Atrial fibrillation (AF), the most common type of cardiac arrythmia, has been a huge concern of public health. It affects more than 6 million people in the United States and over 33 million people worldwide. In the current standard of care, an electrogram and geometry map is generated by electroanatomic mapping (EAM) using a mapping catheter, to determine the origins of irregular heart rhythm. Followed by radiofrequency ablation (RFA) using ablation catheter, the targeted sites are ablated as lesions to change the electrical conduction pathway of abnormal electrogram, thus restoring the patients to normal sinus heart rhythm with minimally invasive procedure. However, a significant proportion of patients suffer from AF recurrences and requires repeated procedures, due to the lack of reliable methods to assess the cardiac structural substrates which are the potential maintaining mechanism of AF signals. In recent years, optical imaging modalities are developed to compensate this limitation, among which near-infrared spectroscopy (NIRS) is a catheter-based technique to enable direct, independent characterization of cardiac tissue pathology from spectrum morphology. In this thesis, we validate the capability of NIRS to generate map with repeatability and identify AF substrate to improve the efficacy of treatment. First, a near-infrared imaging spectroscopy was combined with an electromagnetic tracking modality, and the system was operated with high acquisition speed and real-time display to generate high-density map. Further, the robustness of NIRS optical parameters was assessed under blood mapping and various, large catheter-tissue contact angle, to simulate the dynamic circumstance of clinical procedures. A classification algorithm was introduced to predict lesion probability including both PBS and blood data, as well as to evaluate the mapping equivalence of blood and PBS. Next, the spatial resolution and the sampling density requirement of NIRS mapping method was characterized based on small gap, and the spectral properties of gap was assessed comparing to normal tissue and lesion by statistical analysis and machine learning. Lastly, we demonstrate the identification of human left atrial complex substrates using NIRS catheter with different source-detector-separations (SDSs), and reported the spectral features for the AF-related structures such as fibrosis and adipose. To summarize, the catheter-based NIRS technology is robust for in-vivo application and structural target localization, with the potential to enhance the recognition of underlying AF pathology and improve treatment efficacy.

Exercise-induced hypoalgesia (EIH) is the reduction in pain sensitivity following exercise. High-intensity or prolonged exercise is typically required to elicit an EIH response, but there is limited evidence suggesting that low-load resistance exercise with blood flow restriction (LL+BFR) may be able to elicit a robust EIH response. The purpose of these investigations was to assess the magnitude, duration, and proposed mechanisms of EIH following LL+BFR, LL with normobaric systemic hypoxemia, BFR only without exercise, high-load exercise, and a control intervention. The first study evaluated local and systemic pain pressure threshold and tolerance responses one-hour post-exercise. The results indicated that LL+BFR induced similar EIH responses to high-load resistance exercise 0- and 15-minutes post-exercise but only LL+BFR elicited an EIH response present 60-minutes post-exercise. The second study evaluated neuromuscular and perceptual responses, both proposed EIH mechanisms, during exercise. Similar neuromuscular responses were observed in all interventions. Participants reported higher ratings of perceived exertion during LL+BFR and high-load exercise, and higher levels of perceived pain during LL+BFR. These results suggested that despite high levels of motor unit recruitment, there were divergent EIH responses. However, increased pain during exercise may be a mediating factor of EIH after resistance exercise. The third study evaluated peripheral and central cardiovascular responses, which have also been hypothesized to mediate EIH. LL+BFR resulted in greater increases in systolic blood pressure during the first set of exercise, and diastolic blood pressure during all sets of exercise. LL+BFR and BFR only attenuated changes in heart rate variability (HRV). LL+BFR induced the largest increase in deoxyhemoglobin and total hemoglobin and lowered tissue saturation index. BFR only progressively increased oxyhemoglobin and total hemoglobin levels. The local and systemic cardiovascular responses suggested that prolonged EIH following LL+BFR could be related to increased central or peripheral cardiovascular stress.

