Electrospray ionization mass spectrometry (ESI-MS) is a powerful method to monitor organometallic reactions. It is fast at generating spectrum, soft to fragile organometallic compounds and sensitive to intermediates in low concentration. When coupled with the pressurized sample infusion (PSI) that helps to continuously inject reacting solution to the MS, both an inert-gas atmosphere and real-time reaction monitoring can be achieved. Also collision induced dissociation (CID) of MS can be used to probe the relative binding affinities of phosphine ligands in ruthenium complexes. PSI ESI-MS can be coupled with Fourier transform infrared spectroscopy (FTIR) to monitor the rhodium-catalyzed hydroacylation simultaneously. This technique expands the dynamic range to 5 magnitudes. The effect of mass-transfer in heterogeneous hydrogenation of charge-tagged alkyne was also studied by PSI ESI-MS. In this study cross area, stirring effect, catalyst loading and hydrogen concentration were considered and tested. Also in the study an interesting finding reveals in heterogeneity of the solution. Relative binding affinities of different phosphine ligands were attained from comparing the relative intensities of fragmentation products from MS/MS. And the phosphine ligand substitution reaction was monitored by the ESI-MS in a real-time manner. A competitive dissociative substitution mechanism was proposed and confirmed by the simulation and modeling of COPASI. / Graduate

<p>Naučna rasprava izložena u ovoj tezi bavi se analizom<br />kvaliteta električne energije. Visok nivo električne<br />energije podrazumeva da su napon napajanja i struja<br />potrošača idealne sinusoide sa tačno određenom<br />amplitudom i učestanošću. Bilo kakva odstupanja od<br />idealnog nazivaju se izobličenja i najčešće se<br />karakterišu sa harmonicima.<br />Poslednjih godina dolazi do naglog razvoja<br />poluprovodničkih komponenata. Takve komponente su<br />uticale na ubrzan razvoj snažnih uređaja energetske<br />elektronike. Ti uređaji su nelinearnog karaktera, što<br />dovodi do pojave harmonika u signalima napona i struja<br />elektroenergetskog sistema. Prvi problem kojim se bavi<br />ova teza je analiza talasnih oblika struja ispravljača.<br />Metode primenjene za analizu su wavelet transformacija<br />(VT) i modulated overlapped transformacija (MLT). MLT<br />nadoknađuje nedostatak VT da dekomponuje signal u<br />odgovarajuće podopsege koji mogu sadržati i više<br />harmonika i daje tačnu informaciju o svakom harmoniku.<br />Obe metode su pogodne za offline analizu. Za online analizu<br />predložen je hibridni metod baziran na diskretnoj<br />Furijeovoj transformaciji (DFT) i adaptivnom pojasnom<br />filteru (EPLL). Hibridni metod je zadržao dinamički<br />odziv DFT-a, dok je EPLL obezbedio sinhronizaciju sa<br />osnovnom učestanošću sistema. Hibridni metod daje<br />dovoljno tačnu informaciju o osnovnom i višim<br />harmonicima samo ako su njihove učestanosti ceolobrojni<br />umnožak učestanosti osnovnog harmonika. U slučaju pojave<br />interharmonika, odnosno kada taj odnos više ne važi,<br />hibridni metod ne daje tačne rezultate. Za analizu takvih<br />signala predložen je novi metod, koji je baziran na<br />adaptivnom diskretnom pojasnom filteru (ANF) t.j. metod<br />koristi diskretni pojasni filter za modelovanje<br />harmonijskih komponenata u ulaznom signalu, dok se<br />prošireni Kalmanov filter (EKF) koristi kao adaptivni<br />mehanizam. Novi metod je preuzeo osobinu ANF-a da može<br />adaptivno da prati promene učestanosti i osobinu EKF-a<br />da ima bolji dinamički odziv. Metode su implementirane<br />na digitalnom procesoru za obradu signala i upoređene sa<br />postojećim metodama. Metode pokazuju prednosti u odnosu<br />na druge metode.</p> / <p>Scientific research in this thesis discusses power quality<br />analysis. High power quality assumes that both the voltage<br />power supply and the load current are ideal sinusoidal signals<br />with a precisely defined amplitude and frequency. Any<br />deviations from this ideal vaweform are considered as distortion<br />and are characterised by harmonics.<br />Over the last few decades, there has been a rapid development<br />of semiconductor components. Such components made an<br />impact on the fast development of power electronics devices.<br />These devices are nonlinear, introducing harmonics in both<br />voltage and current of the power grid. The first issue researched<br />in this thesis is the analysis of the rectifier voltage and current<br />waveforms. Methods used for the analysis are the wavelet<br />transform (WT) and the modulated overlapped transform (MLT).