This research investigates various applications of diffuse correlation spectroscopy (DCS) on in-vivo human muscle tissue, both at rest and during dynamic exercise. Previously suspected muscle tissue relative blood flow (rBF) baseline shift during extended measurement with DCS and DCS-Near infrared spectroscopy (NIRS) hybrid optical systems are verified, quantified, and resolved by redesign of optical probe and alteration in optical probe attachment methodology during 40 minute supine bed rest baseline measurements. We then translate previously developed occlusion techniques, whereby rBF and relative oxygen consumption rV̇O2 are calibrated to initial resting absolute values by use of a venous occlusion (VO) and arterial occlusion (AO) protocol, respectively, to the lower leg (gastrocnemius) and these blood flows are cross validated at rest by strain gauge venous plethysmography (SGVP). Methods used to continuously observe 0.5Hz, 30% maximum voluntary isometric contraction (MVIC) plantar flexion exercise via dynamometer are adapted for our hybrid DCS-Imagent diffuse optical flow-oximeter in the medial gastrocnemius. We obtain healthy control muscle tissue hemodynamic profiles for key parameters BF, V̇O2, oxygen saturation (StO2), deoxyhemoglobin, oxyhemoglobin, and total hemoglobin concentrations ([Hb], [HbO2], and THC respectively), as well as systemic mean arterial pressure (MAP) and pulse rate (PR), at rest, during VO/AO, during dynamic exercise and during 15 minute recovery periods. Next, we began investigation of muscle tissue hemodynamic disease states by performing a feasibility pilot study using limited numbers of controls and peripheral arterial disease (PAD) patients using the translated methods/techniques to determine the ability of our technology to assess differences in these populations.

In this thesis methodological developments have been made for the description of flexible conjugated dyes in room temperature spectrum calculations. The methods in question target increased accuracy and efficiency by combining classical molecular dynamics (MD) simulations with time-dependent response theory spectrum calculations. For absorption and fluorescence spectroscopies a form of conformational averaging is used, where the final spectrum is obtained as an average of spectra calculated for geometries extracted from ground and excited state MD simulations. For infrared and Raman spectroscopies averaged spectra are calculated based on individual spectra, obtained for zero-temperature optimized molecular structures, weighted by conformational statistics from MD trajectories. Statistics for structural properties are also used in both cases to gain additional information about the systems, allowing more efficient utilization of computational resources. As it is essential that the molecular mechanics description of the system is highly accurate for methods of this nature to be effective, high quality force field parameters have been derived, describing the molecules of interest in either the MM3 or CHARMM force fields. These methods have been employed in the study of three systems. The first is a platinum(II) actylide chromophore used in optical power limiting materials, for which a ultraviolet/visible absorption spectrum has been calculated. The second is a family of molecular probes called luminescent conjugated oligothiophenes, used to detect and characterize amyloid proteins, for which both absorption and fluorescence spectra have been calculated. Finally, infrared and Raman spectra have been calculated for a group of branched oligothiophenes used in organic solar cells. In addition, solvation effects have been studied for conjugated poly\-eletrolytes in water, resulting in the development of two solvation models suitable for this class of molecules. The first uses a quantum meachanics/molecular mechanics (QM/MM) description, in which the solute mole\-cule is described using accurate quantum mechanical methods while the surrounding water molecules are described using point charges and polarizable point dipoles. The second discards the water entirely and removes the ionic groups of the solute. The QM/MM model provides highly accurate results while the cut-down model gives results of slightly lower quality but at a much reduced computational cost. Finally, a study of protein-dye interactions has been performed, with the goal of explaining changes in the luminescence properties of the LCO chromophores when in the presence of amyloid proteins. Results were less than conclusive.

Pentameric ligand-gated ion channels (pLGICs) are membrane bound receptors found in the nervous system. They are responsible for detecting neurotransmitters released from neurons and subsequently mediating responses of the cells on which they are found. Thus, pLGICs play an invaluable role in communication between cells of the nervous system and understanding their function is pivotal to understanding how the nervous system works in general. One factor which is known to mediate pLGIC function is lipids found in the membrane environment in which pLGICs are embedded. This dissertation explores the various ways in which lipids interact with and modulate the function of pLGIC. Potential mechanisms and biological consequences of this modulation will be presented and discussed within the context of our current state of knowledge of pLGIC and nervous system function.

