Single crystals of (Mg₉₉.₇₅Mn₀.₂₅)₂P₂O₇ have been investigated by esr through the temperature range from room temperature to 200ºC. One phase transition was observed extended through the temperature range between 59.5ºC to 63ºC where the α-and β phase coexist. Accurate spectra were recorded at 74ºC, 84ºC and 94ºC at the three magnetic axis, and the spin-Hamiltonian parameters were obtained from these data. The phase transition mechanism and the significance of the spin-Hamiltonian parameters in the theory of S-state splitting are discussed in the light of current literature. / Thesis / Master of Science (MSc)

<p> Near Medicine Hat, Alberta, Pleistocene deposits are exposed on numerous bluffs along the South Saskatchewan River. The Quaternary beds are very fossiliferous, yielding a large number of mammal bones and teeth. The enamel (calcium hydroxyapatite) portion of teeth within the sediments, is used to date the deposits with the electron spin resonance (ESR) dating method. The ESR age is strongly dependent on the dose rate which in turn depends on the uranium accumulation in the tooth fragments. Two U uptake models are used based on an early and a continuous, linear accumulation of uranium.</p> <p> At young, well dated sites the ESR ages are in relatively good agreement with independent estimates. For slightly older samples (approx. 100 ka), the linear U uptake model comes closer to the estimated age at one site, but at another site, the early U uptake model agrees more favourably with the estimated age. Based on the ESR ages, several older sites can be assigned to interglacial stages 7, 9 and 13, however, these ages are much younger than those determined by faunal and stratigraphic correlation (>0.5 Ma). Samples with extremely high U contents in dentine and enamel gave unreliable ESR results. These samples may have experienced a late stage of U accumulation.</p> / Thesis / Master of Science (MSc)

<p> The principal subject of this thesis is to experimentally determine the beta attenuation patterns in tooth enamel layers, and to examine the predictions of two theoretical models which are involved in the beta dose calculations of ESR dating. One of the models is based on empirical equations (Yokoyama, 1982) and employed by R.Grün (1986) in the DATA software of ESR dating, the other is based on the "one group" transport theory which was incorporated in the ROSY dating programme (B.J. Brennan, et al., 1997).</p> <p> The theoretical bases of Grün's approximation (i.e. the empirical approach) and the "one group" transport theory are discussed. Their predictions of beta attenuation under 2-π geometry are compared with the results of Monte Carlo simulations, and were then compared with the results of our experimental work, which show clear inclination to the predictions of "one group" theory and Monte Carlo. The previous experiment of Aitken et al.(1985) is also described and its flawed geometric arrangement is discussed.</p> <p> In this study, two sets of experiments are performed. The first set used pitchblende as the irradiator and employed the configuration of irradiator-absorber-detector, which is aimed to reassess the experiment of Aitken et al. (1985). The second set of our experiments used a pure beta source of 90Sr(90Y) and employed the innovative configuration of tooth enamel pellets in a hole of tooth enamel holder, which substantially solved the problem encountered in the first set (e.g. gamma background subtraction and non-2π geometry, etc.).</p> <p> Based on our experimental results as well as the discussion of Aitken et al.'s experiment, a conclusion is drawn that the "one group" theory is more reliable in predicting beta doses in ESR dating samples, and consequently, it challenges the ESR ages calculated by DATA software which employs the empirical approach. The comparison of ESR ages calculated by the two dating programmes is shown, and some revisions of published ESR ages based on DATA programme demonstrate the great significance of our experimental results.</p> / Thesis / Master of Science (MSc)

No description available.

