No description available.

Techn. University, Diss., 2003--Berlin.

No description available.

Electron spin echo envelope modulation (ESEEM) spectroscopy is widely used to study the radical pairs created during the primary steps of photosynthesis. In this thesis the analysis of ESEEM spectra is improved, and some new applications and variations of this experiment suggested. Experimental spectra from species such as P⁺Q^-_A, the secondary radical pair formed in the reaction centre of the bacterium Rhodobacter sphaeroides, give information about the exchange and dipolar couplings between the radicals. The model used to analyse the data affects the results; this thesis suggests two improvements. First, the effect of anisotropic hyperfine couplings in the radicals is considered by the addition of a single spin-1/2 nucleus to the model. This approach suggests that previous models neglecting the effect of nuclei may have been slightly in error. Secondly, several model fittings are performed in the time domain. This approach avoids the Fourier transformation to the frequency domain so that experimental dead-time does not corrupt the data. An excellent fit to experimental data is found with a model containing one spin-1/2 nucleus on each radical. The hyperfine coupling parameters resulting from the fit are consistent with independent experimental results. Use is made of the method of Cramér-Rao lower bounds to assess the precision to which experimental parameters are determined from a time domain curve fitting. It is shown that the lower bounds may also be used to determine the optimum sampling strategy for the experiment. An example is given of the novel use of ESEEM to determine the distance between the radicals in the strongly coupled, uncorrelated radical pair Q^-_AQ^-_B ESEEM has not yet been used for this purpose, and the simulated spectra produced here indicate that the experiment could be used to evaluate the dipolar coupling and hence the inter-radical distance. This thesis considers the possibility of performing ESEEM at higher frequencies than are usually considered. Calculations show that the increased resolution of the g-tensors allow an experiment performed at the W-band frequency of 95 GHz to make a correlation between the relative orientations of the radicals and the dipolar axis, information which has previously been unavailable from a single experiment.

A Ressonância Magnética Nuclear em baixa resolução (RMN-BR) vem sendo aplicada no controle e certificação de qualidade na indústria. Para acelerar e automatizar as análises tem sido proposto o uso de RMN online, com carreamento de amostras por uma esteira. Apesar do grande potencial, as metodologias utilizadas podem provocar o aquecimento da amostra, causando erros nas medidas, além de reduzir a vida útil do equipamento. Assim, nesse trabalho de doutorado foram desenvolvidas sequências de eco de spin para medidas de RMN-BR online utilizando baixa potência de RF (radiofrequência), baseadas nas técnicas CP, Carr-Purcell, e CPMG, Carr-Purcell-Meiboom-Gill, utilizando baixos ângulos de refocalização, LRFA (Low Refocusing Flip Angle). Observou-se que LRFA de 45&deg; (CPMG45) pode fornecer valores de tempo de relaxação transversal (T2) com erros inferiores a 5% em campos magnéticos (B0) com homogeneidade equivalente a largura de linha de &Delta;&nu; &le; 15 Hz. Em B0 menos homogêneos (&Delta;&nu; &ge; 100 Hz), a escolha dos LRFA deve considerar a redução do sinal e o aumento de T2, que se torna dependente do tempo de relaxação longitudinal (T1). CP90 produz ecos entre os pulsos de refocalização que decaem para valores mínimos dependente de T2* (constante de tempo do Decaimento Livre da Indução). O sinal obtido por CP90 aumenta de valores mínimos para o regime de estado estacionário (EE) com constante de tempo T* = 2T1T2/(T1+T2) e amplitude MCP90 = M0T2/(T1+T2), a mesma constante e a mesma amplitude observada para o sinal de Precessão Livre em Onda Contínua (CWFP - Continuous Wave Free Precession), por isso foi denominada CP-CWFP. A principal vantagem de CP-CWFP ocorre para amostras com T1 ~ T2. CP-CWFP apresenta um decaimento abrupto da amplitude do sinal antes de aumentar e alcançar o EE. Essa diferença na amplitude torna o ajuste de T* menos dependente da razão sinal/ruído, sendo mais eficiente que CWFP para medidas de T1 e T2 em B0 baixos, onde T1 e T2 tendem a ter valores similares. No método de alternância de fase (AF) em CPMG90AF (y\'/-y\') e CP90AF (x\'-x\') os sinais entraram num EE, nesse caso CPMG90AF e CP90AF tiveram comportamentos similares ao CP-CWFP, sendo mais uma alternativa para obtenção de T1 e T2. Para CPMG, a redução do ângulo de refocalização para 90&deg; equivale a uma redução de 75% da potência incidida na amostra. CP-CWFP pode ser uma técnica mais robusta para análises em espectrômetros de RMN de bancada em controle de qualidade industrial, com B0 < 0,5 T (20 MHz) e em ferramentas de RMN utilizadas em poços de petróleo com B0 ~ 0,05 T (2 MHz). As análises por métodos estatísticos demonstraram que CPMG e CPMG90, CWFP e CP-CWFP apresentam alta correlação entre si, demonstrando que uma técnica pode substituir a outra nas análises online de sementes oleaginosas. / Low Resolution Nuclear Magnetic Resonance (LR-NMR) has been applied in quality control and certification in industry. To speed up the analysis the online NMR has been proposed. Despite LR-NMR online potential, some problems related to equipment overload occurs. It is due to methodologies used that can cause an increase in sample temperature and consequently errors in measurements as well reduction on equipment durability. Thus, Carr-Purcell, CP and Meiboom-Gill, CPMG using low refocusing flip angles (LRFA) were developed. It was observed that LRFA as low as 45&deg; (CPMG45) can provide transverse relaxation time values (T2) with errors below 5% for homogeneous field (&Delta;&nu; &le; 15Hz). For a less homogeneous magnetic field (&Delta;&nu; &ge; 100 Hz) the choice of the LRFA has to take into account the reduction in the intensity of the CPMG signal and the increase in the time constant of the CPMG decay that also becomes dependent on longitudinal relaxation time (T1). The Carr-Purcell (CP) pulse sequence, with LRFA, produces echoes midway between refocusing pulses that decay to a minimum value dependent on T2* (Free Induction Decay time constant - FID). When &tau; &gt; T2*, the signal increased to reach a Steady-State Free Precession regime (SSFP) after the minimum value and was composed of FID signal after each pulse and an echo, before the next pulse. CP90 signal increased from the minimum value to the steady-state regime with a time constant (T*) = 2T1T2/(T1+T2), identical to the time constant observed Continuous Wave Free Precession (CWFP). The Steady-State amplitude obtained with CP90 (MCP90) = M0T2/(T1+T2) was identical to CWFP. Therefore, this sequence was named CP-CWFP because it is a CP sequence that produces results similar to the CWFP. However, CP-CWFP is a better sequence than CWFP for measuring the longitudinal and transverse relaxation times in single scan, when the sample exhibits T1 ~ T2. When phase alternation is applied in CPMG90AF (y\'/-y\') e CP90AF (x\'-x\') the signal reaches a Steady-State. CPMG90AF and CP90AF showed similar behavior to CP-CWFP, so one more alternative method to measure T1 and T2. Therefore, the T2 measurements can be performed with 90&deg; refocusing pulses (CPMG90), which use only 25% of the RF power used in conventional CPMG. This reduces the heating problem in the probe and reduces the power deposition in the samples. The CP-CWFP sequence can be a useful method in low-resolution NMR and can be widely used in the agriculture, food and petrochemical industries because those samples tend to have similar relaxation times in low magnetic fields.

