Thesis (MSc Food Sc )--Stellenbosch University, 2002. / ENGLISH ABSTRACT: The oxidative stability of crude, cold-pressed mango kernel fat (MKF) was determined over a period of 240 days using the peroxide value (PV), conjugated diene value (CD) and p-anisidine value (AV) tests. The changes in fatty acid profile were monitored with gas chromatography and the oxidative status of MKF effectively predicted by FT-NIR spectroscopy. Results obtained from the different methods complemented each other and indicated the stable character of mango kernel fat against oxidative deterioration. The fatty acid profile constituted palmitic acid (CI6:0; 8.43%), stearic acid (CI8:0; 34.98%), oleic acid (CI8:1 cis; 48.05%), linoleic acid (CI8:2; 6.60%) and arachidic acid (C20:0; 1.73%). Trace amounts of C16:1 (0.56%), C18:1 trans (0.25%), C18:3 (0.43%), C20:1 (0.25%) and C22:0 (0.40%) were also found. The freshly pressed MKF had a peroxide value of 2.7 meq.kg", CD value of 0.07% and an AV of 2.2 mmol.kg", After 40 days of storage, the peroxide values of MKF stored with and without exposure to a limited amount of oxygen at 5, 15,25 and 40°C increased to 5 meq.kg" and 4 meq.kg" respectively. Emulsification of MKF had a stabilising effect (maximum PV = 2.8 meq.kg'), while exposure to UV light had a catalysing effect (maximum PV = 5 meq.kg'). These maximum values, decreased after 40 days. The CD values of MKF samples stored with and without exposure to oxygen at 5, 15,25 and 40°C increased to 0.18% and 0.16%, respectively at day 40. The CD values of samples exposed to light increased to 0_20% and the emulsified samples showed similar values to that of the MKF samples not exposed to oxygen. The conjugated diene values remained stable after day 40. The p-anisidine values of the MKF samples both stored with and without exposure to oxygen at 5, 15, 25 and 40°C varied between 0.5 and 5 mmol.kg". The weak correlation to the measurement of nonanal, as well as the low levels of 2-alkenals produced by the MKF, resulted in these low and sometimes non-linear values. The peroxide, conjugated diene and p-anisidine values obtained for MKF stored at 25°C over 240 days were low due to the low content of polyunsaturated fatty acids in MKF. This compared favourably with the higher values attained for sunflower, canola and olive oil, which are all rich in polyunsaturated fatty acids. The minimal changes observed in the fatty acid profile of mango kernel fat indicated the stability of the saturated fatty acids (CI6:0 and CI8:0) and oleic acid. In addition, the instability of linoleic and linolenic acids was evident due to oxidative deterioration. A decrease of 7.41% and 12.80% was observed between day 0 and 240 for the C18:2/C16:0 and C18:2/C18:0 ratios respectively. The prediction of the oxidative status of the MKF samples by near infrared spectroscopy were possible after the development of calibration models from a total data set of 300 samples of which one-third was used for independent validation. Principle component analysis (PCA) indicated classification at 0, 40 and the remaining (80 - 240) days. The best calibration model for PV yielded a SEP (standard error of prediction) of 0.46 meq.kg", correlation coefficient (r) of 0.95, bias of 0.02 and a root mean square error of prediction (RMSEP) of 0.46 meq.kg". The CD calibration model had a correlation coefficient of 0.89, SEP of 0.01 %, bias of 0.001 and RMSEP of 0.01% when developed on a data set with no pre-processing applied. The AV calibration had a SEP of 0.32 mmol.kg", bias of 0.03, RMSEP of 0.32 mmol.kg" and rof 0.93. The C18:2 and C18:3 models were built using partial least squares (PLS) regression and the values obtained for SEP were 0.31% and 0.054%, RMSEP 0.32% and 0.05%, bias 0.05 and 0.01 and correlation coefficcients were 0.82 and 0.54 respectively. The calibrations for CI8:1, C18:0 and C16:0 yielded weaker correlations. Good correlations were obtained when calibrating the CI8:2/CI6:0 and C18:2/CI8:0 ratios. / AFRIKAANSE OPSOMMING: Die oksidatiewe stabiliteit van ru, koud-geperste mango kern vet (MKV) (Mangifera indica L.) is oor 'n periode van 240 dae bepaal deur gebruik te maak van die peroksiedwaarde (PV), gekonjugeerde dieen waarde (CD) en p-anisidien waarde (AV) toetse. Die veranderinge in die vetsuurprofiel is gemonitor deur gaschromatografie en die oksidatiewe status van MKV is akkuraat voorspel word deur Fourier transformasie naby infrarooi (FT-NIR) spektroskopie. Die resultate van die verskillende toetsmetodes komplementeer mekaar goed en dui die stabiliteit van mango kern vet teen oksidatiewe verval aan. Die vetsuurprofiel is saamgestel uit palimitiensuur (C16:0; 8.43%), steariensuur (C18:0; 34.98%), oleïensuur (C18:1 cis; 48.05%), linoleïensuur (C18:2; 6.60%) en aragiedsuur (20:0; 1.73%). Spoorhoeveelhede C16:1 (0.56%), C18:1 trans (0.25%), C18:3 (0.43%), C20:1 (0.25%) en C22:0 (0.40%) is ook geïdentifiseer. Die vars geperste MKF het 'n peroksiedwaarde van 2.7 meq.kg", 'n CD waarde van 0.07% en 'n AV waarde van 2.2 mmol.kg" getoon. Na afloop van 40 dae opbergingsperiode by 5, 15, 25 en 40°C het die PV van MKV met 'n beperkte blootstelling aan suurstof na 5 meq.kg" vermeerder, terwyl die waardes van monsters sonder suurstofblootstelling na 4 meq.kg" vermeerder het. Emulsifisering van MKV het 'n stabiliserende effek (maksimum PV = 2.8 meq.kg") terwyl blootstelling aan ultraviolet (UV) lig 'n kataliserende effek (maksimum PV = meq.kgl ) op oksidasie gehad het. Hierdie maksimum waardes het na 40 dae afgeneem. Die CD waardes van MKF monsters opgeberg by 5, 15, 25 en 40°C en met beperkte blootstelling aan suurstof het vermeerder tot 0.18% terwyl die monsters sonder suurstofblootstelling by bogenoemde temperature vermeerder het tot 0.16% na 40 dae. Die gekonjugeerde dieen waardes van die monsters blootgestel aan UV lig het vermeerder tot 0.20%; terwyl die geëmulsifiseerde monsters waardes soortgelyk aan die MKV monsters sonder blootstelling aan suurstof getoon het. Gekonjugeerde dieen waardes het gestabiliseer vanaf dag 40. Die p-anisidienwaardes van MKV monsters opgeberg by temperature van 5,15, 25 en 40°C, met en sonder blootstelling aan suurstof, het varieer tussen 0.5 en 5 mmol.kg". Die swak korrellasie tussen nonanal produksie en p-anisidienwaardes, sowel as die klein hoeveelhede 2-alkenale geproduseer, was verantwoordelik vir hierdie lae en nie linêere waardes. Die peroksied, gekonjugeerde dieen en p-anisidienwaardes wat verkry is nadat MKV by 25°C in 240 opgeberg is, was laag weens die klein persentasie poli-onversadigde vetsure teenwoordig in die vet. Dit vergelyk goed met die hoë waardes wat verkry is vir sonneblom-, canola- en olyfolie wat almal ryk aan poli-onversadigde vetsure is. Die minimale veranderinge in die vetsuurprofiel van MKF dui op die stabiliserende invloed van versadigde vetsure (C16:0 en C18:0) en oleïensuur. Die onstabiliteit van linoleïen- en lineensuur duidelik uit hierdie vetsure se oksidatiewe verval. 'n Afname van 7.41% en 12.80% is waargeneem tussen dae 0 en 240 vir die C18:2/C16:0 en C18:2/C18:0 verhoudings, onderskeidelik. Die voorspelling van die oksidatiewe status van die MKF monsters met behulp van FT-NIR spektroskopie was moontlik deur die ontwikkeling van kalibrasie modelle. 'n Totale datastel van 300 monsters, waarvan ongeveer 'n derde vir validasie aangewend is, is gebruik vir die kalibrasiemodelle. Met behulp van PCA (hoojkomponent analise) kon drie klassifiseerbare groepe by 0, 40 en 80-240 dae onderskei word. Die beste kalibrasiemodel vir PV het 'n standaardfout van voorspelling (SEP) van 0.46 meq.kg", 'n korrellasiekoëffisient (r) van 0.95, 'n oorhelling van 0.02 en 'n standaardfout van voorspelling (RMSEP) van 0.46 meq.kg" gehad. Die CD kalibrasiemodel (geen voorafverwerking) het 'n r van 0.89, SEP van 0.01% oorhelling van 0.001 en RMSEP van 0.01% gehad. Die AV kalibrasie het 'n SEP van 0.32 mmol.kg', oorhelling van 0.03, RMSEP van 0.32 mmol.kg" en r van 0.93 gehad. Die C18:2 en C18:3 modelle is saamgestel deur PLS (partial least squares) regressie. Waardes verkry vir C18:2 en C18:3 was onderskeidelik: SEP 0.32% en 0.05%, RMSEP, 0.32% en 0.05%, oorhelling 0.05 en 0.01 en r 0.82 en 0.54. In die geval van C18:1, C18:0 en C16:0, het die kalibrasies swakker statistiek korrellasies getoon. Goeie korrellasies is verkry tydens kalibrasie vir die C18:2/C16:0 en C18:2/C18:0 verhoudings.

