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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
621

An NMR study of 2-ethyl-1-butyllithium and of 2-ethyl-1-butyllithium/lithium 2-ethyl-1-butoxide mixed aggregates

Ferreira, Aluisio V. C. 05 1900 (has links)
A 1H, 13C, and 6Li NMR study of 2-ethyl-1-butyllithium indicated that 2-ethyl-1-butyllithium exists only as a hexameric aggregate over the entire temperature range of 25 to - 92.1 ° C in cyclopentane. Reacting 2-ethyl-1-butyllithium with 2-ethyl-1-butanol resulted in alkyllithium/lithium alkoxide mixed aggregates, apparently of the form Ra(RO)bLia+b. A multinuclear, variable temperature NMR study of samples with O:Li ratios of 0.2 and 0.4 showed, in addition to the alkyllithium, the formation of four mixed aggregates, one of them probably an octamer. Higher O:Li ratio samples showed the formation of several other mixed aggregates. Mixing 2-ethyl-1-butyllithium with independently prepared lithium 2-ethyl-1-butoxide formed the same mixed aggregates formed by in situ synthesis of lithium alkoxide. Lithium 2-ethyl-1-butoxide also exists as aggregates in cyclopentane.
622

Investigation in to the Effect of Spin Locking on Contrast Agent Relaxivity

Haigh, Julian Saunders 12 August 2015 (has links)
The current trend in magnetic resonance imaging (MRI) is towards higher external magnetic field strengths (B0) to take advantage of increased sensitivity and signal to noise ratio (SNR). Unfortunately, as (B0) increases the effectiveness (relaxivity) of clinical gadolinium (Gd3+)-based contrast agents (CAs) administered to enhance image contrast is significantly reduced. Excellent soft tissue contrast can be generated with current agents despite their non-optimum relaxivities but necessitates large doses. The limits of detection of a CA at high B0 fields can be lowered by recovering the lost relaxivity and is a pre-requisite to the goal of molecular imaging in which CAs are bound to biomarkers of pathology that exist at very low concentrations. Traditional methods for increasing the detectability of CAs have focused on optimizing critical parameters identified from the Solomon-Bloembergen-Morgan (SBM) theory that affect relaxivity. Gains in relaxivity with these methods to date have been modest and are far from the theoretical maximum possible. Although researchers continue to investigate novel complexes that provide improved relaxivities, any such complex would require a lengthy and costly approval process with the U.S. Food and Drug Administration (FDA). Therefore, a method that affords improved relaxivities of current clinically approved CAs, particularly at high B0 fields, that could be adopted into clinical practice rapidly, is of great interest. Spin locking is a nuclear magnetic resonance (NMR) technique that was introduced for imaging in 1985, but has received very little attention in combination with Gd3+-based CAs. The technique employs a low power long duration radiofrequency (RF) pulse (B1) parallel to the net magnetization in the x,y-plane. This locks the magnetization into lower precessional frequencies around an "effective" field (Beff) that is reduced with respect to B0 but maintains the high field advantages required for imaging. When considered in the rotating frame, longitudinal relaxation of the magnetization against Beff exhibits shorter time constants (T1p) expected at these lower precessional frequencies. This leads to higher relaxivities, which has implications for increasing CA detectability. The experiments described herein show that rotating frame longitudinal relaxivities (r1p) for current clinical Gd3+-based CAs are essentially independent of the strength of the spin lock pulse (yB1) as predicted by theory. This result is important because it allows the value of yB1 to be neglected when comparing r1p of Gd3+-based CAs across several B0 fields. The magnetic field dependence of r1p for all clinical agents showed that relaxivity, lost by moving to higher fields, could be "recovered" and that r1p was sensitive to the rotational correlation time constant (TR) of the agent. Using high molecular weight Nanoassembled capsules (NACs) containing a Gd3+-based CA to probe this finding further, we were able to generate relaxivities at high field up to an order of magnitude greater than clinical agents at current imaging fields. These are beyond anything previously reported, or likely to be, with current techniques. Finally, we demonstrated that by spin locking Mn2+ agents, relaxivities at high field increased by a factor of ~ 30 than without spin locking, due to their larger dependence on scalar coupling. These findings show the potential of spin locking to increase detection limits dramatically at high field and are an exciting development towards the goal of molecular imaging.
623

