897 resultados para Nuclear magnetic resonance spectroscopy


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Speech has both auditory and visual components (heard speech sounds and seen articulatory gestures). During all perception, selective attention facilitates efficient information processing and enables concentration on high-priority stimuli. Auditory and visual sensory systems interact at multiple processing levels during speech perception and, further, the classical motor speech regions seem also to participate in speech perception. Auditory, visual, and motor-articulatory processes may thus work in parallel during speech perception, their use possibly depending on the information available and the individual characteristics of the observer. Because of their subtle speech perception difficulties possibly stemming from disturbances at elemental levels of sensory processing, dyslexic readers may rely more on motor-articulatory speech perception strategies than do fluent readers. This thesis aimed to investigate the neural mechanisms of speech perception and selective attention in fluent and dyslexic readers. We conducted four functional magnetic resonance imaging experiments, during which subjects perceived articulatory gestures, speech sounds, and other auditory and visual stimuli. Gradient echo-planar images depicting blood oxygenation level-dependent contrast were acquired during stimulus presentation to indirectly measure brain hemodynamic activation. Lip-reading activated the primary auditory cortex, and selective attention to visual speech gestures enhanced activity within the left secondary auditory cortex. Attention to non-speech sounds enhanced auditory cortex activity bilaterally; this effect showed modulation by sound presentation rate. A comparison between fluent and dyslexic readers' brain hemodynamic activity during audiovisual speech perception revealed stronger activation of predominantly motor speech areas in dyslexic readers during a contrast test that allowed exploration of the processing of phonetic features extracted from auditory and visual speech. The results show that visual speech perception modulates hemodynamic activity within auditory cortex areas once considered unimodal, and suggest that the left secondary auditory cortex specifically participates in extracting the linguistic content of seen articulatory gestures. They are strong evidence for the importance of attention as a modulator of auditory cortex function during both sound processing and visual speech perception, and point out the nature of attention as an interactive process (influenced by stimulus-driven effects). Further, they suggest heightened reliance on motor-articulatory and visual speech perception strategies among dyslexic readers, possibly compensating for their auditory speech perception difficulties.

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Cardiovascular diseases (CVD) are, in developed countries, the leading cause of mortality. The majority of premature deaths and disability caused by CVD are due to atherosclerosis, a degenerating inflammatory disease affecting arterial walls. Early identification of lesions and initiation of treatment is crucial because the first manifestations quite often are major disabling cardiovascular events. Methods of finding individuals at high risk for these events are under development. Because magnetic resonance imaging (MRI) is an excellent non-invasive tool to study the structure and function of vascular system, we sought to discover whether existing MRI methods are able to show any difference in aortic and intracranial atherosclerotic lesions between patients at high risk for atherosclerosis and healthy controls. Our younger group (age 6-48) comprised 39 symptomless familial hypercholesterolemia (FH) patients and 25 healthy controls. Our older group (age 48-64) comprised 19 FH patients and 18 type 2 diabetes mellitus (DM) patients with coronary heart disease (CHD) and 29 healthy controls. Intracranial and aortic MRI was compared with carotid and femoral ultrasound (US). In neither age-group did MRI reveal any difference in the number of ischemic brain lesions or white matter hyperintensities (WMHIs) - possible signs of intracranial atherosclerosis - between patients and controls. Furthermore, MRI showed no difference in the structure or function of the aorta between FH patients and controls in either group. DM patients had lower compliance of the aorta than did controls, while no difference appeared between DM and FH patients. However, ultrasound showed greater plaque burden and increased thickness of carotid arterial walls in FH and DM patients in both age-groups, suggesting a more advanced atherosclerosis. The mortality of FH patients has decreased substantially after the late 1980´s when statin treatment became available. With statins, the progression of atherosclerotic lesions slows. We think that this, in concert with improvements in treatment of other risk factors, is one reason for the lack of differences between FH patients and controls in MRI measurements of the aorta and brain despite the more advanced disease of the carotid arteries assessed with US. Furthermore, whereas atherosclerotic lesions between different vascular territories correlate, differences might still exist in the extent and location of these lesions among different diseases. Small (<5 mm in diameter) WMHIs are more likely a phenomenon related to aging, but the larger ones may be the ones related to CVD and may be intermediate surrogates of stroke. The image quality in aortic imaging, although constantly improving, is not yet optimal and thus is a source of bias.

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A membrane with interpenetrating networks between poly(vinyl alcohol) (PVA) and poly(styrene sulfonic acid) (PSSA) coupled with a high proton conductivity is realized and evaluated as a proton exchange membrane electrolyte for a direct methanol fuel cell (DMFC). Its reduced methanol permeability and improved performance in DMFCs suggest the new blend as an alternative membrane to Nafion membranes. The membrane has been characterized by powder X-ray diffraction, scanning electron microscopy, time-modulated differential scanning calorimetry, and thermogravimetric analysis in conjunction with its mechanical strength. The maximum proton conductivity of 3.3×10−2 S/cm for the PVA–PSSA blend membrane is observed at 373 K. From nuclear magnetic resonance imaging and volume localized spectroscopy experiments, the PVA–PSSA membrane has been found to exhibit a promising methanol impermeability, in DMFCs. On evaluating its utility in a DMFC, it has been found that a peak power density of 90 mW/cm2 at a load current density of 320 mA/cm2 is achieved with the PVA–PSSA membrane compared to a peak power density of 75 mW/cm2 at a load current density of 250 mA/cm2 achievable for a DMFC employing Nafion membrane electrolyte while operating under identical conditions; this is attributed primarily to the methanol crossover mitigating property of the PVA–PSSA membrane.