<br />The MLT overcomes the drawback of the WT, which<br />decomposes the signal into subbands that can contain more<br />harmonics, and gives accurate information about every<br />harmonic. Both methods are suitable for offline analysis. For<br />online analysis, a hybrid method is proposed, based on the<br />discrete Fourier transform (DFT) and the adaptive notch filter<br />(EPLL). The hybrid method retains a good dynamic response of<br />the DFT whereas the EPLL provides a synchronisation with the<br />fundamental system frequency. The hybrid method provides<br />accurate information on the fundamental and the higher<br />harmonics only if their frequencies are integer multiples of the<br />fundamental frequency. In the case of interharmonics, i.e. when<br />this integer ratio is not valid, the hybrid method does not provide<br />accurate results. In order to analyse such signals, a new<br />method is proposed. It is based on discrete adaptive notch filter<br />(ANF), i.e. the method uses a discrete notch filter for modeling<br />the harmonic components in the input signal, whereas an<br />Extended Kalman Filter (EKF) is used as an adaptation<br />algorithm. The adaptive notch Kalman filter inherited the<br />property of the ANF to adaptively track changes in the<br />frequency and the property of the EKF to have a faster dynamic<br />response. Methods have been implemented in a digital signal<br />processor and compared with the existing ones. The methods<br />show advantages compared to other methods.</p>

Current transformer saturation will cause the secondary current distortion. When saturation occurs, the secondary current will not be linearly proportional to the primary current, which may lead to maloperation of protection devices. This thesis researches and tests two detecting methods: Fast Fourier Transform (FFT) and Wavelet Transform based methods. Comparing these two methods, FFT has a better performance in steady state saturation, and Wavelet Transform can determine singularity to provide the moment of distortion. The Jiles-Atherton (J-A) theory of ferromagnetic hysteresis is one approach used in electromagnetics transient modeling. With decades of development, the J-A model has evolved into different versions. The author summarizes the different models and implements J-A model in both MATLAB and Simulink.

Challenges encountered in pathogen identification and detection include the genetic heterogeneity of strains within species of some foodborne pathogens, isolation of injured cells, mixed strains or mixed species contamination of foods, and differentiation between viable and dead cells. The first objective of this research was to evaluate an isolation medium that was based on time-delayed release (5 to 6 h) of selective agents in tablet format to a modified Listeria recovery enrichment broth (mLRB) medium for enhanced and rapid recovery of injured Listeria. The second objective involved the use of Fourier transform infrared (FT-IR) spectroscopy and chemometric analysis for the differentiation of: Listeria monocytogenes epidemic clones (ECs); viable versus heat-killed populations; different mixed strains and mixed species of Listeria; and different injury treatments and repair in Listeria populations. Nitrite- or acid-injured Listeria at approximately 10 CFU/ml were recovered in mLRB medium, and cell populations enumerated at various times (12 to 48 h) of incubation at 37oC. Analysis of variance revealed that acid-injured Listeria populations in mLRBS6 (mLRB plus the selective agents at 6 h) were significantly higher (P < 0.05) than those in mLRBS0 (mLRB plus the selective agents at 0 h) at 24 h; however, the differences in populations on these two media were not significant for nitrite-injured Listeria. Cell populations of four strains of Listeria recovered in mLRBTD (mLRB plus the time-delayed release tablets of the selective agents) were significantly higher than when those strains were enriched in the U.S. Food and Drug Administration (FDA), International Organization for Standardization (ISO), and U.S. Department of Agriculture (USDA) broths at 24 h. Comparison between artificially contaminated milk and meat samples with a four-strain cocktail of Listeria resulted in cell populations that were significantly higher (P < 0.05) on mLRBTD for contaminated meat than on mLRBTD for contaminated milk at 24 h. FT-IR spectroscopy in the mid-infrared region (4000 to 600 cm-1) and chemometrics was successfully applied to discriminate L. monocytogenes strains belonging to the same EC (ECII or ECIV) (100% accurate spectral classification), intact and heat-killed populations of each EC strain (100% accurate spectral classification), and spectral wavenumbers 1650 to 1390 cm-1 were used to differentiate heat-killed from intact populations. FT-IR spectroscopy and chemometrics in the wavelength region 1800 to 900 cm-1 could successfully discriminate different mixed strains of L. monocytogenes (98.15% accurate spectral classification) and different mixed species of L. monocytogenes and L. innocua (92.06% accurate spectral classification) from individual strains; Wavelength range 1800 to 900 cm-1 was successfully used to discriminate between intact, acid-injured, and heat-injured Listeria, with repaired cells from acid and heat treatments clustering closer to intact cells (93.33% of spectra accurately classified). Delayed-addition of selective agents to broth medium improves recovery of injured Listeria by allowing repair time, could minimize contamination through manual addition of selective agents, and saves analyst time; FT-IR spectroscopy is a highly discriminatory and reproducible technique that can be used for the differentiation of strains and various physiological states of Listeria.