Production of and demand for Canadian canola meal have been increased yearly. In order to improve the competitiveness of canola meal domestically and internationally, as well as to develop potential markets for canola meal, it is necessary to develop canola meal-based products that have high feed values and can be easily transported. The objectives of this research were: 1) to investigate the effects of temperature and time of conditioning during pelleting process on the nutritive values of canola meal in terms of chemical profiles, protein and carbohydrate subfractions, and energy values, using the AOAC procedures, CNCPS v6.1 and NRC (2001), respectively; 2) to detect the effects of temperature and time of conditioning during the pelleting process on rumen degradation and intestinal digestion characteristics and predicted protein supply of canola meal, using the in situ procedure, the three-step in vitro procedure, and the NRC 2001 model; and 3) to determine pelleting-induced changes in spectral characteristics of molecular structures of canola meal using Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) with univariate and multivariate analysis, and reveal the relationship between molecular structures of protein and carbohydrate and nutrient values, rumen degradation and intestinal digestion characteristics, and predicted protein supply of canola meal. Three different conditioning temperatures (70, 80 and 90ºC) and two different conditioning time (50 and 75 sec) were applied in this research. Two different batches of canola meal from a commercial feed company were selected. A randomized complete block design (RCBD) with 3 × 2 factorial arrangement was employed in this research. Molecular spectral functional groups related to protein, cellulosic compounds, and carbohydrates were used in the spectral study. This research indicated: 1) soluble crude protein (SCP) was decreased and neutral detergent insoluble CP (NDICP) was increased with increasing temperature; 2) the lowest protein rumen degradation of pellets was observed at conditioning temperature of 90 ºC and protein rumen degradation was increased by pelleting; 3) the amount of protein digested in the small intestine tended to increase with increasing conditioning temperature; 4) pelleting under different temperatures and time in the current study shifted the protein digestion site to the rumen, rather than to the small intestine; 5) with respect to predicted protein supply, based on the NRC 2001 model, increasing conditioning temperature tended to increase the metabolizable protein supply of canola meal pellets to dairy cattle; 6) changes in the molecular structure of canola meal induced by pelleting can be detected by ATR-FTIR; 7) not only protein molecular structure characteristics but also carbohydrate molecular structure characteristics play important roles in determining nutrient values, rumen degradation and intestinal digestion characteristics, and the predicted protein supply of canola meal.