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Lipid analysis is commonly performed by gas chromatography (GC) in laboratory conditions. Spectroscopic techniques, however, are non-destructive and can be implemented noninvasively in vivo. Excess fat (triglycerides) in visceral adipose tissue and liver is known predispose to metabolic abnormalities, collectively known as the metabolic syndrome. Insulin resistance is the likely cause with diets high in saturated fat known to impair insulin sensitivity. Tissue triglyceride composition has been used as marker of dietary intake but it can also be influenced by tissue specific handling of fatty acids. Recent studies have shown that adipocyte insulin sensitivity correlates positively with their saturated fat content, contradicting the common view of dietary effects. A better understanding of factors affecting tissue triglyceride composition is needed to provide further insights into tissue function in lipid metabolism. In this thesis two spectroscopic techniques were developed for in vitro and in vivo analysis of tissue triglyceride composition. In vitro studies (Study I) used infrared spectroscopy (FTIR), a fast and cost effective analytical technique well suited for multivariate analysis. Infrared spectra are characterized by peak overlap leading to poorly resolved absorbances and limited analytical performance. In vivo studies (Studies II, III and IV) used proton magnetic resonance spectroscopy (1H-MRS), an established non-invasive clinical method for measuring metabolites in vivo. 1H-MRS has been limited in its ability to analyze triglyceride composition due to poorly resolved resonances. Using an attenuated total reflection accessory, we were able to obtain pure triglyceride infrared spectra from adipose tissue biopsies. Using multivariate curve resolution (MCR), we were able to resolve the overlapping double bond absorbances of monounsaturated fat and polyunsaturated fat. MCR also resolved the isolated trans double bond and conjugated linoleic acids from an overlapping background absorbance. Using oil phantoms to study the effects of different fatty acid compositions on the echo time behaviour of triglycerides, it was concluded that the use of long echo times improved peak separation with T2 weighting having a negligible impact. It was also discovered that the echo time behaviour of the methyl resonance of omega-3 fats differed from other fats due to characteristic J-coupling. This novel insight could be used to detect omega-3 fats in human adipose tissue in vivo at very long echo times (TE = 470 and 540 ms). A comparison of 1H-MRS of adipose tissue in vivo and GC of adipose tissue biopsies in humans showed that long TE spectra resulted in improved peak fitting and better correlations with GC data. The study also showed that calculation of fatty acid fractions from 1H-MRS data is unreliable and should not be used. Omega-3 fatty acid content derived from long TE in vivo spectra (TE = 540 ms) correlated with total omega-3 fatty acid concentration measured by GC. The long TE protocol used for adipose tissue studies was subsequently extended to the analysis of liver fat composition. Respiratory triggering and long TE resulted in spectra with the olefinic and tissue water resonances resolved. Conversion of the derived unsaturation to double bond content per fatty acid showed that the results were in accordance with previously published gas chromatography data on liver fat composition. In patients with metabolic syndrome, liver fat was found to be more saturated than subcutaneous or visceral adipose tissue. The higher saturation observed in liver fat may be a result of a higher rate of de-novo-lipogenesis in liver than in adipose tissue. This thesis has introduced the first non-invasive method for determining adipose tissue omega-3 fatty acid content in humans in vivo. The methods introduced here have also shown that liver fat is more saturated than adipose tissue fat.

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Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.

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A direct observation of ferroelectric domains in x-irradiated KH2AsO4 and KD2AsO4 using electron paramagnetic resonance (EPR), and in the case of KH2AsO4 also using electron-nuclear double-resonance (ENDOR), is reported. The nature of the observed domain splittings and consequently the effects of an externally applied electric field on the EPR and ENDOR spectra are explained. Moreover, the higher resolution possible with the ENDOR technique, has, for the first time, made it possible to use protons as microscopic probes and to identify in general lines from individual domains in all directions.

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The proton magnetic resonance spectra of single crystals of Na2Zn(SO4)2·4H2O have been investigated and the orientations of the water molecules have been determined. Using the heavy atom structure determined by X-rays a system of hydrogen bonds between water and sulphate oxygens has been proposed.

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Proton magnetic resonance spectra of single crystals of two Tutton's salts, K2Zn (SO4)2.6H22O and K2Mg (SO4)2.6H2O, have been studied and the orientations of the water molecules in the structure have been determined. Using the heavy-atom structure of (NH4) 2Mgt(SO4)2.6H2O as determined by x-ray diffraction, a system of hydrogen bonds between the water and sulfate oxygens in Tutton's salts has been proposed. It appears that the x-ray structure needs considerable refinement.