The closed shell structures of certain all-carbon fragments originally observed in mass spectroscopy experiments leads to the enhanced stability of these species, known as fullerenes, which have excited sufficient interest amongst chemists and physicists over the last decade to warrant the award of the 1996 Nobel Prize for Chemistry to their discoverers. ¶ Studies of the stability, symmetry, and consequent remarkable properties of fullerenes began in earnest in 1991 with the development of a technique enabling the production and purification of macroscopic quantities of material. The best known and most widely studied fullerene is the truncated icosahedral C[subscript 60] molecule, which forms the basis of the present work. ¶ One important property of C[subscript 60] is that it forms salts with sufficiently electropositive species, such as the alkali metals. The resulting salts contain C[subscript 60] anions and are known as fullerides. Certain of these salts display metallic behaviour, and some superconduct at temperatures as high as 33 K. ¶ Three aspects of fulleride research are addressed in this work. These are: i) the preparation, crystal structure determination and superconductivity characterization of several new fullerides, particularly those including ammonia as an additional intercalant; ii) the electronic structure of the C[superscript n-, subscript 60] (n = 1 - 6) anions, as probed by solution-phase near infrared absorption spectroscopy; and iii) the molecular dynamics of a number of fullerides, superconducting and non-superconducting, by inelastic neutron scattering. ¶ This work has grown out of an Honours project also concerning C[subscript 60], the combined duration of the two studies covering essentially the entire history of this widely and competitively studied field.

<p>The European Union Water Framework Directive (WFD), with initiatives to manage surface water resources, has increased the need for fast and inexpensive methods for monitoring conditions in streams. The objective of this thesis is to assess the potential of near-infrared spectroscopy (NIRS) of epilithic material to become such method. NIRS, which is a technique that is commonly used in industry for process monitoring and quality control of products, registers the chemical properties of organic material on a molecular level. Epilithic material, i.e. the layer of dead and alive material that covers stone surfaces in streams, is continuously influenced by the stream water that flows over it, and it has the potential to integrate chemical and biological conditions over time. The temporal integration is a significant factor, since conditions in streams can change within hours or days. The thesis consists of two published papers. In the first paper a new sampler for epilithic material, the Stone Brusher, was described and the performance evaluated. The Stone Brusher is designed to take qualitative or semi-quantitative samples of epilithic material from stones at 7–50 cm water depth. The epilithic material is dislodged from the stone surface with a rotating brush enclosed in a chamber, and the material is drawn up directly into the sample bottle with an air-cylinder. The operator takes a sample quickly and without putting hands into the water. The sampler is made of plastic, stainless steel and aluminium and weighs 3.1 kg. It is designed to meet the demand for standardized sampling for research and environmental monitoring and to improve working conditions for sampling personnel. The equipment allows sampling from surfaces of bedrock and large stones that cannot be lifted from the bottom. Using data of near-infrared spectroscopy and diatom analyses, this new sampler was evaluated in comparison to the toothbrush method, a primitive method which is the current standard in EU. The results indicate that the Stone Brusher reduces sampling variability compared with the toothbrush method.</p><p>In the second paper, the Stone Brusher was used to collect epilithic material from 65 sites (42 uncontaminated and 23 contaminated) from streams in the widespread mining area called the Skellefte-district in Västerbotten, northern Sweden, in order to test the hypothesis that impact on the epilithic material caused by emissions from mining and mining-related industries can be detected using NIRS. The epilithic material was filtered onto glass fibre filters, measured by NIRS, and the results were modelled using Principal Component Analysis (PCA). The NIRS approach was evaluated by comparing it with the results of chemical and diatom analyses of the same samples. Based on PCA, the NIRS data distinguished contaminated from uncontaminated sites and performed slightly better than chemical analyses and clearly better than diatom analyses. Of the streams designated a priori as contaminated, 74 % were identified as contaminated by NIRS, 65 % by chemical analysis and 26 % by diatom analysis. Unlike chemical analyses of water or of epilithic material samples, NIRS data reflect biological impacts in the streams. Given that, and the simplicity of NIRS-analyses, further studies to assess the use of NIRS of epilithic material are justified. NIRS has the potential to become a fast method for screening in regions where large numbers of streams occur to find impacted streams or as a routine method for temporal monitoring in selected streams for early detection of environmental impact, similar to process monitoring in industry.</p>