Making Nuclear Magnetic Hyperpolarization Practical through Storage in Disconnected Eigenstates

Claytor, Kevin E. January 2015 (has links)
<p>There are two fundamental limitations in magnetic resonance: the poor signal amplitude and the short duration before the system return to equilibrium. Hyperpolarization methods solve the problem of signal amplitude, however, the duration of the hyperpolarized signal is still limited by the spin-lattice relaxation time, T1. Disconnected eigenstates provide a mechanism by which hyperpolarization can be stored for several times T1. This thesis contributes to the knowledge of these states in four important ways. First, the decay of hyperpolarized magnetization of gas is simulated in lung tissue with a contrast agent, yielding insights about the optimal field strength for imaging. Second, I show that it is possible to rapidly discover and characterize disconnected eigenstates by showing that they can be measured without synthesizing the isotopically labeled compound. Third, I extend the spin systems that can support disconnected eigenstates by expanding the theory to include spin-1 nuclei. Finally, I show that disconnected states with long lifetimes can be populated in conjunction with hyperpolarization techniques to simultaneously yield large signal amplitudes for long durations. </p><p>Applications of hyperpolarized spin order are likely to be in complex geophysical or biological structures. Understanding the effect of the inhomogeneous fields created when such structures are placed in a magnetic field on hyperpolarized spin order is a necessity to characterize the experimental signal. An example case of hyperpolarized 3He and 129Xe diffusing through lung tissue is examined. In particular a Monte Carlo simulation tool, combined with a magnetic field map of the inhomogeneous field created by mouse lung tissue, is used to determine the dephasing rate of hyperpolarized 3He and 129Xe in the presence of SuperParamagnetic Iron Oxide Nanoparticles (SPION). Contributions to the dephasing rate include the inhomogeneous field, the SPION magnetic field, and dephasing caused by collisions with the confining geometry. The sensitivity of either gas to SPION increases with increasing SPION concentration and decreasing field strength.</p><p>There are some general rules about what makes for a disconnected eigenstate (or singlet state) with a long lifetime. However, no systematic experimental study has been undertaken due to the cost and time-constraints of synthesizing the labeled species for study. I show that synthesis is not a barrier for characterizing the long-lived states. Instead the lifetimes may be determined by using the naturally occurring doubly-labeled isotopomer. I verified this method with two compounds, diphenyl acetylene (DPA) and diethyl oxylate (DEO). The former was determined to have a singlet lifetime TS = 251.40 ±3.16 s from the synthesized species, while the naturally occurring isotopomer yielded a lifetime TS = 202 ±55.30 s, both substantially longer than the spin-lattice relaxation time, T1 = 1.63 ±0.01s. In DEO, the lifetime from the disconnected eigenstate was determined to be TS = 14.62 ±0.76 s (synthesized), TS = 19.32 ±3.16 s (naturally occurring). This method is applied to a range of compounds ranging from simple four-spin systems, such as diacetylene (TS = 48.80 ±22.74 s, T1 = 18.66 ±1.16 s) to eight spin systems in dimethylmaleic anhydride (TS = 27.25 ±3.39 s, T1 = 9.38 ±0.43 s). Additionally, a family of compounds including naphthalene (TS = 4.37 ±0.34 s, T1 = 11.33 ±4.89 s), biphenyl (TS = 3.09 ±0.66 s, T1 = 4.69 ±0.10 s), and DPA show that the rotation of the phenyl rings and intermolecular dipole-dipole relaxation can be critical to the relaxation dynamics.</p><p>One particular method of accessing the disconnected eigenstate involves coupling a chemically equivalent spin-1/2 pair asymmetrically to an auxiliary spin-1/2 pair. I demonstrate that the disconnected state may still be accessed when the auxiliary nuclei are spin-1. This has two distinct advantages. When the auxiliary nuclei change from proton to deuterium, the couplings are reduced by a factor of ~6.5 which prevents the disconnected state from relaxing as rapidly back to equilibrium. This is demonstrated in diacetylene-d2 and DPA-d10, where the singlet lifetime was extended by a factor of ~1.7 via deuteration (TS,1H = 49 ±23 s, TS,2H = 83 ±30 s for diacetylene and TS,1H = 274 ±6.1 s, TS,2H = 479 ±83 s for DPA). Additionally, by reducing the coupling strength, deuteration allows additional structural moieties to be explored, such as RDC=CDR. One such structure is explored in trans-ethylene-d2, where the singlet character of the protons can be accessed by the reduced coupling to the deuterium. Additionally, this allows for a relatively strong deuterium-deuterium scalar coupling, requiring modification to the theory. This is carried out analytically, and implications for the relaxation properties are performed using a spin-dynamics numerical simulation. The lifetime of the disconnected state was determined to be TS = 30.2 ±12.3 s, compared to the T1 = 1.1 ±0.2 s at high concentration (270 mM), and increasing to TS = 117. ±9.80 s at low concentration (52 mM). The variation in long lifetime is attributed to intermolecular dipole-dipole relaxation.</p><p>Ultimately, the gains in lifetime from using disconnected eigenstates provide a means to the practical implementation of hyperpolarization in a wider range of experiments. A recent hyperpolarization method, Signal Amplification By Reversible Exchange in Shield Enables Alignment Transfer to Heteronuclei (SABRE-SHEATH) is shown to directly hyperpolarize long lived spin order in a diazirine containing molecule. Diazirine rings are three member N=N-C groups that can replace a methylene group and serve as a versatile MR and optical molecular tag. Hyperpolarization is accomplished by bubbling parahydrogen through a solution containing the diazirine and an iridium catalyst. Due to the chemical inequivalence of the 15N of the diazirine, hyperpolarization of longitudinal magnetization and singlet character could be observed by transfer to the high field spectrometer. Signal enhancements of over 14,000 were observed. The magnetic field strength required for buildup of magnetization and singlet character was derived and is in agreement with the experiment. The magnetization lifetime was observed to be T1 = 5.75 ±0.18 minutes and independent of field strength, while the lifetime of the singlet character was observed to be as long as TS = 30.1 ±13.4 minutes at low field (3 Gauss).</p><p>The combination of these experiments – understanding lifetimes in inhomogeneous magnetic fields that will be encountered in experiment, identification of disconnected eigenstates with long lifetimes via the naturally occurring isotopomer and extending these lifetimes even further with deuteration, and finally, the direct generation of long-lived hyperpolarized spin order – allows a measurement that required hyperpolarized spin order for the enhanced signal amplitude, to be carried out.</p> / Dissertation
624