Digitized acoustical signals of Byzantine music performed by Iakovos Nafpliotis are used to extract the fundamental frequency of each note of the diatonic scale. These empirical results are then contrasted to the theoretical suggestions and previous empirical findings. Several parametric and non-parametric spectral parameter estimation methods are implemented. These include: (1) Phase vocoder method, (2) McAulay-Quatieri method, (3) Levinson-Durbin algorithm,(4) YIN, (5) Quinn & Fernandes Estimator, (6) Pisarenko Frequency Estimator, (7) MUltiple SIgnal Characterization (MUSIC) algorithm, (8) Periodogram method, (9) Quinn & Fernandes Filtered Periodogram, (10) Rife & Vincent Estimator, and (11) the Fourier transform. Algorithm performance was very precise. The psychophysical aspect of human pitch discrimination is explored. The results of eight (8) psychoacoustical experiments were used to determine the aural just noticeable difference (jnd) in pitch and deduce patterns utilized to customize acceptable performable pitch deviation to the application at hand. These customizations [Acceptable Performance Difference (a new measure of frequency differential acceptability), Perceptual Confidence Intervals (a new concept of confidence intervals based on psychophysical experiment rather than statistics of performance data), and one based purely on music-theoretical asymphony] are proposed, discussed, and used in interpretation of results. The results suggest that Nafpliotis' intervals are closer to just intonation than Byzantine theory (with minor exceptions), something not generally found in Thrasivoulos Stanitsas' data. Nafpliotis' perfect fifth is identical to the just intonation, even though he overstretches his octaveby fifteen (15)cents. His perfect fourth is also more just, as opposed to Stanitsas' fourth which is directionally opposite. Stanitsas' tendency to exaggerate the major third interval A4-F4 is still seen in Nafpliotis, but curbed. This is the only noteworthy departure from just intonation, with Nafpliotis being exactly Chrysanthian (the most exaggerated theoretical suggestion of all) and Stanitsas overstretching it even more than Nafpliotis and Chrysanth. Nafpliotis ascends in the second tetrachord more robustly diatonically than Stanitsas. The results are reported and interpreted within the framework of Acceptable Performance Differences.