Lipid molecules form thin biological membranes that envelop all living cells, and behave as two-dimensional liquid sheets immersed in bulk water. The interactions of such biomembranes with their environment lay the foundation of a plethora of biological processes rooted in the mesoscopic domain - length scales of 1-1000 nm and time scales of 1-1000 ns. Research in this intermediate regime has for a long time been out of reach for conventional experiments, but breakthroughs in computer simulation methods and scattering experimental techniques have made it possible to directly probe static and dynamic properties of biomembranes on these scales. Biomembranes are soft, with a relatively low energy cost of bending, and are thereby influenced by random, thermal fluctuations of individual molecules. Molecular dynamics simulations show how in-plane (density fluctuations) and out-of-plane (undulations) motions are intertwined in the bilayer in the mesoscopic domain. By novel methods, the fluctuation spectra of lipid bilayers can be calculated withdirect Fourier analysis. The interpretation of the fluctuation spectra reveals a picture where density fluctuations and undulations are most pronounced on different length scales, but coalesce in the mesoscopic regime. This analysis has significant consequences for comparison of simulation data to experiments. These new methods merge the molecular fluctuations on small wavelengths, with continuum fluctuations of the elastic membrane sheet on large wavelengths, allowing electron density profiles (EDP) and area per lipid to be extracted from simulations with high accuracy. Molecular dynamics simulations also provide insight on the small-wavelength dynamics of lipid membranes. Rapidly decaying density fluctuations can be described as propagating sound waves in the framework of linearized hydrodynamics, but there is a slow, dispersive, contribution that needs to be described by a stretched exponential over a broad range of length- and time scales - recent experiments suggest that this behavior can prevail even on micrometer length scales. The origin of this behavior is discussed in the context of fluctuations of the bilayer interface and the molecular structure of the bilayer itself. Connections to recent neutron scattering experiments are highlighted. / QC 20111014 / Modelling of biological membranes