O trabalho envolve o estudo de amostras de poli(o-metoxianilina) (POMA) , dopadas com ácido trifluoracético (TFA) através das técnicas de espectroscopia de Ressonância Paramagnética Eletrônica (RPE) de onda contínua e pulsada. O sinal de RPE observado é atribuído a elétrons desemparelhados na cadeia polimérica, denominados pólarons. Uma vez que estes pólarons possuem carga elétrica e spin eletrônico, os estudos de RPE podem fornecer informações a respeito de sua mobilidade e sobre as propriedades de transporte no material em escala microscópica. O efeito da presença de oxigênio molecular, O2, (S=1), sobre a forma da linha CW é estudado em função do grau de dopagem e do envelhecimento das amostras. O alargamento observado da linha de RPE deve-se a processos de colisão entre o pólaron móvel e os spins localizados do O2. Durante uma colisão, os dois spins interagem entre si através de interações de troca magnética, produzindo spin-flips simultâneos. Uma vez que os spins fixos estão fortemente acoplados com a rede, o processo de relaxação spin-rede do pólaron torna-se muito eficiente, produzindo o alargamento da linha. Como resultado deste processo de colisões, a dependência da largura de linha em função da temperatura mostra um máximo em torno de 190 K. Modelos teóricos serão apresentados, a partir dos quais serão estimados os valores para a mobilidade do pólaron, raio de ação da interação pólaron-oxigênio e constantes de acoplamento. Amostras sintetizadas na presença de oxigênio possuem tempos de relaxação muito curtos em toda a faixa de temperatura estudada (2-280 K), impossibilitando a observação da RPE pulsada. Amostras envelhecidas mostram um comportamento diferente, característico da substituição do oxigênio por água, que leva ao cancelamento do efeito de alargamento. Nestas amostras, assim como em amostras sintetizadas em atmosfera inerte, estudos adicionais de RPE pulsada permitem, através de técnicas associadas ao eco de spins eletrônicos, ESE, a obtenção dos tempos de relaxação spin-spin e spin-rede, assim como o estudo das interações hiperfinas entre pólaron e núcleos vizinhos, 1H, 13C e 14N, que não são resolvidas no espectro CW. A quantificação e qualificação de núcleos interagentes, os quais possuem desdobramentos hiperfinos fracos, podem ser realizadas através das técnicas uni e bidimensionais, como ESEEM, 2DESEEM e HYSCORE. / Continuous wave (CW) and pulsed Electron Paramagnetic Resonance (EPR) techniques are used to study structural and dynarnical properties of poly(o-metoxyaniline) (POMA) doped in trifluoroacetic (TFA) solution. The observed EPR spectrum is attributed to chain unpaired electron spins named polarons. Since polarons carry both charge and spin, EPR studies can provide information about charge transport properties of the material on a microscopic scale. The width of the EPR signal reflects the interaction of the polarons with their environments. In the present study, special attention is given to the EPR linewidth, which is usually broadened by the presence of molecular oxygen, O2, (S=1). The oxygen induced linewidth is explained by the mutual spin flips occurring during the collision of a mobile polaron with fixed paramagnetic O2. The temperature dependence of the linewidth shows a maximum around 190K associated with these collision processes. Such effects are studied as a function of doping concentration, sample aging and vacuum conditions. From a theoretical model proposed in the field, some parameters, associated with the polaron mobility and exchange interaction between polaron and oxygen, are estimated. All synthesized samples have very short spin relaxation times in all the studied temperature range (2-280K), making impossible their observation by the pulsed EPR techniques. Aged samples show a different behavior; their long relaxation times seem to indicate that the substitution of O2 by H2O has promoted the canceling of the broadening effect. Studies are under progress to establish a sample preparation procedure in which the resulting samples are free of molecular oxygen. Aged samples have been used to perform preliminary studies conducted by the pulsed EPR techniques. Spin-echo spectroscopy and relaxation time measurements were interpreted on the basis of the interaction of the polaron with neighboring nuclei, such as 1H, 13C e 14N, which are not resolved in the CW spectra. To better understand the nature of the CW and pulsed EPR spectroscopy, one special chapter will introduce the several techniques, which are commonly employed in our research.

In this thesis we used ESR to investigate magnetic properties of low D vandium and copper oxides in which small quantum spins are arranged in 1D chains and 2D layers. The thesis covers five different low dimensional spin systems. They turned out to be experimental reliazation of some of the most intersiting theoritical models in the field of quantum magnetism.

