In the past two decades polymer/clay nanocomposites (PCNs) have emerged as promising materials that exhibit remarkably improved properties when compared to conventional composites and pristine polymers. Such improvements strongly depend on the dispersion of clay nanoparticles in the polymer matrix. In spite of great efforts expended in characterizing clay dispersion, effective, simple and quantitative techniques are still needed. This work addresses this challenge by presenting new aspects of 1H solid-state NMR for quantifying clay dispersion in PCNs filled with clay containing paramagnetic ions. Employing these 1H solid-state NMR methods, some structure-processing-deformation relationships of PCNs were derived, and basic insights into nuclear relaxation and spin diffusion in PCNs were gained as well. Detailed models and analyses were described for 1H spin-lattice relaxation in the presence of paramagnetic clays in PCNs. Relaxation recovery was analytically correlated to clay dispersion in two ways: one is the initial relaxation recovery which is related to clay surface area, and the other is the spin-lattice relaxation time which is related to interparticle spacing. These two NMR observables were employed to quantitatively observe the evolution of clay morphology in poly(propylene)/clay (PP/MMT) nanocomposites upon equibiaxial stretching, as well as upon in situ uniaxial deformation. The initial relaxation recovery was independently utilized to determine the polymer-clay interfacial surface area and the degree of clay exfoliation. We demonstrated the capabilities of our models in quantitatively characterizing several materials, including poly(vinyl alcohol), nylon 6, poly(å-caprolactone) (PCL), poly(lactic acid) (PLA) and PP nanocomposites. These results were used to examine the dependence of clay morphology upon processing (strain ratio, strain rate, temperature), deformation (extension), component characteristics (polymer molecular weight, clay surface modification) and clay content. Effects of paramagnetic Fe3+ concentration and external magnetic field strength on 1H spin-lattice relaxation in PCNs were also investigated and discussed. In particular, low field separates the initial relaxation recovery into two stages: one related to clay content and the other related to the polymer-clay interfacial surface area. The low field was observed to enhance the paramagnetic contribution to the spin-lattice relaxation rate, increasing its sensitivity to clay morphology. In addition, measurements of long-distance spin diffusion coefficients for a variety of polymers and paramagnetic characteristics of organically modified clay were explored. Overall, the utility of NMR relaxometry in characterizing PCNs has been significantly expanded and successfully demonstrated in this dissertation.

Study of rare-earth manganites has been a very active research area in the last few years in condensed matter physics. This is due to the interesting phenomena such as (1) colossal magneto resistance (2) charge, orbital and spin ordering and (3) phase separation exhibited by these materials as a function of doping, pressure and temperature [1-3]. There is a lot of experimental data available in literature on different doped manganites, but no satisfactory and complete theoretical understanding is available yet. Though different theoretical models proposed are able to explain certain individual physical properties, a unified theory is missing which can comprehensively explain the full phase diagram. The study of such complex systems requires a probe that is sensitive to various interactions observed in manganites such as spin-spin interactions, spin-lattice interactions, spin-orbit interactions, crystal field interactions and the magnetic environment of the spins. Electron paramagnetic resonance (EPR) being sensitive to these interactions is an ideal probe for investigating these strongly correlated systems. A number of EPR studies have been reported in the paramagnetic phase of manganites, throwing light on the complex spin dynamics present in the manganites [4-10]. There are a few reports in the ferromagnetic state of manganites [11-12]. In recent years, a few studies reporting the observation of phase separation using EPR have also been published [13-15]. Charge ordering phase is the other