La spectroscopie infrarouge à matrice à plan focal (PAIRS) est utilisée pour étudier la déformation et la relaxation des polymères à très haute vitesse, soit de 46 cm/s, grâce à sa résolution temporelle de quelques millisecondes. Des mesures complémentaires de spectroscopie infrarouge d’absorbance structurale par modulation de la polarisation (PM-IRSAS) ont été réalisées pour suivre des déformations plus lentes de 0,16 à 1,6 cm/s avec une résolution temporelle de quelques centaines de millisecondes. Notre étude a permis d’observer, à haute vitesse de déformation, un nouveau temps de relaxation (τ0) de l’ordre d’une dizaine de millisecondes qui n’est pas prédit dans la littérature. Le but de cette étude est de quantifier ce nouveau temps de relaxation ainsi que de déterminer les effets de la température, de la masse molaire et de la composition du mélange sur ce dernier. Des mesures effectuées sur du polystyrène (PS) de deux masses molaires différentes, soit 210 et 900 kg/mol, à diverses températures ont révélé que ce temps est indépendant de la masse molaire mais qu’il varie avec la température. Des mesures effectuées sur des films composés de PS900 et de PS deutéré de 21 kg/mol, ont révélé que ce temps ne dépend pas de la composition du mélange et que la longueur des chaînes de PS n’a aucun impact sur celui-ci. D’autres mesures effectuées sur des films de PS900 mélangé avec le poly(vinyl méthyl éther) (PVME) ont révélé que ce temps est identique pour le PS900 pur et le PS900 dans le mélange, mais qu’il est plus court pour le PVME, de l’ordre de quelques millisecondes. / Planar array infrared spectroscopy (PAIRS) was used to study the fast deformation and relaxation of polymers at s draw rate of 46 cm/s, giving millisecond time resolution. Complementary measurements by polarization modulation infrared structural absorbance spectroscopy (PM-IRSAS) were conducted to probe slower deformations (0.16 to 1.6 cm/s) with a time resolution of a few hundreds of milliseconds. Our study allowed the observation, after fast deformation, of a new relaxation time (τ0), on the order of tens of milliseconds, which was not predicted in the literature. The aim of this work is to quantify this new relaxation time and to determine how it is affected by molecular weight, temperature, and blending. Measurements performed on polystyrene (PS) with two different molecular weights (210 and 900 kg/mol) at various temperatures revealed that the new relaxation time is independent of the molecular weight, but that it varies with temperature. Measurements performed on film blends of PS900 with deuterated PS of low molecular weight (21 kg/mol) indicated that this time is unaffected by blending and that the PS chain length has no impact on it. Measurements on films of PS blended with poly(vinyl methyl ether) (PVME) revealed that it is identical for pure PS and for PS in the blends, but that it is shorter, on the order of few milliseconds, for PVME.

Die intratracheale Applikation von Perfluorcarbonen (PFC) in ungeschädigte Lungen, z.B. als Röntgenkontrastmittel und zur PFC-induzierten cerebralen Kühlung, wird derzeit diskutiert. Ob es aufgrund der Dichte und Sauerstofflöslichkeit der PFC zu einer Beeinflussung der cerebralen Oxygenierung und Hämodynamik durch die pulmonale PFC Applikation kommt, ist bisher unbekannt. Änderungen der Konzentration von cerebralem oxygeniertem und totalem Hb koennen mittels Near-infrared Spectroscopy gemessen werden. I.) Effekt durch die PFC-Applikation in gesunde Lungen neugeborener Ferkel: Es wurden zwei verschiedene Applikationsgeschwindigkeiten (30 ml PFC pro kg Körpergewicht als Bolusgabe versus 1,5 ml/min pro kg) und zwei Füllvolumen (30 versus 10 ml/kg) verglichen. Die Bolusgabe bewirkt einen sofortigen Abfall des PaO2 und der cerebralen Oxygenierung, bei langsamer Gabe des gleichen Volumens ist dies weniger ausgeprägt. Mit 10 ml/kg PFC fand sich nahezu keine Beeinflussung der Parameter. II.) Effekte der Änderung der FiO2 in PFC-gefüllten Lungen: Hierfür wurden Änderungen der FiO2 unter konventioneller Druckbeatmung vor PFC-Applikation und unter PFC-Füllung (30 oder 10 ml/kg PFC) verglichen. Beide PFC-Volumen (mit FiO2 1,0) bedingten PaO2-Werte wie unter CMV mit FiO2 von 0,5. Mit 30 ml/kg PFC kam es unter FiO2 von 0,5 zur Abnahme des cerebralen oxygenierten Hb. Zusammenfassend ergibt sich, dass die Applikation von 10 ml PFC/kg bevorzugt werden sollte. Bei kompletter Füllung der Lungen werden durch langsame Applikation cerebrale Nebenwirkungen minimiert. In PFC-gefüllten gesunden Lungen ist zum Erhalt der systemischen und cerebralen Oxygenierung die FiO2 zu erhöhen. / Intratracheal administration of perfluorochemicals (PFC) has been suggested for reasons other than respiratory insufficiency, such as pulmonary imaging and PFC-associated brain cooling. Due to their high density and oxygen solubility, PFC application has been described to affect systemic hemodynamics and oxygenation during liquid ventilation. Whether the PFC application into healthy lungs or changes in inspired oxygen fraction (FiO2) in PFC-filled healthy lungs affects cerebral hemodynamics is not known. Changes in the concentration of cerebral oxygenated and