The double CUE domain of chromatin remodelling factor SMARCAD1

West, Philip M. January 2012 (has links)
ATP-dependent chromatin remodellers represent a class of proteins that restructure chromatin through the action of a conserved helicase-like ATPase domain. Remodellers typically have several accessory binding domains alongside the ATPase. These confer target specificity and most commonly recognise histone post-translational modifications. SMARCAD1 is a ubiquitous chromatin remodeller involved with DNA replication and re- pair. It binds directly to PCNA at the site of DNA replication and recruits co-repressor KAP1 in order to silence newly produced chromatin. In contrast to most other chromatin remodellers, SMARCAD1 does not contain several different types of accessory domains. Only two CUE do- mains have been identified in addition to the SMARCAD1 core ATPase domain. CUE domains are a type of helical ubiquitin-binding domain. This thesis presents the findings of an investigation into the structure and function of the SMARCAD1 double CUE domain. The solution NMR structure is presented with results from NMR binding experiments mapped onto the structure. Each CUE domain was found to be an independent helix bundle connected by a dynamic flexible linker. The N-terminal CUE domain, CUE-1, binds ubiquitin and has an adjacent SUMO (a ubiquitin-like protein) binding motif on a protruding extended helix. The C-terminal CUE domain, CUE-2, has a very similar structure to several published CUE domains but does not bind ubiquitin due to a charged substitution at a highly conserved CUE consensus position. The SMARCAD1 double CUE domain binds KAP1 from nuclear extract and is likely to mediate the interaction between SMARCAD1 and KAP1. SMARCAD1 double CUE domain is not involved with PCNA binding.
625