L’imagerie hyperspectrale est maintenant très développée dans les applications de télédétection. Il y a principalement deux manières de construire les imageurs associés : la première méthode utilise un réseau et une fente, et l’image spectrale est acquise ligne par la ligne le long de la trajectoire du porteur. La seconde est basée sur le principe de la spectrométrie par transformée de Fourier (TF). Certains des systèmes utilisés sont construits de manière à enregistrer l’interférogramme de chaque point de la scène suivant le déplacement dans le champ. Le spectre de la lumière venant d’un point de la scène est alors calculé par la transformée de Fourier de son interférogramme. Les imageurs classiques basés sur des réseaux sont plus simples à réaliser et les données qu’ils fournissent sont souvent plus faciles à interpréter. Cependant, les spectro-imageurs par TF fournissent un meilleur rapport signal sur bruit si la source principale de bruit vient du détecteur.Dans la première partie de cette thèse, nous étudions l’influence de différents types de bruit sur les architectures classiques et TF afin d’identifier les conditions dans lesquelles ces dernières présentent un avantage. Nous étudions en particulier l’influence des bruits de détecteur, de photons, des fluctuations de gain et d’offset du détecteur et des propriétés de corrélation spatiale des fluctuations d’intensité du spectre mesuré. Dans la seconde partie, nous présentions la conception, la réalisation et les premiers résultats d’un imageur basé sur un interféromètre de Michelson à dièdres statique nommé DéSIIR (Démonstrateur de Spectro-Imagerie Infrarouge). Les premiers résultats montrent, qu’en mode spectromètre simultané, DéSIIR permet la restitution du spectre avec les spécifications requises dans le cadre des applications recherchées, c'est-à-dire détecter avec une résolution d environ 25 cm-1 un object de quelques degrés plus chaud que le fond de la scène et présentant une signature spectrale entre 3 et 5 juin. En mode spectromètre imageur, après recalage des images, il est possible de reconstruire le spectre de chaque point de la scène observée. / Hyperspectral imaging is now very important in remote sensing applications. There are two main ways to build such imagers : the first one uses a grating and a slit, and the spectral image is acquired line by line along the track of the carrier. The second way is to use the principle of Fourier transform (FT) spectrometry. Some of these systems are built in such a way that they record the interferogram of each point of the scene as it moves through the field of view. The spectrum of the light coming from a particular point is then calculated by the Fourier transform of its interferogram. Classical gratting-based spectral imagers are easier to build and the data they provide a better signal to noise ratio if the main source of noise comes from the detector.In the first part of this thesis, we study the influence of various types of noise on the classic and TF-based architectures to identify the conditions in which these last ones present an advantage. We study particularly the influence of detector noise, photons noise, detector gain and offset fluctuations and spatial correlation properties of the intensity fluctuations. In the second part, we present the conception, the realization and the first results of an imager bases on a Michelson interferometer with dihedrons named DéSIIR (“Démonstrateur de Spectro Imagerie Infrarouge”). The first results show that, in simultaneous spectrometer mode, DéSIIR allows the reconstruction of the spectrum with respect to the specific requirements, which are to be able to detect an objet of some degrees warmer than the background of the scene observed with a resolution of about 25 cm -1. In imager mode, this reconstruction is performed for each point of the scene.

Pour répondre au besoin de miniaturisation des spectromètres de terrain travaillant dans l’infrarouge, l’ONERA a développé un nouveau concept baptisé MICROSPOC. Ce dispositif est un détecteur infrarouge auquel a été intégré un interféromètre à deux ondes, constituant un spectromètre statique par transformée de Fourier. Ce plan focal infrarouge modifié, qui fusionne la fonction interférométrique et la fonction de détection, associé à une optique de tête simplifiée, permet d’envisager la réalisation d’instruments très compacts. L’objectif de cette thèse est de concevoir un spectromètre infrarouge miniature basé sur le dispositif MICROSPOC. Dans un premier temps, un travail théorique a été mené, dans l’objectif de dimensionner un système optique très compact. Notre choix s’étant orienté vers un système optique de collection (le détecteur voit une source étendue à distance finie), l’étude de l’acceptance angulaire de MICROSPOC dans ces conditions d’éclairement est indispensable afin de prévoir le contraste et la forme des franges d’interférence. Les résultats montreront la grande acceptance angulaire de MICROSPOC.Dans un second temps, un démonstrateur basé sur un composant MICROSPOC et sur le système optique simplifié a été réalisé. Ce démonstrateur a été caractérisé en laboratoire puis utilisé sur le terrain lors d’une campagne de mesures. Ces différentes exploitations ont montré la robustesse de l’instrument malgré l’obtention d’interférogrammes présentant divers défauts.Dans un troisième temps, une chaîne de traitement a été développée afin d’estimer un spectre à partir d’un interférogramme obtenu à l’aide du démonstrateur. Du fait des caractéristiques intrinsèques de MICROSPOC, la transformée de Fourier n’est pas la meilleure solution pour estimer un spectre. Nous