total Hb can be measured by near-infrared spectroscopy (NIRS). I.) Initial effects of PFC application into healthy lungs of newborn piglets: Two different filling modes (rapid versus slow) and two different filling volumes (slow filling of 30 versus 10 ml PFC/kg body weight) were compared. Rapid filling caused an immediate drop of systemic and cerebrale oxygenation, which was less prominent by filling 30 ml/kg PFC slowly. Almost no changes for all parameters were found with 10 ml kg/PFC. II.) Effects of variations in FiO2 in the PFC filled lungs of healthy piglets: Changes in FiO2 during conventional mechanical ventilation (CMV) prior to PFC-application and in the PFC-filled lungs (30 ml/kg or 10 ml/kg PFC) were compared. Both PFC-volumes (at a FiO2 of 1.0) caused PaO2-values that were similar to CMV with FiO2 of 0.5. In the 30 ml/kg PFC group a reduction of cerebral oxygenated Hb was found at FiO2 of 0.5. According to the data application of 10 ml/kg PFC should be preferred. If complete filling of the lung is needed, the slow administration of PFC minimizes cerebral side effects. In PFC- filled healthy lungs an increase in FiO2 is necessary to maintain systemic and cerebral oxygenation.

Thesis submitted in fulfilment of the requirements for the degree Master of Technology Chemistry in the Faculty of (Science) Supervisor: Professor T.N. van der Walt Bellville campus Date submitted: October 2011 / It is important to quantify polymeric components in a coating because they greatly influence the performance of a coating. The difficulty associated with analysis of polymers by Fourier transform infrared (FTIR) analysis’s is that colinearities arise from similar or overlapping spectral features. A quantitative FTIR method with attenuated total reflectance coupled to multivariate/ chemometric analysis is presented. It allows for simultaneous quantification of 3 polymeric components; a rheology modifier, organic opacifier and styrene acrylic binder, with no prior extraction or separation from the paint. The factor based methods partial least squares (PLS) and principle component regression (PCR) permit colinearities by decomposing the spectral data into smaller matrices with principle scores and loading vectors. For model building spectral information from calibrators and validation samples at different analysis regions were incorporated. PCR and PLS were used to inspect the variation within the sample set. The PLS algorithms were found to predict the polymeric components the best. The concentrations of the polymeric components in a coating were predicted with the calibration model. Three PLS models each with different analysis regions yielded a coefficient of correlation R2 close to 1 for each of the components. The root mean square error of calibration (RMSEC) and root mean square error of prediction (RMSEP) was less than 5%. The best out-put was obtained where spectral features of water was included (Trial 3). The prediction residual values for the three models ranged from 2 to -2 and 10 to -10. The method allows paint samples to be analysed in pure form and opens many opportunities for other coating components to be analysed in the same way.

Pelchem, a commercial subsidiary of Necsa (South African Nuclear Energy Corporation), produces a range of commercial fluorocarbon products while driving research and development initiatives to support the fluorine product portfolio. One such initiative is to develop improved analytical techniques to analyse product composition during development and to quality assure produce. Generally the C–F type products produced by Necsa are in a solution of anhydrous HF, and cannot be directly analyzed with traditional techniques without derivatisation. A technique such as vibrational spectroscopy, that can analyze these products directly without further preparation, will have a distinct advantage. However, spectra of mixtures of similar compounds are complex and not suitable for traditional quantitative regression analysis. Multivariate data analysis (MVA) can be used in such instances to exploit the complex nature of spectra to extract quantitative information on the composition of mixtures. A selection of fluorocarbon alcohols was made to act as representatives for fluorocarbon compounds. Experimental design theory was used to create a calibration range of mixtures of these compounds. Raman and infrared (NIR and ATR–IR) spectroscopy were used to generate spectral data of the mixtures and this data was analyzed with MVA techniques by the construction of regression and prediction models. Selected samples from the mixture range were chosen to test the predictive ability of the models. Analysis and regression models (PCR, PLS2 and PLS1) gave good model fits (R2 values larger than 0.9). Raman spectroscopy was the most efficient technique and gave a high prediction accuracy (at 10% accepted standard deviation), provided the minimum mass of a component exceeded 16% of the total sample. The infrared techniques also performed well in terms of fit and prediction. The NIR spectra were subjected to signal saturation as a result of using long path length sample cells. This was shown to be the main reason for the loss in efficiency of this technique compared to Raman and ATR–IR spectroscopy. It was shown that multivariate data analysis of spectroscopic data of the selected fluorocarbon compounds could be used to quantitatively analyse mixtures with the possibility of further optimization of the method. The study was a representative study indicating that the combination of MVA and spectroscopy can be used successfully in the quantitative analysis of other fluorocarbon compound mixtures. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Pelchem, a commercial subsidiary of Necsa (South African Nuclear Energy Corporation), produces a range of commercial fluorocarbon products while driving research and development initiatives to support the fluorine product portfolio. One such initiative is to develop improved analytical techniques to analyse product composition during development and to quality assure produce. Generally the C–F type products produced by Necsa are in a solution of anhydrous HF, and cannot be directly analyzed with traditional techniques without derivatisation. A technique such as vibrational spectroscopy, that can analyze these products directly without further preparation, will have a distinct advantage. However, spectra of mixtures of similar compounds are complex and not suitable for traditional quantitative regression analysis. Multivariate data analysis (MVA) can be used in such instances to exploit the complex nature of spectra to extract quantitative information on the composition of mixtures. A selection of fluorocarbon alcohols was made to act as representatives for fluorocarbon compounds. Experimental design theory was used to create a calibration range of mixtures of these compounds. Raman and infrared (NIR and ATR–IR) spectroscopy were used to generate spectral data of the mixtures and this data was analyzed with MVA techniques by the construction of regression and prediction models. Selected samples from the mixture range were chosen to test the predictive ability of the models. Analysis and regression models (PCR, PLS2 and PLS1) gave good model fits (R2 values larger than 0.9). Raman spectroscopy was the most efficient technique and gave a high prediction accuracy (at 10% accepted standard deviation), provided the minimum mass of a component exceeded 16% of the total sample. The infrared techniques also performed well in terms of fit and prediction. The NIR spectra were subjected to signal saturation as a result of using long path length sample cells. This was shown to be the main reason for the loss in efficiency of this technique compared to Raman and ATR–IR spectroscopy. It was shown that multivariate data analysis of spectroscopic data of the selected fluorocarbon compounds could be used to quantitatively analyse mixtures with the possibility of further optimization of the method. The study was a representative study indicating that the combination of MVA and spectroscopy can be used successfully in the quantitative analysis of other fluorocarbon compound mixtures. / Thesis (M.Sc. (Chemistry))--North-West University, Potchefstroom Campus, 2012.

Afin de progresser dans la compréhension de la structure de vibration-rotation de l'acétylène dans son état électronique fondamental, un modèle global a été développé avec succès pour trois de ses isotopologues, permettant d'attribuer de nouvelles données de spectres enregistrés sous diverses conditions expérimentales. L'ensemble des programmes d'analyse rovibrationnelle globale conçus à l'Université Catholique de Louvain par le Pr. A. Fayt et al. ont été utilisés pour répondre aux demandes de collaborateurs tels que les Prs. A. Campargue, A. Jolly ou encore R. Georges dans le cadre de plusieurs problèmes de type spectroscopique, notamment pour des applications astrophysiques. Le modèle global et son pouvoir prédictif mis ainsi à l'épreuve, nous avons démontré la validité de nos jeux de paramètres pour ces trois molécules.<p><p>Concernant l'isotopologue principal, $H^{12}C^{12}CH$, 14 nouvelles bandes ont été mises à jour à partir de spectres enregistrés en CRDS à Grenoble par A. Campargue et al. Une analyse rovibrationnelle globale a été effectuée jusqu'à une énergie de 8600 cm$^{-1}$. 10750 raies ont été ajustées simultanément sur les 12137 attribuées dans la littérature. 266 paramètres ont été déterminés par la méthode de moindres-carrés. La déviation standard sans dimension du fit est de 0.92. La bande $u_{5}$-$u_{4}$, centrée vers 117 cm$^{-1}$ a été simulée. La valeur du moment de transition associé, $ / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