interesting phase, which is not understood from EPR point of view [16-19]. Recently there are a few reports on suppression of CO phase by reducing the particle size from micro to nano range [20-22]. In this thesis we present the results of Electron Magnetic Resonance (EMR) (EPR in the paramagnetic phase and FMR: ferromagnetic resonance in the ferromagnetic phase) studies supported by magnetization and magneto-transport studies of the following : (1) various magnetic phases in the two electron doped manganite Ca1-xCexMnO3 (CCMO) (2) Charge ordered phase vs. ferromagnetic metallic phase as a function of Cr and Ni doping at the Mn site of Nd0.5Ca0.5MnO3 (NCMO) and comparison between the effect of the two dopants, and (3) a study of nano-sized particles (with different particle size) of Cr doped NCMO. Chapter 1 of the thesis consists of a brief introduction to the general features of manganites describing various phenomena and the interactions underlying them. Further we have written a detailed overview of EPR studies in manganites describing the current level of understanding in the area. In this chapter we have also described the experimental methodology and the analysis procedure adopted in this work. Chapter 2 reports the magnetization, transport and electron paramagnetic resonance studies (EPR) on two electron-doped manganites Ca1-xCexMnO3 (0.075 ≤ x ≤ 0.20). The various compositions of CCMO were prepared by solid-state synthesis and characterized by different techniques like XRD, SEM, EDX, and ICPAES. Our magnetization and transport results are consitent with the earlier reports [23-25]. For compositions x ≥ 0.13, all the EPR parameters viz. intensity, linewidth and the resonance field show signatures of a CO phase and at low temperature coexistence of two magnetic phases. x = 0.1 composition shows the most interesting results. Though the EPR intensity and resonance field indicate the presence of a CO phase, the EPR linewidth shows behaviour of a spin-disordered phase which we attribute to a possible spin-liquid phase [26]. The linewidth for x = 0.11 composition shows a combination of a CO and a spin-disorderd phase. For low composition x = 0.075, we observe a weak ferromagnetic phase and later on at low temperatures an antiferromagnetic phase. We do not observe the CO phase for this composition. In chapter 3, we present the magnetization, magnetotransport and EMR studies on Cr doped NCMO (0.0 ≤ x ≤ 0.10) [27]. The samples were prepared by solid-state synthesis and characterized by various techniques like XRD, SEM, EDX, and ICPAES. The magnetization studies show that the Cr doping induces ferromagnetic phase at low temperatures. With the increase of Cr doping the magnetization increases at the expense of the CO phase and for higher doping CO phase disappears completely. The Cr doping induces insulator-metal transition and with increase of Cr doping the metallic phase increases. The doped samples show high CMR, almost 100%, near the TC. The EMR studies in the paramagnetic phase indicate a CO phase for low Cr doping and the presence of short-range dynamical CO-OO correlations for higher Cr doping, which were not observed in magnetization studies. We observe two EPR signals at low temperatures for the Cr doped samples. For 3% doping, the two signals appear well above TC whereas for higher doping (5%, 10%) the two signals were observed in the FM phase. We rule out the possibility of the two-signal behaviour arising from the coexistence of two magnetic phases. For higher doping, the presence of two signals in FM phase can be attributed to magnetic anisotropy. With increase of Cr doping, magnetic anisotropy decreases which is also supported by reduction of magnetic anisotropy in magnetization measurements. But it cannot explain the observation of two signals above TC in the 3% doped sample. In chapter 4, we present the magnetization, magnetotransport and EMR studies on Ni doped NCMO (0.0 ≤ x ≤ 0.10). The samples were prepared by solid-state synthesis and characterized by various techniques like XRD, SEM, EDX, and ICPAES. The magnetization studies show that the Ni doping induces ferromagnetic phase at low temperatures. With the increase of Ni doping, though the CO phase is suppressed, the FMM phase also weakens which is different from the behaviour observed in Cr doped