A Ressonância Magnética Nuclear em baixa resolução (RMN-BR) vem sendo aplicada no controle e certificação de qualidade na indústria. Para acelerar e automatizar as análises tem sido proposto o uso de RMN online, com carreamento de amostras por uma esteira. Apesar do grande potencial, as metodologias utilizadas podem provocar o aquecimento da amostra, causando erros nas medidas, além de reduzir a vida útil do equipamento. Assim, nesse trabalho de doutorado foram desenvolvidas sequências de eco de spin para medidas de RMN-BR online utilizando baixa potência de RF (radiofrequência), baseadas nas técnicas CP, Carr-Purcell, e CPMG, Carr-Purcell-Meiboom-Gill, utilizando baixos ângulos de refocalização, LRFA (Low Refocusing Flip Angle). Observou-se que LRFA de 45&deg; (CPMG45) pode fornecer valores de tempo de relaxação transversal (T2) com erros inferiores a 5% em campos magnéticos (B0) com homogeneidade equivalente a largura de linha de &Delta;&nu; &le; 15 Hz. Em B0 menos homogêneos (&Delta;&nu; &ge; 100 Hz), a escolha dos LRFA deve considerar a redução do sinal e o aumento de T2, que se torna dependente do tempo de relaxação longitudinal (T1). CP90 produz ecos entre os pulsos de refocalização que decaem para valores mínimos dependente de T2* (constante de tempo do Decaimento Livre da Indução). O sinal obtido por CP90 aumenta de valores mínimos para o regime de estado estacionário (EE) com constante de tempo T* = 2T1T2/(T1+T2) e amplitude MCP90 = M0T2/(T1+T2), a mesma constante e a mesma amplitude observada para o sinal de Precessão Livre em Onda Contínua (CWFP - Continuous Wave Free Precession), por isso foi denominada CP-CWFP. A principal vantagem de CP-CWFP ocorre para amostras com T1 ~ T2. CP-CWFP apresenta um decaimento abrupto da amplitude do sinal antes de aumentar e alcançar o EE. Essa diferença na amplitude torna o ajuste de T* menos dependente da razão sinal/ruído, sendo mais eficiente que CWFP para medidas de T1 e T2 em B0 baixos, onde T1 e T2 tendem a ter valores similares. No método de alternância de fase (AF) em CPMG90AF (y\'/-y\') e CP90AF (x\'-x\') os sinais entraram num EE, nesse caso CPMG90AF e CP90AF tiveram comportamentos similares ao CP-CWFP, sendo mais uma alternativa para obtenção de T1 e T2. Para CPMG, a redução do ângulo de refocalização para 90&deg; equivale a uma redução de 75% da potência incidida na amostra. CP-CWFP pode ser uma técnica mais robusta para análises em espectrômetros de RMN de bancada em controle de qualidade industrial, com B0 < 0,5 T (20 MHz) e em ferramentas de RMN utilizadas em poços de petróleo com B0 ~ 0,05 T (2 MHz). As análises por métodos estatísticos demonstraram que CPMG e CPMG90, CWFP e CP-CWFP apresentam alta correlação entre si, demonstrando que uma técnica pode substituir a outra nas análises online de sementes oleaginosas. / Low Resolution Nuclear Magnetic Resonance (LR-NMR) has been applied in quality control and certification in industry. To speed up the analysis the online NMR has been proposed. Despite LR-NMR online potential, some problems related to equipment overload occurs. It is due to methodologies used that can cause an increase in sample temperature and consequently errors in measurements as well reduction on equipment durability. Thus, Carr-Purcell, CP and Meiboom-Gill, CPMG using low refocusing flip angles (LRFA) were developed. It was observed that LRFA as low as 45&deg; (CPMG45) can provide transverse relaxation time values (T2) with errors below 5% for homogeneous field (&Delta;&nu; &le; 15Hz). For a less homogeneous magnetic field (&Delta;&nu; &ge; 100 Hz) the choice of the LRFA has to take into account the reduction in the intensity of the CPMG signal and the increase in the time constant of the CPMG decay that also becomes dependent on longitudinal relaxation time (T1). The Carr-Purcell (CP) pulse sequence, with LRFA, produces echoes midway between refocusing pulses that decay to a minimum value dependent on T2* (Free Induction Decay time constant - FID). When &tau; &gt; T2*, the signal increased to reach a Steady-State Free Precession regime (SSFP) after the minimum value and was composed of FID signal after each pulse and an echo, before the next pulse. CP90 signal increased from the minimum value to the steady-state regime with a time constant (T*) = 2T1T2/(T1+T2), identical to the time constant observed Continuous Wave Free Precession (CWFP). The Steady-State amplitude obtained with CP90 (MCP90) = M0T2/(T1+T2) was identical to CWFP. Therefore, this sequence was named CP-CWFP because it is a CP sequence that produces results similar to the CWFP. However, CP-CWFP is a better sequence than CWFP for measuring the longitudinal and transverse relaxation times in single scan, when the sample exhibits T1 ~ T2. When phase alternation is applied in CPMG90AF (y\'/-y\') e CP90AF (x\'-x\') the signal reaches a Steady-State. CPMG90AF and CP90AF showed similar behavior to CP-CWFP, so one more alternative method to measure T1 and T2. Therefore, the T2 measurements can be performed with 90&deg; refocusing pulses (CPMG90), which use only 25% of the RF power used in conventional CPMG. This reduces the heating problem in the probe and reduces the power deposition in the samples. The CP-CWFP sequence can be a useful method in low-resolution NMR and can be widely used in the agriculture, food and petrochemical industries because those samples tend to have similar relaxation times in low magnetic fields.