Non-invasive methods to evaluate skeletal muscle oxidative capacity have beenemerging as a viable substitute for invasive methods in recent years. One ofthose methods utilises near-infrared spectroscopy (NIRS) to calculate V O2mrecovery off-kinetics following an exercise. The data analysis of the measuredsignals from the NIRS is still done manually in a time-consuming and dauntingprocess. The present thesis aimed to develop software, associated with theNIRS method, capable of analysing the recovery from a repeated arterialocclusion protocol following an exercise to assess muscle oxidative capacity.Additionally, to analyse the recovery from ischemic preconditioning as a singletest to assess muscle oxidative capacity. A method that has never been utilisedbefore.11 active, healthy subjects were analysed to calculate their recovery rate.Subjects underwent ischemic preconditioning before exercising for 6 minutesat 80% of gas exchange threshold. A repeated arterial occlusion protocol wascarried out after the exercise. A software was developed in R that utilised linearregression as well as exponential fitting to calculate the recovery rate of eachsubject during both the ischemic preconditioning and the occlusion protocol.The calculated results were compared to predetermined recovery rate results ofeach subject. The calculated results of the repeated arterial occlusion protocolgave similar results to the predetermined ones and even more data on eachsubject’s recovery from an exercise. The calculated results of the ischemicpreconditioning were promising and implied that ischemic preconditioning asa single test can be utilised as a method to assess muscle oxidative capacity.However, further research is required to confirm it. / Icke-invasiva metoder för att utvärdera skelettmuskulaturens oxidativa förmågahar på senare år blivit en användbar ersättning för invasiva metoder. Nearinfrared spectroscopy (NIRS) är en utav dessa metoder och har använts föratt beräkna V O2m återhämtning off-kinetics efter träning. Dataanalysen av deuppmätta signalerna från NIRS görs fortfarande manuellt i en tidskrävandeoch felbenägen process. Syftet med den här uppsatsen var att utveckla enprogramvara som kopplad till NIRS metoden, kan analysera återhämtningenfrån ett protokoll med upprepade arteriella ocklusioner efter träning för attutvärdera skelettmuskulaturens oxidativa förmåga. Dessutom att analyseraåterhämtningen från ischemic preconditioning som ett enda test för att utvärderaskelettmuskulaturens oxidativa förmåga. En metod som aldrig tidigare använts.11 aktiva, friska försökspersoner analyserades för att beräkna deras återhämtningshastighet.Försökspersonerna genomgick ischemic preconditioning innan de tränadei 6 minuter med 80% av gasutbyteströskeln. Ett protokoll med upprepadearteriella ocklusioner genomfördes efter träningen. En programvara utveckladesi R som använde sig av linjär regression och monoexponentiell funktionsanpassningför att beräkna återhämtningshastigheten för varje försöksperson under bådeichemic preconditioning och ocklusionprotokollet. De beräknade resultatenjämfördes med förutbestämda resultat av återhämtningshastigheten för varjeförsöksperson. De beräknade resultaten av ocklusionprotokollet gav liknanderesultat som de förutbestämda och gav ännu fler uppgifter om varje försökspersonåterhämtning efter träning. De beräknade resultaten av ischemic preconditioningvar lovande och indikerade att ischemic preconditioning som ett enda testkan användas som en metod för att utvärdera skelettmuskulaturens oxidativaförmåga. Det krävs dock ytterligare forskning för att bekräfta detta.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / Two cationic polymerizable surfactants (surfmers), (11-acryloyloxyundecyl)dimethyl-(2-hydroxyethyl)ammonium bromide (Ethanol surfmer) and (11-acryloyloxyundecyl)-dimethylethylammonium bromide (Ethyl surfmer) were synthesized and characterized. Characterization was done using, conductivity, Fourier transform infra-red spectroscopy (FT-IR), electrospray mass spectrometry (ESMS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), small angle X-ray scattering (SAXS) and polarized light microscopy with a heating stage. These surfmers and the commercial surfactant cetyltrimethylammonium bromide (CTAB) were used for functionalization of sodium montmorillonite (Na+-MMT), thereby forming organophilic MMT. The functionalization of MMT dispersions was carried out by ion exchange of the sodium ions in Na+-MMT by surfactants in aqueous media. Organophilic MMT clays were then dispersed in styrene and subsequently polymerized by a free radical reaction to yield polystyrene-clay nanocomposites. This in-situ intercalative polymerization process resulted in an exfoliated structure for Ethyl surfmer modified clay, a partially exfoliated structure for Ethanol surfmer modified clay and an intercalated structure for CTAB modified clay. These nanocomposite structures were confirmed by SAXS and transmission electron microscopy (TEM). The nanocomposites exhibited enhanced thermal stability. All the nanocomposites exhibited an inferior storage modulus (GI) at low clay contents relative to polystyrene. At higher clay loadings there was an increase in GI which was dependent on the level of clay dispersion and the clay content. All the nanocomposites showed an increase in glass transition temperature (Tg), regardless of the amount of clay and the level of clay dispersion. There was a shift towards higher temperatures and broadening of the tan δ peak, which was in turn dependent on the amount of clay and level of clay dispersion. Molecular masses of polystyrene-clay nanocomposites were in the range 105 g/mol for bulk polymerization relative to 103 g/mol for solution polymerization as revealed by gel permeation chromatography (GPC).