NCMO. The Ni doping induces insulator-metal transition and with increase of Ni doping, the metallic phase weakens. The magnetic anisotropy increases with increase of Ni doping as obtained from magnetization measurements and the EMR data also corroborates the same fact. The EMR studies in the paramagnetic phase indicate a CO phase for low Ni doping and the presence of short-range dynamical CO-OO correlations for higher Ni doping, which were not observed in magnetization studies. We observe two signals in the FM phase, which again can be attributed to the magnetic anisotropy. In chapter 5, we present EMR studies on nano-particles of Cr doped NCMO for x = 0.03. We have prepared nano-particles of three different sizes by the sol-get route. The samples were characterized by various techniques like XRD, SEM, EDX, and ICPAES. The particle sizes are 50, 100, 200 nm. We also compare the results of nano samples with the bulk samples. The ac susceptibility measurements show that the FM phase increases with the reduction of particle size. The EMR measurements show that the magnetic anisotropy decreases with decrease of particle size. The EMR linewidth in the paramagnetic phase increases with the decrease of particle size. The EMR intensity also increases with the reduction of particle size consitent with the magnetization results. The EMR results show that the reduction of particle size is one more way of inducing FM phase more effectively. Also the CO phase gets suppressed with the reduction of particle size. The two-signal feature is observed for all the particles. For nano-sized particles, the two signals appear in FM phase whereas in bulk sample they appeared well above TC. For 50 nm sized particles, the two signals appear well below 40 K. Thus we conclude that with decrease of particle size, the magnetic anisotropy decreases. The thesis concludes with a brief writeup summarizing the results and indicating possible future directions of research in the area.

No description available.

Thesis (Ph.D.)--Ohio University, March, 2010. / Title from PDF t.p. Includes bibliographical references.

abstract: Microwave properties of low-loss commercial dielectric materials are optimized by adding transition-metal dopants or alloying agents (i.e. Ni, Co, Mn) to tune the temperature coefficient of resonant frequency (τf) to zero. This occurs as a result of the temperature dependence of dielectric constant offsetting the thermal expansion. At cryogenic temperatures, the microwave loss in these dielectric materials is dominated by electron paramagnetic resonance (EPR) loss, which results from the spin-excitations of d-shell electron spins in exchange-coupled clusters. We show that the origin of the observed magnetically-induced shifts in the dielectric resonator frequency originates from the same mechanism, as described by the Kramers-Kronig relations. The temperature coefficient of resonator frequency, τf, is related to three material parameters according to the equation, τf = - (½ τε + ½ τµ + αL), where τε, τµ, and αL are the temperature coefficient of dielectric constant, magnetic permeability, and lattice constant, respectively. Each of these parameters for dielectric materials of interest are measured experimentally. These results, in combination with density functional simulations, developed a much improved understanding of the fundamental mechanisms responsible for τf. The same experimental methods have been used to characterize in-situ the physical nature and concentration of performance-degrading point defects in the dielectrics of superconducting planar microwave resonators. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

Orientadores: Gilberto Medeiros Ribeiro e Jose Antonio Brum / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-11T11:01:49Z (GMT). No. of bitstreams: 1 Alegre_ThiagoPedroMayer_D.pdf: 15787837 bytes, checksum: a41c0877b93a156734db9d614610e2f4 (MD5) Previous issue date: 2008 / Resumo: Esta tese consistiu na proposição e implementação de um sistema para processamento de informação quântica, focando a instrumentação necessária. Os aspectos físicos da computação, como a energia associada, entropia de Shannon, entre outros conceitos básicos observados na perspectiva de física, foram revistos. Pontos quânticos semicondutores de InAs:GaAs foram eleitos como