O trabalho envolve o estudo de amostras de poli(o-metoxianilina) (POMA) , dopadas com ácido trifluoracético (TFA) através das técnicas de espectroscopia de Ressonância Paramagnética Eletrônica (RPE) de onda contínua e pulsada. O sinal de RPE observado é atribuído a elétrons desemparelhados na cadeia polimérica, denominados pólarons. Uma vez que estes pólarons possuem carga elétrica e spin eletrônico, os estudos de RPE podem fornecer informações a respeito de sua mobilidade e sobre as propriedades de transporte no material em escala microscópica. O efeito da presença de oxigênio molecular, O2, (S=1), sobre a forma da linha CW é estudado em função do grau de dopagem e do envelhecimento das amostras. O alargamento observado da linha de RPE deve-se a processos de colisão entre o pólaron móvel e os spins localizados do O2. Durante uma colisão, os dois spins interagem entre si através de interações de troca magnética, produzindo spin-flips simultâneos. Uma vez que os spins fixos estão fortemente acoplados com a rede, o processo de relaxação spin-rede do pólaron torna-se muito eficiente, produzindo o alargamento da linha. Como resultado deste processo de colisões, a dependência da largura de linha em função da temperatura mostra um máximo em torno de 190 K. Modelos teóricos serão apresentados, a partir dos quais serão estimados os valores para a mobilidade do pólaron, raio de ação da interação pólaron-oxigênio e constantes de acoplamento. Amostras sintetizadas na presença de oxigênio possuem tempos de relaxação muito curtos em toda a faixa de temperatura estudada (2-280 K), impossibilitando a observação da RPE pulsada. Amostras envelhecidas mostram um comportamento diferente, característico da substituição do oxigênio por água, que leva ao cancelamento do efeito de alargamento. Nestas amostras, assim como em amostras sintetizadas em atmosfera inerte, estudos adicionais de RPE pulsada permitem, através de técnicas associadas ao eco de spins eletrônicos, ESE, a obtenção dos tempos de relaxação spin-spin e spin-rede, assim como o estudo das interações hiperfinas entre pólaron e núcleos vizinhos, 1H, 13C e 14N, que não são resolvidas no espectro CW. A quantificação e qualificação de núcleos interagentes, os quais possuem desdobramentos hiperfinos fracos, podem ser realizadas através das técnicas uni e bidimensionais, como ESEEM, 2DESEEM e HYSCORE. / Continuous wave (CW) and pulsed Electron Paramagnetic Resonance (EPR) techniques are used to study structural and dynarnical properties of poly(o-metoxyaniline) (POMA) doped in trifluoroacetic (TFA) solution. The observed EPR spectrum is attributed to chain unpaired electron spins named polarons. Since polarons carry both charge and spin, EPR studies can provide information about charge transport properties of the material on a microscopic scale. The width of the EPR signal reflects the interaction of the polarons with their environments. In the present study, special attention is given to the EPR linewidth, which is usually broadened by the presence of molecular oxygen, O2, (S=1). The oxygen induced linewidth is explained by the mutual spin flips occurring during the collision of a mobile polaron with fixed paramagnetic O2. The temperature dependence of the linewidth shows a maximum around 190K associated with these collision processes. Such effects are studied as a function of doping concentration, sample aging and vacuum conditions. From a theoretical model proposed in the field, some parameters, associated with the polaron mobility and exchange interaction between polaron and oxygen, are estimated. All synthesized samples have very short spin relaxation times in all the studied temperature range (2-280K), making impossible their observation by the pulsed EPR techniques. Aged samples show a different behavior; their long relaxation times seem to indicate that the substitution of O2 by H2O has promoted the canceling of the broadening effect. Studies are under progress to establish a sample preparation procedure in which the resulting samples are free of molecular oxygen. Aged samples have been used to perform preliminary studies conducted by the pulsed EPR techniques. Spin-echo spectroscopy and relaxation time measurements were interpreted on the basis of the interaction of the polaron with neighboring nuclei, such as 1H, 13C e 14N, which are not resolved in the CW spectra. To better understand the nature of the CW and pulsed EPR spectroscopy, one special chapter will introduce the several techniques, which are commonly employed in our research.