Adenosine triphosphate (ATP) is the major carrier of chemical energy in cells. The diffusion of ATP in hydrogels, which have a structural resemblance to the natural extracellular matrix, is therefore of great importance to understand many biological processes. In continuation of our recent studies of ATP diffusion in poly(ethylene glycol) diacrylate (PEG-DA) hydrogels by pulsed field gradient nuclear magnetic resonance (PFG-NMR), we present precise diffusion measurements of ATP in aqueous solutions of PEG-DA polymers, which are not cross-linked to a three-dimensional network. The dependence of the ATP diffusion on the polymer volume fraction in the hydrogels, φ, was found to be consistent with the predictions of a modified obstruction model or the free volume theory in combination with the sieving behavior of the polymer chains. The present measurements of ATP diffusion in aqueous solutions of the polymers revealed that the diffusion coefficient is determined by φ only, regardless of whether the polymers are cross-linked or not. These results seem to be inconsistent with the free volume model, according to which voids are formed by a statistical redistribution of surrounding molecules, which is expected to occur more frequently in the case of not cross-linked polymers. The present results indicate that ATP diffusion takes place only in the aqueous regions of the systems, with the volume fraction of the polymers, including a solvating water layer, being blocked for the ATP molecules. The solvating water layer increases the effective volume of the polymers by 66%. This modified obstruction model is most appropriate to correctly describe the ATP diffusion in PEG-DA hydrogels.

Magnetic resonance imaging is an essential tool for assessing soft tissues. The desire for increased signal-to-noise and improved tissue contrast has spurred development of imaging systems operating at magnetic fields exceeding 3.0 Tesla (T). Unfortunately, traditional imaging methods are of limited utility on these systems. Novel imaging methods are required to exploit the potential of high field systems and enable innovative clinical studies. This thesis presents methodological advances for human brain imaging at 4.7 T. These methods are applied to assess sub-cortical gray matter in multiple sclerosis (MS) patients. Safety concerns regarding energy deposition in the patient precludes the use of traditional fast spin echo (FSE) imaging at 4.7 T. Reduced and variable refocusing angles were employed to effectively moderate this energy deposition while maintaining high signal levels; an assortment of time-efficient FSE images are presented. Contrast changes were observed at low angles, but images maintained a clinically useful appearance. Heterogeneous transmit fields hinder the measurement of transverse relaxation times. A post-processing technique was developed to model the salient signal behaviour and enable accurate transverse relaxometry. This method is robust to transmit variations observed at 4.7 T and improves multislice imaging efficiency. Gradient echo sequences can exploit the magnetic susceptibility difference between tissues to enhance contrast, but are corrupted near air/tissue interfaces. A correction method was developed and employed to reliably produce a multitude of quantitative and qualitative image sets. Using these techniques, transverse relaxation times and susceptibility field shifts were measured in sub-cortical nuclei of relapsing-remitting MS patients. Abnormalities in the globus pallidus and pulvinar nucleus were observed in all quantitative methods; most other regions differed on one or more measures. Correlations with disease duration were not observed, reaffirming that the disease process commences prior to symptom onset. The methods presented in this thesis enable efficient qualitative and quantitative imaging at high field strength. Unique challenges, notably patient safety and field variability, were overcome via sequence implementation and data processing. These techniques enable visualization and measurement of unique contrast mechanisms, which reveal insight into neurodegenerative diseases, including widespread sub-cortical gray matter damage in MS.

Entangled polymeric fluids subjected to shear display a stress plateau through a range of shear rates. The formation of this plateau is often attributed to an entanglement-disentanglement transition in scientific literature. However, to our best knowledge in situ studies recovering the intermediate scattering function of polymer dynamics under shear have until now never been performed. This thesis documents the successful development of a high viscosity shear device whose interaction with polarized neutrons is small enough to allow use for Neutron Spin Echo spectroscopy. Further, first measurements towards the direct observation of the variation of the degree of entanglement throughout increasing shear are documented, albeit yet for too short Fourier times to measure beyond Rouse dynamics.