candidatos para a implementação física do sistema; em particular, focou-se no grau de liberdade de spin do elétron. Conseqüentemente, investigaram-se as propriedades de tensor-g dos elétrons aprisionados em pontos quânticos e o grau de polarização de spin, como função do campo magnético e da temperatura. Naturalmente, as propriedades eletrônicas, como o potencial de confinamento e as transições ópticas, foram caracterizadas e modeladas através da teoria de massa efetiva, assumindo-se um potencial de confinamento lateral parabólico. Dado que o grau de liberdade de spin foi eleito, construiu-se um sistema de medidas de ressonância paramagnética de spins. Optou-se por não se utilizar sistemas comerciais padrão. Em lugar disto, foi projetada uma montagem conectorizada, onde o material semicondutor se encontra dentro de umchip desenhado para concentrar o campo magnético de microonda sobre o dispositivo, campo este necessário para a realização de ressonância paramagnética. O chip consistiu basicamente de uma cavidade de microfita de meia onda. Foi construída também uma cavidade com duas entradas, permitindo o controle arbitrário da polarização aplicada à amostra. Finalmente, a leitura de estados quânticos de spin em centros paramagnéticos é demonstrada através de detecção óptica. A alta sensibilidade desse tipo de detecção permite que um único defeito seja mapeado. A seletividade, tanto do ponto de vista das transições ópticas quanto das transições de spin, é estudada e manipulada, utilizando-se da montagem experimental de cavidades ressonantes. Adicionalmente, perspectivas de experimentos sobre a integração e utilidade do sistema são apresentados / Abstract: This thesis proposes and implements a system for quantum information processing, focusing primarily on the associated instrumentation. The basic physical aspects for computation, such as the associated energy and Shannon's entropy, were revisited. InAs:GaAs quantum dots were elected as the physical system of choice for this implementation; in particular, the spin degree of freedom of the trapped electrons was utilized. Therefore, the electronic properties of the quantum dots, as well the g-tensor and the polarization degree, were investigated as a function of the temperature and magnetic field. It was possible to describe the electronic properties within the effective mass formalism, assuming a parabolic lateral confinement. Since the spin degree of freedom was elected as the basis for the quantum computation, a system for spin paramagnetic resonance was devised. The choice for not using a commercial system was made. Instead, a connectorized setup was designed, permitting the semiconductor material to be within a chip, and additionally allowing for focusing the microwave magnetic field above the device. Basically, this chip consisted of a half-wavelength microstrip cavity. A second microstrip cavity with two input ports was also designed to allow the arbitrary control of microwave polarization delivered to the sample. Finally, the quantum state read-out was demonstrated through an optical technique on Nitrogen-Vacancy complexes in diamond. The high sensitivity of the system allows for single spin detection. The selectivity for the optical and spin transitions was characterized and manipulated, using the resonant cavity experimental setup. As a perspective, experiments exploring integration issues on the system are shown / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Submitted by Erika Demachki (erikademachki@gmail.com) on 2015-01-29T17:17:40Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Tese - Sebastião Antônio Mendanha Neto - 2014.pdf: 7092471 bytes, checksum: 12e06f6af9661e3416fd2248ee25333c (MD5) / Approved for entry into archive by Erika Demachki (erikademachki@gmail.com) on 2015-01-29T17:41:44Z (GMT) No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Tese - Sebastião Antônio Mendanha Neto - 2014.pdf: 7092471 bytes, checksum: 12e06f6af9661e3416fd2248ee25333c (MD5) / Made available in DSpace on 2015-01-29T17:41:44Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Tese - Sebastião Antônio Mendanha Neto - 2014.pdf: 7092471 bytes, checksum: 12e06f6af9661e3416fd2248ee25333c (MD5) Previous issue date: 2014-04-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The interactions of terpenes with membranes