The fate and behaviour of hydrophobic organic compounds (e.g. pesticides) in soils are largely controlled by sorption processes. Recent findings suggest that the chemical properties of soil organic carbon (OC) significantly control the extent of sorption of such compounds in soil systems. However, currently there is no practical tool to integrate the effects of OC chemistry into sorption predictions. Therefore, the K [subscript]oc model, which relies on the soil OC content (foc), is used for predicting soil sorption coefficients (K[subscript]d) of pesticides. The K[subscript]oc model can be expressed as K[subscript]d = K[subscript]oc × foc, where K[subscript]oc is the OC-normalized sorption coefficient for the compound. Hence, there is a need for a prediction tool that can effectively capture the role of both the chemical structural variation of OC as well as foc in the prediction approach. Infrared (IR) spectroscopy offers a potential alternative to the K[subscript]oc approach because IR spectra contain information on the amount and nature of both organic and mineral soil components. The potential of mid-infrared (MIR) spectroscopy for predicting K[subscript]d values of a moderately hydrophobic pesticide, diuron, was investigated. A calibration set of 101 surface soils from South Australia was characterized for reference sorption data (K[subscript]d and K[subscript]oc) and foc as well as IR spectra. Partial least squares (PLS) regression was employed to harness the apparent complexity of IR spectra by reducing the dimensionality of the data. The MIR-PLS model was developed and validated by dividing the initial data set into corresponding calibration and validation sets. The developed model showed promising performance in predicting K[subscript]d values for diuron and proved to be a more efficacious than the K[subscript]oc model. The significant statistical superiority of the MIR-PLS model over the K[subscript]oc model was caused by some calcareous soils which were outliers for the K[subscript]oc model. Apart from these samples, the performance of the two compared models was essentially similar. The existence of carbonate peaks in the MIR-PLS loadings of the MIR based model suggested that carbonate minerals may interfere or affect the sorption. This requires further investigation. Some other concurrent studies suggested excellent quality of prediction of soil properties by NIR spectroscopy when applied to homogenous samples. Next, therefore, the performance of visible near-infrared (VNIR) and MIR spectroscopy was thoroughly compared for predicting both foc and diuron K[subscript]d values in soils. Some eleven calcareous soils were added to the initial calibration set for an attempt to further investigate the effect of carbonate minerals on sorption. MIR spectroscopy was clearly a more accurate predictor of foc and K[subscript]d in soils than VNIR spectroscopy. Close inspection of spectra showed that MIR spectra contain more relevant and straightforward information regarding the chemistry of OC and minerals than VNIR and thus useful in modelling sorption and OC content. Moreover, MIR spectroscopy provided a better (though still not great) estimation of sorption in calcareous soils than either VNIR spectroscopy or the K[subscript]oc model. Separate research is recommended to fully explore the unusual sorption behaviour of diuron in calcareous soils. In the last experiment, two dimensional (2D) nuclear magnetic resonance/infrared heterospectral correlation analyses revealed that MIR spectra contain specific and clear signals related to most of the major NMR-derived carbon types whereas NIR spectra contain only a few broad and overlapped peaks weakly associated with aliphatic carbons. 2D heterospectral correlation analysis facilitated accurate band assignments in the MIR and NIR spectra to the NMR-derived carbon types in isolated SOM. In conclusion, the greatest advantage of the MIR-PLS model is the direct estimation of Kd based on integrated properties of organic and mineral components. In addition, MIR spectroscopy is being used increasingly in predicting various soil properties including foc, and therefore, its simultaneous use for K[subscript]d estimation is a resource-effective and attractive practice. Moreover, it has the advantage of being fast and inexpensive with a high repeatability, and unlike the K[subscript]oc approach, MIR-PLS shows a better potential for extrapolating applications in data-poor regions. Where available, MIR spectroscopy is highly recommended over NIR spectroscopy. 2D correlation spectroscopy showed promising potential for providing rich insight and clarification into the thorough study of soil IR spectra. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1415416 / Thesis (Ph.D.) - University of Adelaide, School of Earth and Environmental Sciences, 2009