l’avons montré en nous intéressant aux effets des disparités de longueur d’onde de coupure du détecteur sur l’estimation d’un spectre. Nous nous sommes alors tournés vers une approche consistant à utiliser la caractérisation spectrale de l’instrument pour inverser la mesure. Cette approche donne des résultats satisfaisants.Enfin, le but principal de cette thèse a été élargi par la conception et la réalisation de différents démonstrateurs combinant une fonction d’imagerie à une fonction de spectrométrie. Les premières pistes pour la conception d’un spectromètre qui tient dans la main ont été données. / In order to satisfy the need for handheld infrared spectrometers, the ONERA developed a new concept called MICROSPOC. This device is an infrared focal plane array with a built-in two-wave wedge-like interferometer and forms a static Fourier-transform spectrometer. This modified focal plane array, which merges the detection function and the interferometric function, in association with a simplified optical system, allows to consider the realisation of a much compact instrument. The goal of this thesis is to design and to realize a miniaturized infrared spectrometer based on the MICROSPOC concept.Firstly, a theoritical work has been led in order to design a compact optical system. Since we have chosen a collection optical system (the focal plane array sees an extended source placed at a finite distance), the study of MICROSPOC angular acceptance in these lightening conditions is needed in order to predict the contrast and the shape of interference fringes. The huge angular acceptance of MICROSPOC will be established with the results of this study.Secondly, a demonstrator based on MICROSPOC device and on the simplified optical system has been realized. This demonstrator has been caracterized in the laboratory and used in real conditions of a measurement campaign. These different exploitations have shown the robustness of the instrument despite some defaults on acquired interferograms.Then, a processing chain has been developed in order to estimate a spectrum from an interferogram acquired with our demonstrator. Considering the MICROSPOC’s own characteristics, the Fourier-transform is not the best way to estimate a spectrum. We have come to this conclusion by studying the effects of cut-off wavelenghts disparities of the detector on the spectrum estimation. At this point we have considered an approach that consists of using the spectral characterization of the instrument in order to inverse the measure. This approach gives satisfying results.Finaly, the main goal has been widened with the design and the realisation of other instruments that combine a spectrometric function and a imaging function. The first elements for the design of a handheld spectrometer have been given.

Objetivou-se avaliar a utilização da metodologia de infravermelho com transformada de Fourier (IVTF) na identificação de adulteração em leite cru. O objetivo no primeiro estudo foio de desenvolver calibração para identificação de adulteração através da comparação do espectro de leite adulterado com um espectro de referência para leite cru. Para construção do espectro referência foram coletadas 800 amostras de diferentes fazendas localizadas na região de estudo no período de agosto de 2009 a março de 2010. Através da análise de componentes principais, foram desenvolvidas oito calibrações com diferentes números de fatores (componentes principais). Para validação das diferentes calibrações, foram coletadas outras 100 amostras da mesma região de estudo. As amostras foram adulteradas com três diferentes adulterantes geralmente utilizados na adulteração do leite cru sendo eles: bicarbonato de sódio (BS), citrato de sódio (CS) e soro de queijo (SO). Para cada adulterante foram utilizadas três diferentes concentrações (BS: 0,05, 0,10 e 0,25 %; CS: 0,025, 0,050 e 0,075% e SO: 5, 10 e 20%). Para avaliação do desempenho das calibrações foram calculadas a especificidade e a sensibilidade para cada adulterante e respectivas concentrações. A especificidade foi de 92,9% na calibração com 12 fatores. Já a sensibilidade variou em função do adulterante, concentração e número de fatores. Todas as amostras adulteradas com bicarbonato foram identificadas corretamente com modelos de 10 fatores e na concentração mais baixa (0,05%). Já para o citrato, somente amostras com concentração de 0,075% foram identificadas em 93,9% dos casos para o modelo de 18 fatores. Amostras adulteradas com soro, mesmo na concentração mais alta (20%) puderam ser identificadas em menos de 47,1% dos casos, talvez pelo tratamento espectral realizado pelo software ASM em que parte do espectro não é considerado na construção das calibrações. A comparação espectral mostrou-se uma técnica interessante para identificação de leite adulterado e que também poderia antecipar a descoberta de novos adulterantes. Já no segundo estudo o objetivo foi desenvolver calibrações para determinação da concentração dos adulterantes bicarbonato de sódio, citrato de sódio e soro de queijo. Para desenvolvimento das calibrações foram utilizadas as amostras adulteradas do primeiro estudo e, para validação, foram coletadas outras 60 amostras que foram novamente adulteradas. O desempenho de cada calibração foi avaliado através da acurácia (Se), limite de detecção (LD) e coeficiente de determinação (R2). Todas as calibrações apresentaram R2 superior a 0,91 com LD de 0,015%, 0,017% e 3,9% para BS, CS e SO, respectivamente. Já a acurácia foi de 0,005%, 0,009 % e 2,26% para BS, CS e SO, respectivamente. Através dos resultados obtidos neste estudo, conclui-se que a metodologia de IVTF pode