The following thesis applies an experimental design framework to investigate properties of electron transfer kinetics and homogeneous catalytic reactions. The approach is model-based and the classical Butler-Volmer description is chosen to describe the fundamental electrochemical reaction at a conductive interface. The methodology focuses on two significant design variables: the applied potential at the electrode and mass transport mode induced by physical arrangement. An important problem in electrochemistry is the recovery of model parameters from output current measurements. In this work, the identifiability function is proposed as a measure of correspondence between the parameters and output variable. Under diffusion-limit conditions, plain Monte Carlo optimization shows that the function is globally non-identifiable, or equivalently the correspondence is generally non-unique. However by selecting linear voltammetry as the applied potential, the primary parameters in the Butler-Volmer description are theoretically recovered from a single set of data. The result is accomplished via applications of Sobol ranking to reduce the parameter set and a sensitivity equation to inverse these parameters. The use of hydrodynamic tools for investigating electron transfer reactions is next considered. The work initially focuses on the rotating disk and its generalization - the rocking disk mechanism. A numerical framework is developed to analyze the latter, most notably the derivation of a Levich-like expression for the limiting current. The results are then used to compute corresponding identifiability functions for each of the above configurations. Potential effectiveness of each device in recovering kinetic parameters are straightforwardly evaluated by comparing the functional values. Furthermore, another hydrodynamic device - the rotating drum, which is highly suitable for viscous and resistive solvents, is theoretically analyzed. Combined with previous results, this rotating drum configuration shows promising potential as an alternative tool to traditional electrode arrangement. The final chapter illustrates the combination of modulated input signal and appro- priate mass transport regimes to express electro-catalytic effects. An AC voltammetry technique plays an important role in this approach and is discussed step-by-step from simple redox reaction to the complete EC′ catalytic mechanism. A general algorithm based on forward and inverse Fourier transform functions for extracting harmonic currents from the total current is presented. The catalytic effect is evaluated and compared for three cases: macro, micro electrodes under diffusion control condition and in micro fluidic environments. Experimental data are also included to support the simulated design results.

A definition of fractional Fourier transform as the generalization of ordinary Fourier transform is given at the beginning. Then due to optical reasons the fractional transform of a so-called chirp functions is considered in both theory and practical simulations. Because of a quadratic phase factor which is common in the definition of the transform and some optical concepts, a comparison between these concepts such as Fresnel diffraction, spherical wave, thin lens and free space propagation and the transform has been done. Finally an optical setup for performing the fractional transform is introduced.

Visual inspection is the current method for determining if a wire rope needs to be removed from service. It can be time consuming and inaccurate. The point of this research is to prove that vibration testing could be used on rope to find damage. For this research, capacitive accelerometers were used. A program ran a Fast Fourier Transform (FFT) as the main analysis. From the data produced, it was determined that a damaged rope's vibration signature was different from the vibration signature of the undamaged rope. There were four different types of vibrations used: an impulse while measuring the axial response, a harmonic excitation while measuring the axial response and both transverses directions. The impulse did not provide consistent results to adequately find damage with an acceptable degree of confidence. The harmonic excitations did provide results that showed a different signature. This was the case for all three directions measured. As a result, it was determined that vibrations can be used to find damage in a wire rope.