The fate and behaviour of hydrophobic organic compounds (e.g. pesticides) in soils are largely controlled by sorption processes. Recent findings suggest that the chemical properties of soil organic carbon (OC) significantly control the extent of sorption of such compounds in soil systems. However, currently there is no practical tool to integrate the effects of OC chemistry into sorption predictions. Therefore, the K [subscript]oc model, which relies on the soil OC content (foc), is used for predicting soil sorption coefficients (K[subscript]d) of pesticides. The K[subscript]oc model can be expressed as K[subscript]d = K[subscript]oc × foc, where K[subscript]oc is the OC-normalized sorption coefficient for the compound. Hence, there is a need for a prediction tool that can effectively capture the role of both the chemical structural variation of OC as well as foc in the prediction approach. Infrared (IR) spectroscopy offers a potential alternative to the K[subscript]oc approach because IR spectra contain information on the amount and nature of both organic and mineral soil components. The potential of mid-infrared (MIR) spectroscopy for predicting K[subscript]d values of a moderately hydrophobic pesticide, diuron, was investigated. A calibration set of 101 surface soils from South Australia was characterized for reference sorption data (K[subscript]d and K[subscript]oc) and foc as well as IR spectra. Partial least squares (PLS) regression was employed to harness the apparent complexity of IR spectra by reducing the dimensionality of the data. The MIR-PLS model was developed and validated by dividing the initial data set into corresponding calibration and validation sets. The developed model showed promising performance in predicting K[subscript]d values for diuron and proved to be a more efficacious than the K[subscript]oc model. The significant statistical superiority of the MIR-PLS model over the K[subscript]oc model was caused by some calcareous soils which were outliers for the K[subscript]oc model. Apart from these samples, the performance of the two compared models was essentially similar. The existence of carbonate peaks in the MIR-PLS loadings of the MIR based model suggested that carbonate minerals may interfere or affect the sorption. This requires further investigation. Some other concurrent studies suggested excellent quality of prediction of soil properties by NIR spectroscopy when applied to homogenous samples. Next, therefore, the performance of visible near-infrared (VNIR) and MIR spectroscopy was thoroughly compared for predicting both foc and diuron K[subscript]d values in soils. Some eleven calcareous soils were added to the initial calibration set for an attempt to further investigate the effect of carbonate minerals on sorption. MIR spectroscopy was clearly a more accurate predictor of foc and K[subscript]d in soils than VNIR spectroscopy. Close inspection of spectra showed that MIR spectra contain more relevant and straightforward information regarding the chemistry of OC and minerals than VNIR and thus useful in modelling sorption and OC content. Moreover, MIR spectroscopy provided a better (though still not great) estimation of sorption in calcareous soils than either VNIR spectroscopy or the K[subscript]oc model. Separate research is recommended to fully explore the unusual sorption behaviour of diuron in calcareous soils. In the last experiment, two dimensional (2D) nuclear magnetic resonance/infrared heterospectral correlation analyses revealed that MIR spectra contain specific and clear signals related to most of the major NMR-derived carbon types whereas NIR spectra contain only a few broad and overlapped peaks weakly associated with aliphatic carbons. 2D heterospectral correlation analysis facilitated accurate band assignments in the MIR and NIR spectra to the NMR-derived carbon types in isolated SOM. In conclusion, the greatest advantage of the MIR-PLS model is the direct estimation of Kd based on integrated properties of organic and mineral components. In addition, MIR spectroscopy is being used increasingly in predicting various soil properties including foc, and therefore, its simultaneous use for K[subscript]d estimation is a resource-effective and attractive practice. Moreover, it has the advantage of being fast and inexpensive with a high repeatability, and unlike the K[subscript]oc approach, MIR-PLS shows a better potential for extrapolating applications in data-poor regions. Where available, MIR spectroscopy is highly recommended over NIR spectroscopy. 2D correlation spectroscopy showed promising potential for providing rich insight and clarification into the thorough study of soil IR spectra. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1415416 / Thesis (Ph.D.) - University of Adelaide, School of Earth and Environmental Sciences, 2009