Tetrathiafulvalene derivatives are remarkable molecules, with various application, reported relatively recently. The radical cation of these compounds has very inter- esting optical, electronic, electrocatalytic superconducting and magnetic properties that have been intensively studied recently. Quantitative in-situ EPR voltammetric spectroelectrochemistry studies of 2-(2-hydroxyethylsulfanyl)-3-(benzylsulfanyl)-6,7- bis(octadecylsulphanyl)tetrathiafulvalene (TTF-Der3) have been carried out with the aim to confirm the oxidation sites, follow-up reactions (after the first electron transfer), and electrochemical behaviour. The diffusion process was confirmed by the depen- dence of current on the square root of the scan rate. It was claimed that the ratio of the number of generated radicals to transferred charge (electrons) for two representative TTF derivatives was determined to 5.5:500 for and 7:500 for TTF, indicating the follow- up reactions. Experiments were performed using the commercially available EPR standards, calibrated for this method (experimental setup). The latter was validated by quantitative EPR with standard 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl radical concentration (1·10−4 mol dm−3). For the ratios the confidence interval was reported for the first time for TTF-Der3 it was...

Electronic inhomogeneities play an important role in the definition of physical properties of correlated systems. To study these inhomogeneities one has to use local probe techniques which can distinguish electronic, magnetic and structural variations at the nanoscale. In the present work the high-field electron spin resonance technique (HF-ESR) is used to probe electronic and magnetic inhomogeneities in two transition-metal element based systems with very different properties. The first system is an iron based hightemperature superconductor, namely a member of a so called 1111-family, the (La,Gd)O1−xFxFeAs compound. Our HF-ESR spectroscopy study on Gd3+ ion has revealed that this material exhibits anisotropic interaction between Gd and Fe layers, which is frustrated in the absence of an external magnetic field. Moreover, the study of the superconducting samples has shown a coexistence of a static short range magnetic order with superconductivity up to high doping levels. The second system is a lightly hole doped cubic perovskite LaCoO3. Here, our HF-ESR investigation, complemented with static magnetometry and nuclear magnetic resonance techniques, has established that the hole doping induces a strong interaction between electrons on neighboring Co ions which leads to a collective high-spin state, called a spin-state polaron. These polarons are inhomogeneously distributed in the nonmagnetic matrix. This thesis is organized in three chapters. The first chapter gives basic ideas of magnetism in solids, focusing on the localized picture. The aim of the second chapter is to introduce the method of ESR. The third chapter is dedicated to the study of 1111-type iron arsenide superconductors. In the first part X-band (9.5 GHz) ESR measurements on 2% and 5% Gd-doped LaO1−xFxFeAs are presented. In the second part a combined investigation of the properties of GdO1−xFxFeAs samples by means of thermodynamic, transport and high-field electron spin resonance methods is presented. The last, fourth chapter presents the investigation of the unexpected magnetic properties of lightly hole-doped LaCoO3 cobaltite by means of the electron spin resonance technique complemented by magnetization and nuclear magnetic resonance measurements.

<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>Ispitana je antioksidativna aktivnost različito pripremljenih napitaka i fermentativnih tečnosti od čajne gljive, i to prvenstveno praćenjem sposobnosti transformacije i stabilizacije reaktivnih hidroksi-radikala i redukcije stabilnih 1,1-difeniI- 2-pikriIhidraziI (DPPH) radikala. Određeni su i neki od metabolita kombuhe koji deluju kao antioksidanti (vitamini B₂ i C), kao i organske kiseline koje stabilizuju napitak od čajne gljive. Osnovne analitičke tehnike kori&scaron;ćene u radu bile su ESR, HPLC, TLC, spektrofotometrija proizvoda enzimskih reakcija i volumetrija.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>The antioxidant activity of differently prepared beverages and fermentative liquids of tea fungus was examined, primarily by following of ability for transformation and stabilization of reactive hydroxyl-radicals and reduction of stable 1,1- diphenyl-2-picrylhydrazyl (DPPH) radicals. Some of the metabolites of kombucha that act as antioxidants (vitamins B2 and C) and organic acids that stabilize tea fungus beverage were determined. The primary used analytical techniques were ESR, HPLC, TLC, spectrophotometry of products of enzymatic reactions and voIumetry.</p><p>&nbsp;</p>