/or S) for nanostructure functionalization. It was observed that the nanoparticles prepared with citric acid and thiourea (GQDs-TU) exhibited a more pronounced increase in photoluminescence (analytical response) when exposed to this biogenic amine. Experimental conditions were fine-tuned to optimize the response profile and obtain the analytical parameters of merit. In the batch assay, the normalized analytical curve (L-L0 concentration versus PUT) was linear (R2 = 0,9498) up to 90 mg L-1 . The limit of quantification (LOQ) was 15,1 mg L-1 and the limit of detection (LOD) was 4,5 g L-1 . Furthermore, the proposed strategy for the indirect determination of putrescine was adapted for a flow injection analysis (FIA) system to increase the analytical frequency, reduce waste, and automate analyte quantification. After optimization of the assay, with the linear range covering the range up to 50 mg L-1 (R2 = 0,9980), the LOD and LOQ values were 3,0 mg L-1 e 9,93 mg L-1 , respectively.

This diploma thesis is focused to the determination of procaine using flow injection and sequential injection analysis coupled with spectrophotometric detection. This determination is based on the reaction of procaine with a colouring agent, 1,2-naphthoquinone-4-sulfonic acid. An orange coloured product is formed, which is determined spectrophotometrically at the wavelength 484 nm. The high of the absorption signal of the product is directly proportional to the concentration of procaine. The aim of this work was to optimize the parameters of both methods of flow analysis so that the limit concentration of procaine can be as low as possible and at the same time, high sensibility is achieved. The next step was to apply these methods on the determination of procaine in real samples. It was found that in flow injection analysis, the absorbance of procaine hydrochloride obeys Beer's law for concentrations from 2.5 to 120 µg/ml. The linear regression equation of calibration graph was y = 0.0059x - 0.0051, with a linear regression correlation coefficient 0.9993. Limit of detection was 0.72 µg/ml. Effects of standing time (stopped-flow), flow rate, concentration of colouring agent, pH and the volume of the sample loop have been examined and optimized. It was also found that in sequential injection...

This master's thesis is focused on the determination of 6-thioguanine (6-T) by DC voltammetry (DCV), differential pulse voltammetry (DPV) and flow injection analysis with electrochemical detection (FIA-ED) on a boron doped diamond electrode (BDDFE). The optimum conditions for determination of 6-T were found and under these conditions, concentration dependences were measured and the limits of quantification (LOQ) were calculated for each method. Medium of 60% methanol and phosphate buffer (PB) pH 2,0 was chosen as optimum for DCV and DPV determination of 6-T at BDDFE. For both DCV and DPV, the linear concentration dependences were obtained in concentration ranges of 6-T from 2 µmol·l-1 to 10 µmol·l-1 with LOQ 0,9 µmol·l-1 for DCV and 1,5 µmol·l-1 for DPV. Lower LOQ was achieved in PB pH 2,0, where LOQ was 0,6 µmol·l-1 for both DCV and DPV, but the problem was lower repeatability. In PB pH 2 6-T was determined by DCV in drinking and river water with LOQ 1,3 µmol·l-1 in both drinking and river water. The possibility of solid phase extraction was investigated as a method for preliminary separation of 6-T from urine. For FIA under optimized conditions (polarization potential 1300 mV, flow rate 5 ml·min1 and sample volume 50 µl) the linear concentrations dependences were obtained in concentration ranges...