The European Union Water Framework Directive (WFD), with initiatives to manage surface water resources, has increased the need for fast and inexpensive methods for monitoring conditions in streams. The objective of this thesis is to assess the potential of near-infrared spectroscopy (NIRS) of epilithic material to become such method. NIRS, which is a technique that is commonly used in industry for process monitoring and quality control of products, registers the chemical properties of organic material on a molecular level. Epilithic material, i.e. the layer of dead and alive material that covers stone surfaces in streams, is continuously influenced by the stream water that flows over it, and it has the potential to integrate chemical and biological conditions over time. The temporal integration is a significant factor, since conditions in streams can change within hours or days. The thesis consists of two published papers. In the first paper a new sampler for epilithic material, the Stone Brusher, was described and the performance evaluated. The Stone Brusher is designed to take qualitative or semi-quantitative samples of epilithic material from stones at 7–50 cm water depth. The epilithic material is dislodged from the stone surface with a rotating brush enclosed in a chamber, and the material is drawn up directly into the sample bottle with an air-cylinder. The operator takes a sample quickly and without putting hands into the water. The sampler is made of plastic, stainless steel and aluminium and weighs 3.1 kg. It is designed to meet the demand for standardized sampling for research and environmental monitoring and to improve working conditions for sampling personnel. The equipment allows sampling from surfaces of bedrock and large stones that cannot be lifted from the bottom. Using data of near-infrared spectroscopy and diatom analyses, this new sampler was evaluated in comparison to the toothbrush method, a primitive method which is the current standard in EU. The results indicate that the Stone Brusher reduces sampling variability compared with the toothbrush method. In the second paper, the Stone Brusher was used to collect epilithic material from 65 sites (42 uncontaminated and 23 contaminated) from streams in the widespread mining area called the Skellefte-district in Västerbotten, northern Sweden, in order to test the hypothesis that impact on the epilithic material caused by emissions from mining and mining-related industries can be detected using NIRS. The epilithic material was filtered onto glass fibre filters, measured by NIRS, and the results were modelled using Principal Component Analysis (PCA). The NIRS approach was evaluated by comparing it with the results of chemical and diatom analyses of the same samples. Based on PCA, the NIRS data distinguished contaminated from uncontaminated sites and performed slightly better than chemical analyses and clearly better than diatom analyses. Of the streams designated a priori as contaminated, 74 % were identified as contaminated by NIRS, 65 % by chemical analysis and 26 % by diatom analysis. Unlike chemical analyses of water or of epilithic material samples, NIRS data reflect biological impacts in the streams. Given that, and the simplicity of NIRS-analyses, further studies to assess the use of NIRS of epilithic material are justified. NIRS has the potential to become a fast method for screening in regions where large numbers of streams occur to find impacted streams or as a routine method for temporal monitoring in selected streams for early detection of environmental impact, similar to process monitoring in industry.

Functional neuroimaging techniques such as near-infrared spectroscopy (NIRS) have been studied in brain-computer interface (BCI) development. Previous research has suggested that the addition of a second brain-monitoring modality may improve the accuracy of a NIRS-BCI. The objective of this study was to determine whether the classification accuracies achievable by a multimodal BCI, which combines NIRS and transcranial Doppler ultrasonography (TCD) signals, can exceed those attainable using a unimodal NIRS-BCI or TCD-BCI. Nine able-bodied subjects participated in the study. Simultaneous measurements were made with NIRS and TCD instruments while participants were prompted to perform a verbal fluency task or to remain at rest, within the context of a block-stimulus paradigm. In five of nine (55.6%) participants, classification accuracies with the NIRS-TCD system were significantly higher (p<0.05) than with NIRS or TCD systems alone. Our results suggest that multimodal neuroimaging may be a promising approach towards improving the accuracy of future BCIs.

Functional neuroimaging techniques such as near-infrared spectroscopy (NIRS) have been studied in brain-computer interface (BCI) development. Previous research has suggested that the addition of a second brain-monitoring modality may improve the accuracy of a NIRS-BCI. The objective of this study was to determine whether the classification accuracies achievable by a multimodal BCI, which combines NIRS and transcranial Doppler ultrasonography (TCD) signals, can exceed those attainable using a unimodal NIRS-BCI or TCD-BCI. Nine able-bodied subjects participated in the study. Simultaneous measurements were made with NIRS and TCD instruments while participants were prompted to perform a verbal fluency task or to remain at rest, within the context of a block-stimulus paradigm. In five of nine (55.6%) participants, classification accuracies with the NIRS-TCD system were significantly higher (p<0.05) than with NIRS or TCD systems alone. Our results suggest that multimodal neuroimaging may be a promising approach towards improving the accuracy of future BCIs.