An NMR Investigation of Aryl Mercury Compounds

Rowland, Keith E. (Keith Edward) 05 1900 (has links)
A variable temperature ^13 C and ^199 Hg NMR study has been conducted for diphenyl-, bis(o-tolyl)-, bis(m-tolyl)-, and bis(2, 6-xylyl)mercury in dimethyl sulfoxide and 1,1,2,2 tetrachloroethane; ^13 C T1 relaxation times are reported as a function of temperature. Barriers to rotation of the aryl rings are obtained. Chemical shifts and couplings in CDCl_3 are given for bis(p-tolyl)-, bis(2, 5-xylyl)-, bis(mesityl)-,phenyl(o-tolyl)-, phenyl(m-tolyl)mercury, and the compounds listed above. The steric interactions of these aryl mercury compounds are discussed.
626

Biofluid analysis to differentiate brain disease

Dickens, Alex January 2011 (has links)
It has been demonstrated that by using 1H NMR spectroscopy in combination with multivariate statistical modelling (PLS) it is possible, using urine samples obtained from rats, to distinguish between different types of CNS lesions. Against this background this thesis will explore whether the combination of 1H NMR and PLS modelling on biofluids can be used q-1eientify biomarkers in .. - different neurological diseases and in clinically relevant animal models of neurologic disease. The results in this thesis demonstrate that it is possible to separate sets of animals at different stages of disease in models of multiple sclerosis and to identify the presence of early brain metastasis. The same methodology was also applied to human biofluids. In MS patient cohorts (RR- MS, PP-MS and SP-MS) it was also possible to differentiate between RR-MS and SP-MS as well between MS and healthy controls. Therapy for these two stages of MS are very different and therefore a rapid test to determine a patient's stage of MS would be hugely beneficial in the clinic. Further investigation revealed that it is possible to separate MS patients from individuals with Alzheimer's disease. Metabolomics was then combined with other eo- variants in a study of cerebrospinal fluid obtained from patients with HIV associated dementia (HAD) to discover whether disease progression could be followed in this manner. The results show that it is possible to detect neurocognitive changes in patients with HAD. Indeed, the results demonstrate. that metabolomics is a far more sensitive tool for the following progression than other non-PLS biomarker techniques and should provide a useful method for early diagnosis of CNS disease and the evaluation of therapy in prospective studies.
627

Estudos biofísicos da proteína P21 de Trypanosoma cruzi / Biophysical studies on protein P21 of Trypanosoma cruzi

Teixeira, Francesco Brugnera 19 March 2019 (has links)
Segundo a Organização Mundial da Saúde, em 2018, entre 6 e 7 milhões de pessoas estavam infectadas pelo parasita Trypanosoma cruzi, agente etiológico da Doença de Chagas. Dentre as piores consequências para os chagásicos estão os problemas cardíacos causados pela infecção, os quais afetam cerca de 25% dos pacientes na fase crônica da doença. Na busca por biomoléculas envolvidas no processo de invasão celular pelo parasita, uma proteína produzida por ele, denominada P21, foi encontrada. Ensaios biológicos mostraram que a proteína P21 de T. cruzi interage com o receptor de quimiocinas CXCR4 e desencadeia diversos processos bioquímicos, como: indução de fagocitose por macrófagos, indução da polimerização de actina e inibição de angiogênese. Os dados sugerem que a P21 também pode desempenhar um papel na cardiomiopatia induzida pelo parasita. Visando contribuir com a caracterização biofísica e estrutural da proteína P21, foi desenvolvido um protocolo para sua obtenção a partir de corpos de inclusão e reenovelamento, o qual forneceu quantidades necessárias da proteína para os experimentos. Espectros de ressonância Magnética Nuclear (RMN) permitiram avaliar de forma precisa a qualidade estrutural da amostra reenovelada frente a proteína P21 produzida de forma solúvel. Resultados de RMN mostraram também que a proteína possui cinco hélices-&alpha; em sua estrutura secundária, uma grande porção desestruturada, além de duas populações conformacionais em equilíbrio. Ainda, corroborando com os dados biológicos encontrados na literatura, um ensaio de interação in vitro indicou que a P21 interage com o receptor CXCR4, sendo a porção N-terminal deste receptor a região envolvida em tal processo. / According to the World Health Organization, in 2018, between 6 and 7 million people were still infected by the parasite Trypanosoma cruzi, the causative agent of Chagas disease. One of the worst aggravations for chagasics is heart disorder caused by the infection, which affects about 25% of patients in the chronic phase of the disease. Searching for biomolecules involved in the parasitic invasion of human cells, a T. cruzi protein called P21 was found. It has a high probability of being secreted or anchored to the membrane. Biological assays have shown that T. cruzi P21 interacts with the CXCR4 chemokine receptor and mediates several biochemical processes, such as: induction of phagocytosis by macrophages, induction of actin polymerization and inhibition of angiogenesis. The data suggests that P21 may also play a role in cardiomyopathy induced by parasite. In order to contribute to the biophysical and structural characterization of P21, a refolding protocol was developed to obtain P21 from inclusion bodies. The protocol provided the necessary amounts of protein required for the experiments. Nuclear Magnetic Resonance (NMR) spectra allowed to accurately evaluate the structural quality of the refolded sample in comparison to the produced soluble P21 protein. NMR spectra also showed five &alpha;-helices in the P21 secondary structure, a large unstructured portion and two ensembles of structures in equilibrium. Furthermore, corroborating with the biological data found in the literature, an in vitro interaction assay indicated that P21 interacts with CXCR4 via the N-terminal portion of the receptor.
628