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Orientador: Lucio Tunes dos Santos / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Matematica, Estatistica e Computação Cientifica / Made available in DSpace on 2018-08-06T01:09:38Z (GMT). No. of bitstreams: 1 Camargo_AnaCarolina_M.pdf: 3666219 bytes, checksum: 1c8c0d68b9fefa425dbd20b478818406 (MD5) Previous issue date: 2006 / Resumo: É comum ser preciso reconstruir funções cujas amostras não estão numa grade igualmente espaçada. Isto é devido ao fato que alguns dos algoritmos mais usados requerem amostras em uma grade Cartesiana regular (uniforme). Portanto, é necessário fazer uma reamostragem uniforme, i.e., interpolar as amostras não uniformes em um conjunto de pontos igualmente espaçados. Neste trabalho, primeiro mostramos que o problema de reamostragem pode ser formulado como um problema de resolver um sistema de equações lineares. Uma solução para este sistema pode ser encontrada utilizando a matriz pseudoinversa, um processo que é impraticável para um número grande de variáveis. A partir de características do problema, é possível desenvolver um algoritmo melhor, o qual usa apenas um número limitado de amostras para calcular cada amostra uniforme, transformando o problema original numa seqüência de sistemas lineares com menos variáveis. O resultado final pode ser visto como ótimo e computacionalmente eficiente. Aplicações são apresentadas para demonstrar a eficiência deste método / Abstract: Its common to be needed to reconstruct functions which samples falls on a nonequally spaced grid. This is due to the fact that some of the most used algorithms require samples in a regular (uniform) Cartesian grid. Therefore, it is necessary to make an uniform resampling, i.e., to interpolate the nonuniform samples in a set of equally spaced points. In this work, it is first shown that the resampling problem can be formulated as a problem of solving a system of linear equations. A solution for this system can be found using the pseudoinverse matrix, a process that is impractical for a large number of variables. From particular characteristics of the problem, it is possible to develop a better algorithm, which only uses a limited number of samples to calculate each uniform sample, transforming the original problem into a sequence of linear systems with less variables. The final result can be viewed as both optimal and computationally efficient. Applications are presented to demonstrate the efficiency of the method / Mestrado / Mestre em Matemática Aplicada

Chronic changes in cardiac load can cause the vertebrate heart to remodel. For ectotherms, ambient temperature can directly alter cardiac load. Therefore, long-term ambient temperature change can initiate a dynamic cardiac remodelling response to preserve cardiac function. The aims of my PhD thesis were to study the effects of chronic temperature change on the ectothermic heart and cardiovascular system, using the cold-active rainbow trout and the cold-dormant freshwater turtle. In contrast to the majority of previous studies, my experiments focused on the passive, rather than active, properties of the heart. In results chapters 3, 4, 5 and 6, I studied the effects of thermal remodelling on the rainbow trout heart. Chronic cold caused a global increase in chamber stiffness, both at the whole chamber and micromechanical level, with an associated myocardial fibrosis. In the ventricle and atrium there was an up-regulation of collagen promoting genes. In the ventricle, I found cold-induced hypertrophy of the spongy myocardium with an up-regulation of hypertrophic growth factors, which was associated with an increase in tissue lipid suggesting an increase in fatty acid oxidation (FAO). In the atrium, there was no hypertrophy, but there was an increase in extra-bundular sinus, suggesting chronic dilation. Chronic warming initiated an opposite response, with increased cardiac compliance associated with an up-regulation of collagen degrading genes in the ventricle and atrium. In the outflow tract (OFT) and atrium, this increased activity of matrix metalloproteinase (MMPs) and in the OFT abundance of MMPs was increased. The warmed ventricle showed atrophy of the spongy myocardium with a decrease in lipid and an increase in glycogen suggesting a switch in cellular energetics from FAO to glycolytic pathways. In chapters 7, 8 and 9, I studied the effects of thermal remodelling on the freshwater turtle heart. I found an in vivo decrease in systemic resistance causing an increased right to left cardiac shunt flow, associated with an increased elastin content of the major outflow vessels. Cold acclimation increased cardiac sensitivity to preload as well as whole chamber passive stiffness and micromechanical stiffness of tissue sections, associated ventricular fibrosis and increased collagen coherency. In addition, chronic cold decreased the gelatinase activity of MMPs and increased mRNA expression of a tissue inhibitor of MMPs. Furthermore, chronic cold was associated with a decrease in tissue lipid and phosphates, but an increase in tissue protein, glycogen and lactate. These changes in tissue biochemistry suggest a switch in cellular energetics from FAO to glycolytic pathways, likely due to the decreased oxygen availability associated with winter inactivity. Overall, the chambers of the ectothermic heart show distinct remodelling phenotypes, which likely reflect their in cardiac function. Thermal remodelling of the fish ventricle serves both cardio-protection, from the haemodynamic strain of changes in cardiac preload and afterload, as well as compensation for the direct effects of temperature. In the turtle, changes in compliance and cellular energetics of the ventricle suggest a cardio-protective mechanism preparing the heart for increased haemodynamic stress and hypoxic or anoxic conditions during inactive winter hibernation.

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The Fourier transform is one of the most useful tools in science and engineering and can be expanded to multi-dimensions and curvilinear coordinates. Multidimensional Fourier transforms are widely used in image processing, tomographic reconstructions and in fact any application that requires a multidimensional convolution. By examining a function in the frequency domain, additional information and insights may be obtained. In this thesis, the development of a symbolic computer algebra toolbox to compute two dimensional Fourier transforms in polar coordinates is discussed. Among the many operations implemented in this toolbox are different types of convolutions and procedures that allow for managing the toolbox effectively. The implementation of the two dimensional Fourier transform in polar coordinates within the toolbox is shown to be a combination of two significantly simpler transforms. The toolbox is also tested throughout the thesis to verify its capabilities.