Les naines brunes sont des astres incapables de déclencher et soutenir des réactions nucléaires dans leur cœur. En l’absence de cette source d’énergie, leur luminosité diminue avec le temps jusqu’à leur extinction complète. Leur flux aux longueurs d’onde de 0,8 à 2,35 μm est particulièrement altéré par l’humidité contenue dans l’atmosphère terrestre, ce qui complique l’étude de ces astres. Le but de la présente recherche est de vérifier si la division par un spectre d’étoile A0 est un moyen de corriger l’altération causée par l’atmosphère terrestre sur cette partie de leur spectre. Tout d’abord, des notions, pertinentes à la compréhension de ce travail, sont abordées. L’introduction présente quelques notions sur les naines brunes et sur l’atmosphère terrestre. Le deuxième chapitre concerne le traitement des données. Il traite de la calibration, de la mise en évidence du problème de non-répétabilité de la position de la fente du spectromètre SIMON ainsi que de ses causes. Il porte aussi sur l’uniformisation de la réponse des pixels et de la soustraction du ciel pour extraire les spectres. La méthode employée pour étudier l’effet de l’atmosphère terrestre sur les spectres de naines brunes y est présentée. Le troisième chapitre analyse les résultats obtenus par l’utilisation de l’étoile de référence de type A0 comme calibration pour corriger le spectre de naine brune, en assumant un même effet de l’atmosphère terrestre sur les deux types d’astres. Nous ne pouvons conclure, avec certitude, que l’absorption tellurique affecte de la même façon les deux spectres ni de quelle façon exactement ils sont affectés. Une recherche supplémentaire nécessitant de nouvelles prises de données à des masses d’air et à des taux d’humidité variés est requise. / Brown dwarfs are celestial bodies unable to sustain nuclear reactions. For this reason their luminosity declines until complete extinction. Their flux, particularly in the band between 0,8 and 2,35 μm, is absorbed by the water vapor in the terrestrial atmosphere. The goal of this research is to find a way to correct this part of their spectra affected by this effect. First, general notions needed to understand the project are exposed. The second chapter concerns the data reduction. The calibration, the problem of the position repeatability of the slit of the spectrometer SIMON and his cause are exposed. It discusses techniques to even up the pixels’ response and the substraction of the sky from the spectra. The method used to study the atmosphere effect on brown dwarf spectra is presented. The third chapter analyses the results that use the A0 reference star to correct the brown dwarf spectrum. We cannot conclude that the A0 spectrum is affected in the same way as the brown dwarf spectrum by the terrestrial atmosphere. The data from a single night do not allow a good analysis of this effect as a function of air mass and humidity level. Others missions are needed.