Mémoire (M.Ress.Renouv.)-- Université du Québec à Chicoutimi, 1993. / Document électronique également accessible en format PDF. CaQCU

Thesis (MSc Food Sc) (Food Science)--University of Stellenbosch, 2005. / Near infrared spectroscopy (NIRS) and UV/Vis spectrophotometric methods were investigated as rapid and/or more economical methods to quantify the major monomeric phenolic compounds, soluble solid content (SSC), total polyphenol content (TPC) and total antioxidant activity (TAA) of green rooibos and Cyclopia genistoides.

Thesis (Msc Food Sc (Food Science))--University of Stellenbosch, 2005. / Near infrared (NIR) spectroscopy prediction models were developed for the rapid determination of the peroxide value, free fatty acid content, specific extinction coefficients at 232 and 270 nm, thiobarbituric acid reactive substances value, pigment, total polyphenol, oleic acid, linoleic acid and saturated fatty acid contents ...

Thesis (MSc Food Sc)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Hectolitre mass (HLM) measurements allow rapid and accurate determination of grain density. HLM devices from different countries (Australia, Canada, France, Germany, South Africa, the United Kingdom and the United States of America [USA]) have been investigated for their effect on the HLM measurements of oats. In addition, the potential of near infrared (NIR) hyperspectral imaging has been evaluated to distinguish between oat samples with different HLM values. Comparing HLM measurements obtained from the respective devices, the USA and the South African devices resulted in significantly (P<0.05) lower HLM values compared to the other devices where as the German device resulted in higher values (P<0.05) than the other devices. HLM values from all the devices were highly correlated with intra-class correlation (ICC) consistency values of at least 0.90. These high correlations would allow direct replacement of the South African device with any of the other devices. The equipment selected as replacement should ideally be calibrated according to the ISO 7971-3 standard (i.e. the device currently used in Germany). HLM values significantly (P<0.05) increased when oat samples were rubbed before measurements were made, indicating the importance of continuation of this sample preparation step. The investigation on the effect of the operator on HLM determinations showed that the unskilled operator measured HLM values significantly different to those obtained by the skilled operator. This emphasises the importance of training in spite of HLM measurements being a simple procedure. A poor correlation (r = 0.18) was found between protein content and HLM values of oat samples. Moisture content significantly affected the HLM values of oats and results clearly showed a decrease in HLM values with increasing moisture content. Scanning electron microscope (SEM) micrographs revealed that the starch granules became swollen and that they increased in size with an increase in moisture content, resulting in a decrease in HLM. NIR hyperspectral imaging offers the testing of individual grains non-destructively. This is often required by plant breeders because they subsequently need to plant selected grains. NIR offers this option to plant breeders. NIR hyperspectral imaging, which combines NIR spectroscopy with digital imaging, was used to distinguish between six oat samples with varying HLM values. NIR spectroscopic differences were observed between the images of the two samples with the highest and lowest HLM values (60.2 and 49.35 kg.hL-1). Less distinct differences were observed in the NIR hyperspectral images of two samples differing by less than 2.0 kg.hL-1. Although mixed oat samples were used, these preliminary results established the possible use of NIR hyperspectral imaging in evaluating oat samples from breeding trials. The use of this technique could also be extended to evaluation of other quality characteristics of oats. / AFRIKAANSE OPSOMMING: Hektolitermassa- (HLM-)metings maak snelle en akkurate bepaling van korreldigtheid moontlik. HLM-toestelle van verskillende lande (Australië, Kanada, Frankryk, Duitsland, Suid-Afrika, die Verenigde Koninkryk en die Verenigde State van Amerika) is ondersoek vir hulle uitwerking op die HLM-metings van hawer. Daarby is die potensiaal van nabyinfrarooi- (NIR-)hiperspektrale beelding geëvalueer om tussen hawermonsters met verskillende HLM-waardes te onderskei. Tydens vergelyking van HLM-metings verkry van die onderskeie toestelle, het die Amerikaanse en die Suid-Afrikaanse toestelle beduidend (P<0.05) laer HLM-waardes opgelewer in vergelyking met die ander toestelle terwyl die Duitse toestel hoër waardes (P<0.05) as die ander toestelle getoon het. Daar was hoë korrelasies tussen die HLM waardes verkry van die apparate met intraklaskorrelasie (IKK) konsekwentheidwaardes van ten minste 0.90. Hierdie hoë korrelasies sou direkte vervanging van die Suid-Afrikaanse toestel met enige van die ander toestelle moontlik maak. Die toerusting gekies as vervanging sou ideaal gesproke in ooreenstemming met die ISO 7971-3 standaard gekalibreer kon word (bv. die toestel wat tans in Duitsland gebruik word). HLM-waardes het beduidend (P<0.05) verhoog toe hawermonsters gevryf is voor metings gemaak is, wat dui op die belang van verlengde gebruik van hierdie stap tydens die voorbereiding van monsters. Die ondersoek na die uitwerking van die operateur op HLM-bepalings het getoon dat die onervare operateur HLM-waardes beduidend verskillend gemeet het teenoor dié verkry deur die ervare operateur. Dit beklemtoon die belang van opleiding ten spyte daarvan dat HLM-metings ’n eenvoudige prosedure is. ’n Swak korrelasie (r = 0.18) is aangetref tussen proteïeninhoud en HLM-waardes van hawermonsters. Voginhoud het die HLM-waardes van hawer beduidend beïnvloed en resultate het duidelik ’n styging in HLM-waardes met verhoging van die voginhoud getoon. Aftaselektronmikroskoop- (AEM-)mikrobeelde het aangedui dat die styselgranules swel en in grootte toeneem met verhoging van die voginhoud, wat aanleiding gee tot ’n verlaging in HLM. NIR-hiperspektrale beelding maak die toets van individuele korrels op niedestruktiewe wyse moontlik. Dit word dikwels deur plantkwekers vereis aangesien hulle na toetsing uitgesoekte korrels moet plant. Nabyinfrarooi bied hierdie opsie aan plantkwekers. NIR-hiperspektrale beelding, wat NIRspektroskopie met digitale beelding kombineer, is gebruik om te onderskei tussen ses hawermonsters met wisselende HLM-waardes. NIR-spektroskopiese verskille tussen die beelde van die twee monsters met die hoogste en laagste HLM-waardes (60.2 en 49.35 kg.hL-1) is waargeneem. Minder duidelike verskille is in die NIR-hiperspektrale beelde van twee monsters wat met minder as 2.0 kg.hL-1 verskil het, waargeneem. Alhoewel gemengde hawermonsters gebruik is, het hierdie voorlopige resultate die moontlike gebruik van NIR-hiperspektrale beelding by die evaluering van hawermonsters van kweekproewe vasgestel. Die gebruik van hierdie tegniek sou ook uitgebrei kon word tot die evaluering van ander kwaliteitseienskappe van hawer.