Análise cinética diferencial explora diferenças em taxas reacionais entre os analitos e um sistema reacional comum; etapas de separação prévia dos analitos podem então ser prescindidas. Sistemas de análise por injeção em fluxo (FIA) se afiguram como uma ferramenta importante para métodos envolvendo essa estratégia, pois permitem um controle preciso da dispersão de reagentes / amostras e da temporização. O objetivo deste trabalho foi então explorar estes dois aspectos favoráveis visando a determinação simultânea de cobre e de níquel, a partir de suas reações com o reagente cromogênico 5-Br-PADAP. Três alíquotas de amostra eram simultaneamente inseridas, por meio de um injetor proporcional, no fluxo transportador reagente (5-Br-PADAP 75 mg L-1 + sistema tampão 0,5 mol L-1 em ácido acético / acetato, pH 4,7) de um sistema FIA em linha única. Durante o transporte em direção ao detector, as zonas estabelecidas se coalesciam, originando uma zona complexa que era monitorada a 562 nm. Os valores locais máximos e mínimos da função concentração / tempo obtida eram considerados para calibração multivariada utilizando a ferramenta quimiométrica PLS-2 (partial least squares - 2). A concentração do reagente, a capacidade tampão, a temperatura, a vazão, os comprimentos do percurso analítico e das alças de amostragem, bem como a distância inicial entre as zonas de amostra estabelecidas foram avaliados para construção dos modelos matemáticos. Estes foram criados a partir de 24 soluções-padrão mistas de Cu2+ e Ni2+ (0,00-1,60 mg L-1 em HNO3 a 0,1% v/v). Duas variáveis latentes foram suficientes para capturar > 98 % das variâncias inerentes ao conjunto de dados e erros médios das previsões (RMSEP) foram estimados em 0,025 e 0,071 mg L-1 para Cu e Ni, salientando a boa precisão do modelo de calibração. O sistema proposto apresenta boas figuras de mérito: fisicamente estável, quando mantido em operação por quatro horas ininterruptas, consumo de 314 \'mü\'g 5-Br-PADAP por amostra, frequência analítica de 33 amostras por hora (165 dados, 66 determinações) e erros nas leituras em sinais de absorbância tipicamente < 5%. Entretanto, verificou-se a inexatidão das previsões efetuadas pelo modelo proposto, quando comparadas aos resultados obtidos por ICP OES. A partir deste fato, tornam-se necessários maiores estudos referentes a este tipo de matriz, bem como de técnicas de mascaramento dos possíveis interferentes presentes / Differential kinetic analysis exploits the differences in reaction rates between the analytes and a common reactant system; prior steps of analyte separation can then be waived. Flow-injection systems (FIA) are considered as an important tool for methods involving such a strategy because they allow precise control of sample / reagent dispersion and timing. The aim of this work was then to exploit these two favorable aspects for the simultaneous determination of copper and nickel using the 5-Br-PADAP chromogenic reagent. Three sample aliquots were simultaneously inserted by means of a proportional injector into reagent carrier stream (75 mg L-1 5-Br-PADAP + 0.5 mol L-1 acetic acid / acetate, pH 4.7) of a single-line FIA system. During transport towards detection, the established zones coalesce themselves, resulting in a complex zone that was monitored at 562 nm. The local maximum and minimum values of the concentration / time obtained function were considered for multivariate calibration using the PLS-2 (partial least squares - 2) chemometric tool. The reagent concentration, buffering capacity, temperature, flow rate and lengths of the analytical path, sampling loops and initial distance between plugs were established and evaluated for the construction of mathematical models. To this end, 24 Cu2+ and Ni2+ (0.00 - 1.60 mg L-1, also 0.1% v/v HNO3) mixed standard solutions were used. Two latent variables were enough to capture > 98% of the variance inherent in the data set and average prediction errors (RMSEP) were estimated as 0.025 and 0.071 mg L-1 for Cu and Ni, emphasizing the good precision the calibration model. The proposed system presents good figures of merit: physical stability when kept in operation for four uninterrupted hours, consumption of 314 \'mü\'g 5-Br-PADAP per sample, sample throughput of 33 h-1 (165 data, 66 determinations) and error readings in absorbance signals typically <5%. However, inaccuracy of the predictions made by the proposed model when compared to results obtained by ICP OES was noted. Thus, further studies involving this type of matrix, as well as masking techniques of potential interferences present, are recommended