The eldana stalk borer (Eldana saccharina Walker) is the most serious pest of the Southern African sugarcane industry, and it is imperative that effective control measures are available to minimize economic damage. Because conventional control methods have had limited success, cultivar resistance is seen as the most viable method of controlling infestation. However, due to the space- and time-consuming nature of the present screening methods, only small numbers of cultivars can be tested relatively late in the Plant Breeding selection programme. Increased resistance in breeding and selection populations is therefore slow. Buds are a preferred entry point of eldana larvae as they are softer than the rind that is present on the rest of the stalk surface. Preliminary results by other workers suggested that near infrared spectroscopy (NIRS) could provide a rapid screening method for the chemical profile in bud scales, the outer coating of buds and therefore the first contact point of an invading larva. If feasible, analysis of samples using this method could be done in the South African Sugar Experiment Station's (SASEX) stage two selection trials, providing an early indication of eldana resistance on large numbers of cultivars, without the necessity of separate trials. However, knowledge of how environments, position of bud scales on the stalk and age affect NIRS is required in order to determine the feasibility of the method. Planting of a trial with an identical set of genotypes across a range of environments, sampled at a number of ages, would provide the necessary information on environmental effects, whilst simultaneously providing the necessary range of samples to develop a calibration between bud scale chemical profiles and eldana resistance ratings. Inheritance patterns of the characteristics being measured is also required if they are to be used in a breeding programme. The original work by Rutherford (1993) was carried out on only five calibration sets (a set of standard clones with relatively well-known eldana resistance ratings), and different sets were not comparable due to what was assumed to be environmental differences between calibration sets. One aspect of the current experiment was to examine more closely the effect of genotype x environment interaction (G x E) on the performance of the NIRS technique under a range of conditions. Two sites were chosen to represent the conditions encountered in trials carried out by SASEX. The crops were sampled at three ages, representing the range of ages at which sugarcane is harvested in South Africa. Two locations on the stalk were also examined, top and bottom, for removal of bud scales, based on the assumption that aging of bud scales may affect chemical composition. A new NIRSystems 6500 instrument was acquired during the course of this study. Data from the new instrument indicated that there were no longer differences between the different calibration sets, and therefore no longer differences between environments. Spectra for different samples were very close, the differences being of the same scale as those recorded with repeated measures of the same samples, or between the readings for the standard solvent solution. This led to the conclusion that the differences observed on the original NIRSystems 5000 instrument were due to instrument error, not environmental differences. More importantly, the different calibration sets were not comparable despite being similar to each other. Prediction from one calibration set to another was low. These observations led to the conclusion that NIRS was not a suitable method for determining chemical compounds associated with tolerance of sugarcane genotypes to eldana borer. The original NIRS instrument was subject to error, and the small number of calibration sets included in the study led to the erroneous conclusion that NIRS was suitable for the prediction of varietal tolerance to eldana. With the acquisition of the new instrument, the errors generated by the old instrument became apparent. With the increase in number of calibration sets included in the study, it also became apparent that a global calibration covering all environments was not possible. An analysis of the heritability of the chemical compounds associated with eldana resistance was also included in this study. A biparental progeny design of 24 crosses with 33 unselected offspring per cross was used. This trial would have been analysed once the calibration had been developed using the environmental trial, and it would have provided knowledge of the breeding behaviour of the chemical compounds associated with tolerance to eldana. Because the NIRS technique proved to be unsuitable for detection of chemical compounds associated with eldana resistance, the heritability of these chemical compounds could not be studied. As the NIRS study did not produce data, the G x E interaction analysis and determination of heritability was applied to the bud scale mass data set. This study showed a relatively low positive correlation between bud scale mass and resistance to eldana. The broad sense heritability estimate for bud scale mass from the G x E interaction analysis was 0.45, and the narrow sense heritability estimate from parent-offspring regression analysis was approximately 0.27, suggesting a low degree of genetic determination in bud scale mass. The G x E interaction analyses gave varying results depending on the method used. The ANOVA analysis suggested that ages, sites and years had an effect on bud scale mass, while deviation from maximum plot showed no significance for G x E interactions. The number and choice of genotypes selected as unstable also varied with the method used to determine the stability of individual genotypes. Regression analysis and rank order analysis revealed a number of unstable genotypes, whilst stability variance and ecovalence, which produced similar results, detected only two unstable genotypes. In the rank order analysis correction of data to remove genotype effect, reduced the number of unstable genotypes, suggesting that the G x E interaction effect was partially confounded with the bud scale mass of the genotypes. This was a more reliable method than the uncorrected rank order analysis, and would be the preferred analysis type of all those tried. / Thesis (M.Sc.)-University of Natal, Pietermaritzburg, 2003.

This study combines noninvasive hybrid diffuse optical spectroscopies [near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS)] with occlusive calibration for continuous measurement of absolute blood flow (BF), tissue blood oxygenation (StO2), and oxygen consumption rate (VO2) in exercising skeletal muscle. Subjects performed rhythmic dynamic handgrip exercise, while an optical probe connected to a hybrid NIRS/DCS flow-oximeter directly monitored oxy-, deoxy-, and total hemoglobin concentrations ([HbO2], [Hb], and [tHb]), StO2, relative BF (rBF), and relative VO2 (rVO2) in the forearm flexor muscles. Absolute baseline BF and VO2 were obtained through venous and arterial occlusions, respectively, and used to calibrate continuous relative parameters. Previously known problems with muscle fiber motion artifact in optical measurements were mitigated with a novel dynamometer-based gating algorithm. Nine healthy young subjects were measured and results validated against previous literature findings. Ten older subjects with fibromyalgia and thirteen age-matched healthy controls were then successfully measured to observe differences in hemodynamic and metabolic response to exercise. This study demonstrates a novel application of NIRS/DCS technology to simultaneously evaluate quantitative hemodynamic and metabolic parameters in exercising skeletal muscle. This method has broad application to research and clinical assessment of disease (e.g. peripheral vascular disease, fibromyalgia), treatment evaluation, and sports medicine.

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.

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.