Desenvolvimento de metodologia de supressão de solvente por espectroscopia localizada por RMN(1H MRS) utilizando pulsos de RF adiabáticos com aplicação em medidas de açúcares em frutas / Development of Solvent Suppression Localized Volume MR Spectroscopy (1H MRS) using Adiabatic RF Pulses with application on fruit sugar quantification

Xavier, Rogério Ferreira 05 December 2005 (has links)
Novas seqüências para supressão de contribuições indesejadas em Imagens e Espectroscopia por Ressonância Magnética Nuclear, tais como as provenientes da água, um solvente que sempre resulta num sinal muito intenso em sistemas biológicos, são motivos de estudo e desenvolvimento com diversas aplicações atuais. O método que estamos propondo aqui, uma versão adiabática de MEGA incorporada nas seqüências PRESS e STEAM, visa a supressão do sinal da água presente no espectro de um volume localizado em uma amostra intacta. Para o campo magnético desse estudo (2.0 Tesla) e pelas características do magneto usado nesses experimentos, o pico do solvente tem o inconveniente de apresentar uma linha espectral muito larga quando comparado com a extensão do deslocamento químico das fiações de açúcar. O resultado indesejado é a sobreposição pelas suas vertentes, das diversas outras linhas espectrais, cujo interesse é de extrema importância, como a de alguns sólidos solúveis de açúcares. O principal problema encontrado é que a separação entre os picos da água e dos açúcares próximos é da ordem de 1 ppm. A metodologia proposta consiste na aplicação de pulsos de gradiente de campo magnético intensos em conjunto com uma seqüência de pulsos de RF adiabáticos e convencionais, seletivos em freqüência e espacialmente, para suprimir o pico da água em uma região espectral muito específica, sem nenhum dano a linearidade de fase do espectro restante. Esse procedimento, aliado a uma localização espacial muito eficiente, aumenta ainda mais o poder de análise desta ferramenta, a 1H MRS. Os resultados obtidos em campo de 2.0Tesla (85 Hz/ppm) mostraram que as seqüências híbridas adiabáticas MEGA-PRESS e MEGA-STEAM são bem eficazes na supressão do pico da água, como era esperado. Além disso, sua aplicação no monitoramento do grau de maturação de frutas intactas através do seu teor de açúcar, se mostrou muito bom dadas as condições experimentais extremamente limiares apresentadas pelo espectrômetro / New sequences for suppression of undesirable contributions in Magnetic Resonance Imaging and Spectroscopy, such as water, a solvent that always represent a very strong peak in biological systems, are object of recent development for several different applications. The method proposed here, an adiabatic version of MEGA incorporated within PRESS and STEAM, aims the suppression of the water peak present on volume selected spectra of intact specimens. For the magnetic field of this study (2.0 Tesla) and for the characteristics of the magnet used in the experiments, the solvent peak has the inconvenience of having a large width as compared to the spread in chemical shift of the sugar fractions. The undesirable result is the superposition on its tail with severa1 spectral lines, whose interest is of extreme importance, such as some sugar solid solutes. The main problem encountered is that the separation between the water peak and the nearest sugar peaks is of the order of 1 ppm. The proposed methodology consists on the application of intense gradient pulses along with a sequence of adiabatic and conventional RF pulses, both frequency and spatially selective, to suppress the water peak in a very specific spectral region, without any disturbance of the phase linearity of the remaining part of the spectrum. This procedure, allied to a very efficient spatial localization, enhances the power of the very well-known tool, the 1H MRS. Results obtained at 2.0Tesla (85 Hz/ppm) show that the hybrid adiabatic sequences MEGA-PRESS and MEGA-STEAM are efficient on suppressing the water peak, as expected. Also, their application on monitoring the degree of ripeness of intact fruits through their sugar content, has shown very good results, considering the extremely limiar experimental conditions presented by the spectrometer
629