ser utilizada para determinação da concentração de bicarbonato de sódio, citrato de sódio e soro de queijo em leite cru. Associada à equipamentos automatizados, é uma opção viável no monitoramento destes adulterantes, tendo o baixo custo operacional e alto desempenho analítico como características adicionais. / The objective of this research was to evaluate the use of the methodology of Fourier Transform Infrared (FTIR) in identifying adulteration in raw milk. The objective of the first study was to develop scales to identify contamination by comparing the spectrum of adulterated milk with a reference spectrum for raw milk. To build the reference spectrum, 800 samples were collected from different farms located in the study area from August 2009 to March 2010. Through the analysis of principal components, eight scales with different numbers of factors (principal components) were developed. To validate the different calibrations, other 100 samples were collected from the same region of study. The samples were adulterated with three different adulterants commonly used in the adulteration of raw milk: sodium bicarbonate (SB), sodium citrate (SC) and whey (W). Each adulterant was used at three different concentrations (SB: 0.05, 0.10 and 0.25%; SC: 0.025, 0.050 and 0.075% and W: 5, 10 and 20%). To evaluate the performance of the calibrations, the specificity and sensitivity for each adulterant and its concentration were calculated. The specificity was 92.9% in the calibration with 12 factors. Sensitivity varied according to the adulterant, concentration and number of factors. All samples adulterated with bicarbonate were accurately identified in the 10-factor model and at the lowest concentration (0.05%). As for citrate, only samples at a concentration of 0.075% were identified in 93.9% of cases for the 18-factor model. Samples adulterated with whey, even at the highest concentration (20%) were identified in less than 47.1% of cases, which maybe attributed to the fact that part of the spectrum is not consideredin the spectral processing performed by ASM software. The spectral comparison proved to be an interesting technique for the identification of adulterated milk and that could also be used to discover new adulterants. In the second study, the aim was to develop calibrations for determining the concentration of sodium bicarbonate, sodium citrate and whey used as raw milk adulterants. To develop the calibrations, adulterated samples of the first study were used and, for validation, other 60 samples were collected and adulterated. The performance of each calibration was evaluated regarding accuracy (Se), detection limit (DL) and determination coefficient (R2). All calibrations presented R2 higher than 0.91 with DL of 0.015%, 0.017% and 3.9% for SB, SC and W, respectively. Accuracy was 0.005%, 0.009% and 2.26% for SB, SC and W, respectively. Results show that the FTIR methodology can be used for determining the concentration of sodium bicarbonate, sodium citrate and whey in raw milk. Associated with automated equipment, it is a feasible option for monitoring these adulterants, presenting low operational costs and high analytical performance as additional features.

Os catalisadores eletroquímicos binários de PtSn/C, PdSn/C e PtPd/C foram sintetizados em diferentes proporções pelo método da redução via borohidreto, posteriormente estes foram caracterizados por microscopia eletrônica de transmissão, difração de raios X, espectroscopia no infravermelho por transformada de Fourier (PtSn/C e PdSn/C) e energia dispersiva de raios X. As atividades eletroquímicas dos diferentes materiais preparados foram avaliadas por intermédio de voltametria cíclica, cronoamperometria e curvas de polarização em célula a combustível alimentada diretamente por etileno glicol em eletrólito alcalino. As curvas de densidade de potência indicaram que os catalisadores eletroquímicos contendo Sn e Pd são mais ativos para a reação de oxidação do etileno glicol, especialmente a composição 70%:30% - relação molar entre os metais suportados em carbono - dos catalisadores PtSn/C, PdSn/C e PtPd/C todos superando as medidas de potência do Pt/C. Este resultado indica que a adição de Sn e Pd favorece a oxidação do etileno glicol em meio alcalino. O melhor desempenho observado para os catalisadores eletroquímicos PtSn/C, PdSn/C e PtPd/C (70%:30%) poderia estar associado à sua maior seletividade quanto a formação de oxalato, ou seja , a formação deste produto resulta em um maior número de elétrons, por consequência em maiores valores de corrente. / Binary electrochemical catalysts PtSn/C, PdSn/C and PtPd/C were synthesized in different proportions by the method of reduction via borohydride. These were characterized by transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy (PtSn/C and PdSn/C) and energy dispersive X-ray. The electrochemical activities of the different materials prepared were evaluated by cyclic voltammetry, chronoamperometry and polarization curves for fuel cell powered directly by ethylene glycol in an alkaline electrolyte. Power density curves indicated that the electrochemical catalysts Sn-containing or Pd-containing are more active for ethylene glycol oxidation reaction, particularly the (70%:30%) composition of PtSn/C, PdSn/C and PtPd/C, all of them exceeding power measurements of Pt/C. These results indicate that the addition of Sn and Pd promotes the oxidation of ethylene glycol in an alkaline medium and this improved performance may be associated with a higher selectivity for the formation of oxalate that results in a larger number of electrons, consequently enhancing the current values.