Desenvolvimento de sistemas eletroquímicos acoplados a RMN de baixo e alto campo para análises in situ / Development of the electrochemical systms coupled to the low and high-field NMR for in situ analysis

Nunes, Luiza Maria da Silva 19 April 2012 (has links)
Neste trabalho é descrito o desenvolvimento de sistemas eletroquímicos (EQ) acoplados com a RMN de baixo e alto campo para análises in situ. Para a análise EQ-RMN de baixo campo, foi construído um sistema eletroquímico para ser utilizado tanto em um espectrômetro RMN-DT (B0= 0,23 T) quanto em um sensor unilateral (B0= 0,4 T). A platina foi utilizada como eletrodo de trabalho e contraeletrodo e um fio de prata como eletrodo de referência. A reação de eletrodeposição do cobre foi monitorada por meio do valor do tempo de relaxação transversal (T2), adquirido através da sequência de CPMG, em intervalos de 10 minutos durante a eletrólise, a potencial constante, no tempo de 3 horas. Ambas as análises, EQ-RMNDT e EQ-RMN Unilateral, apresentaram bom desempenho analítico. No entanto, foi observado que a análise de EQ-RMN Unilateral permitiu o monitoramento da reação eletroquímica com um volume detectável de amostra muito menor, em torno de 300 uL, do aquele para a RMN-DT (2,8 mL). O efeito do campo magnético (B0= 0,4 T) sobre o processo eletrolítico foi avaliado pela técnica de microscopia eletrônica de varredura (SEM). A análise SEM mostrou que o eletrodepósito de cobre obtido sob o efeito do campo apresenta uma morfologia rugosa. Para a análise in situ de EQRMN de alto campo, o sistema eletroquímico foi desenvolvido em um tubo de RMN de 10 mm de diâmetro, para ser utilizado em um espectrômetro de 9,4 T. A fibra de carbono foi o material mais adequado para ser utilizado como eletrodo de trabalho. A sequência de Precessão Livre no Estado Estacionário (SSFP, Steady State Free Precession), que não tem dependência do tempo de relaxação longitudinal T1, e permite a aquisição de centenas de espectros por segundo, foi utilizada para monitorar a eletrólise do 9-cloroantraceno por RMN de 13C. A célula EQ-RMN de alto campo construída possibilitou a aquisição de espectros de RMN de 1H e SSFP de 13C durante a eletrólise do 9-cloroantraceno. O Método da Diagonalizacão Filtrada (FDM, Filter Diagonalization Method) foi utilizado para processar sinais no domínio do tempo de SSFP 13C, para resolver os problemas de anomalia de fase e melhorar a resolução espectral. Os sistemas eletroquímicos construídos apresentaram um bom desempenho analítico para o interfaceamento com a RMN, e as metodologias empregadas propiciaram o monitoramento em tempo real de uma reação eletroquímica. / In this work it is described the development of electrochemical (EC) systems coupled to the Low and High-field NMR for in situ analysis. By low-field NMR-EC analysis, it was constructed an electrochemical system to be utilized both TD-NMR spectrometer (B0= 0.23 T) and unilateral sensor (B0= 0.4 T). Platinum was used as working electrode and counter electrode and a silver wire as reference electrode. The copper electrodeposition reaction was monitored by Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence. The measurements of the transverse relaxation time (T2) were collected in the interval of 10 minutes during electrolysis, constant potential, in 3 hours time. Both in situ analyses, TD-NMR-EC and Unilateral NMR-EC, demonstrated good analytical performance. However, the Unilateral NMR-EC allowed the monitoring copper concentration during electrolysis using detectable volume much smaller, approximately 300 uL, than TD-NMR (2.8 mL). The magnetic field effect (B0= 0.4 T) on electrolytic process was available by scanning electron microscopy (SEM) technique. The SEM analysis showed copper electrodeposits obtained on the field effect observes a rough morphology. For the in situ high-field NMR-EC analysis, the electrochemical system was developed in a tube NMR of 10 mm diameter to be utilized 9.4 T spectrometer. Carbon fiber was the most appropriated material to be used as working electrode. The Steady-state free precession (SSFP) sequence that has no dependence on the longitudinal relaxation time T1, allows it to acquire up to hundreds of spectra per T1 value, it was utilized to monitor the electrolysis of 9-chlroanthracene for 13C NMR. The high-field NMR-EC cell constructed allowed the acquisition of the 1H NMR and 13C SSFP spectra during the electrolysis of 9-chlroanthracene. The Filter Diagonalization Method (FDM) was used to process signals in the time domain of 13C SSFP, to solve problems of phase anomalies and improve the spectra resolution. The electrochemical systems constructed showed good analytical performance for coupling with NMR and the methodologies employed provided of the monitoring in real time of the electrochemical reaction.
630