Thesis (Master of Applied Sciences in Chemistry)--Cape Peninsula University of Technology, 2018. / Biosensors have been on the forefront to provide clinical diagnosis tools for various diseases. Proper selection of biomarkers as well as chemical electrode modification is key in the fabrication of electrochemical biosensors. Hence, electrode modified with nanomaterials devices to improve electroanalytical applications. These nanomaterials were functionalized to improve conductivity, accelerate signal transduction and amplify biorecognition events. Thus, resulting in novel sensing platforms that are highly sensitive and selective towards the target analyte. In this study, gold nanorods (Au NRs) capped with CTAB, zeolitic imidazole framework were synthesised using the seed mediated and hydrothermal method respectively. Composites of gold nanorods with cysteine, ZIF-8 or both were also synthesised. All synthesised materials were characterized using ultraviolet–visible (UV-Vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-Ray diffraction (XRD) and cyclic voltammetry (CV) techniques. The obtained results confirmed the synthesis of the nanomaterials and composites. Identification of the ideal platform for fabrication of a transducer with the best electrochemical response was determined by studying the combinations of the synthesised nanomaterials and composites. The studied parameters were surface coverage, conductivity, rate of electron transfer constant. Cysteine-Au NRs composites platforms, had exceptional properties hence its synthesis optimisation of was undertaken. The effect of CTAB, reaction time, volume and concentration ratio of Au:Cysteine, temperature and pH on the composite properties were assessed. However, this composite’s electrochemical properties decreased when bioconjugated with the antibodies. Hence, the choice of Au NRs CTAB functionalised ZIF-8 (CTABAu/ZIF-8) as the transducer for biosensor applications due to a more favourable biocompatibility. Biosensor fabrication was done by drop coating glassy carbon electrode with the CTABAu/ZIF-8 forming a transducer followed by immobilisation of the antibody (Ab) using a covalent attachment method with glutaraldehyde (GA) as a cross linker. The target analyte, epidermal growth factor (EGF) was interacted with the Ab binding sites via electrostatic forces. All the fabrication steps were optimized for biosensor components, immobilization technique (drop coating and immersion), concentration and incubation time of linker and bioreceptor, as well as the synthesis of the CTABAu-ZIF-8 composites where in situ and ex situ techniques were compared together with the effect of the concentration ratio of Au: ZIF-8. There was also an analysis of optimum pH. Optimum conditions were found to be immersion in 3 % GA and 2 μg/ml Ab, with incubation times of 8, 10 and 5 minutes for GA, Ab and EGF respectively at a pH of 6. The following electroanalytical techniques: cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV) were utilised for EGF detection. The DPV showed better reproducibility, higher currents and better resolution hence; it was the method of choice. The technique’s optimisation involved assessments of the effect of step potential, starting potential and pulse amplitude. The optimum response for pulse amplitude, step potential and starting potential were 60 mV, 20 mV and 0.5 V respectively. The biosensor analytical parameters were linear towards EGF in the concentration range from 2 to 100 nM with a detection limit of 0.58 nM. Reproducibility and repeatability tests were acceptable, and the biosensor had a stability over 80 % within 15 days. There was no interference observed in the presence of glucose and creatine. The EGF biosensor was successfully applied in urine and saliva analysis, obtaining 67.5 and 3.12 nM respectively. This biosensor’s positive outcome strongly suggests its potential as a diagnosis tool for early detection of kidney disease as it was able to detect EGF concentration within physiological levels of EGF in normal kidney function.