Espectrômetro de RMN de campo remoto / NMR spectrometer with remote magnetic field

Kakuda, Eduardo Shiguemi 02 October 1998 (has links)
Nos espectrômetros de RMN convencionais as amostras são colocadas dentro do gap do ímã, onde encontra-se a região de campo magnético mais intenso e homogêneo. Nessa configuração o tamanho do ímã aumenta de acordo com o tamanho da amostra, dificultando a aplicação da RMN para amostras muito volumosas. Uma configuração em que o ímã não precisa aumentar com o volume da amostra tem sido a geração de campo magnético remoto, onde a região ótima de análise, de campo mais intenso e homogêneo, fica fora do gap do ímã. Neste trabalho avaliou-se os métodos de geração de campo magnético remoto por ímã permanente na forma de ferradura e de campo oposto, para aplicação em RMN. Os ímãs na forma de ferradura foram construídos com cilindros de AlNiCo V, com 100mm de comprimento e130mm de diâmetro, e NdFeB. O ímã de campo oposto foi construído com cilindros de NdFeB com 25mm de espessura e 100mm de diâmetro. Utilizando os ímãs na forma de ferradura, não foi possível observar sinal de RMN pois ha um enorme gradiente de campo que restringe a área útil de análise. Com o ímã de campos opostos foi possível observar o sinal de RMN externamente ao gap do ímã com um campo da ordem de 1,75KGauss. Mesmo com esse ímã a homogeneidade não e muito alta, mas é suficiente para avaliações quantitativas de teores de óleo e umidade em sementes, bem como a cinética de absorção de água pelas sementes. Analisou-se também o comportamento dos modelos angulados para estes dois tipos, mas não se obteve resultados satisfatórios / In a conventional NMR spectrometer the samples are placed inside of the magnet where is situated the most intense and homogeneous area. In this configuration the size of the magnet increases with the volume of the sample, hindering the applications of NMR to very large samples. A way to eliminate this problem is to use magnets that generate a remote magnetic field, where the intense and homogeneous area is outside it. In this work we evaluated two types of magnets for remote NMR. One is a U shaped magnet and the other is a magnet with opposite field. The U shaped magnets were built with two AlNICo V cylinders, seizing 100 mm in length and 130 mm in diameter or two NdFeB cylinders, seizing 25 mm in length and 100 mm in diameter. The magnet with opposite field was build with two cylinders NdFeB. With the U shaped magnet it was not possible to observe the NMR signal due to an enormous magnetic field gradient that restricts the useful area of analysis. Using the magnet with opposite field, it was possible to observe NMR signal outside the magnet with a field of the order of 1,75 KGauss. With this magnet the homogeneity was not very high but it was enough to perform qualitative and quantitative evaluation of oil and humidity in seeds and the kinetics of water absorption by them. The performance of the angled models was analyzed for the two types, but the results obtained were not satisfactory

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