of erythrocyte, fibroblasts, stratum corneum and the model membranes of 1,2-dipalmitoylsn -glycero-3-phosphocholine were investigated by using the the electron paramagnetic resonance and fluorescence spectroscopic of lipophilic probes. It has been shown that when added at high concentrations to systems having a high lipid/solvent ratio, terpenes such as 1,8-cineol, α-terpineol, (+)-limonene and nerolidol are able to self-stabilize in molecular aggregates which can extract the bilayers lipids. Studies on the hemolytic and cytotoxic potential of various terpenes showed that cell damage caused by these molecules are concentration dependent and that among the studied terpenes, nerolidol and α-terpineol are the most hemolytic and cytotoxic, while (+)-limonene and 1,8-cineole are the least hemolytic and cytotoxic. However, the low correlation between these two tests indicates that the processes involved in each case are not completely dependent. It was also shown that once embedded in the membrane, terpenes increase the fluidity of lipid bilayers and decrease the temperature of the main phase transition. Differences between increased fluidity promoted by sesquiterpene nerolidol and all monoterpenes studied were observed. Meanwhile, in a comparison of the effect of the monoterpenes studied, no significant differences in their ability to increase membrane fluidity were detected. Furthermore, it was demonstrated by using confocal and atomic force microscopy and fluorescence spectroscopy that the 1,2-distearoylsn -glycero-3-(Aurora nanoparticles) is better incorporated in lipid membranes under fluid phase and that the addition of 0.1% of these conjugated nanoparticles do not produces large variations in membrane fluidity and no causes substantial morphological changes of lipid bilayers. / As intera¸c˜oes de terpenos com membranas de eritr´ocito, fibroblastos, estrato c´orneo e membrana modelo composta de 1,2-dipalmitoil-sn -glicero-3-fosfocolina foram investigadas por meio das espectroscopias de ressonˆancia paramagn´etica eletrˆ onica e de fluorescˆencia por meio do uso de sondas lipof´ılicas. Foi poss´ıvel demonstrar que quando adicionados em altas concentra¸c˜oes `a sistemas que possuem uma alta rela¸c˜ao lip´ıdio/solvente, terpenos como o 1,8-cineol, α-terpineol, (+)-limoneno e nerolidol s˜ao capazes de se estabilizar em agregados moleculares capazes de extrair os lip´ıdios das bicamadas. Estudos sobre o potencial hemol´ıtico e citot´oxico de v´arios terpenos demostraram que os danos celulares causados por estas mol´eculas s˜ao dependentes da concentra¸c˜ao e que dentre os terpenos estudados, nerolidol e terpineol s˜ao os mais hemol´ıticos e citot´oxicos enquanto limoneno e cineol s˜ao os menos hemol´ıticos e citot´oxicos. Entretanto, a baixa correla¸c˜ao entre estes dois testes indica que os processos envolvidos em cada caso n˜ao s˜ao totalmente dependentes. Ficou demonstrado ainda que uma vez incorporados nas membranas, os terpenos aumentam a fluidez das bicamadas lip´ıdicas e diminuem a temperatura de sua transi¸c˜ao de fase principal. Diferen¸cas entre o aumento de fluidez promovido pelo sesquiterpeno nerolidol e por todos os monoterpenos estudados foram verificadas. Contudo, uma compara¸c˜ao entre o efeito dos monoterpenos estudados, n˜ao aponta para diferen¸cas significativas entre suas capacidades de aumento de fluidez. Al´em disso, foi demostrado atrav´es das microscopias confocal e de for¸ca atˆomica e da espectroscopia de fluorescˆencia que a 1,2-distearoil-sn -glicero-3-(Nanopart´ıculas Aurora) ´e melhor incorporada em membranas lip´ıdicas em fase fluida e que a adi¸c˜ao de 0,1% destas nanopart´ıculas conjugadas n˜ao produz grandes varia¸c˜oes na fluidez e n˜ao provoca mudan¸cas morfol´ogicas substanciais das bicamadas lip´ıdicas.

Orientador: Eneida de Paula / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Biologia / Made available in DSpace on 2018-08-07T20:44:09Z (GMT). No. of bitstreams: 1 Prete_PauloSergioCastilho_D.pdf: 3376950 bytes, checksum: fd06e65f64531668e35cf4a9cb817913 (MD5) Previous issue date: 2006 / Resumo: Surfatantes ou detergentes são compostos anfifílicos que, na presença de água, têm a característica de formar agregados micelares. Surfatantes induzem a desestruturação de outros agregados como bicamadas sendo, por isso, usados para ruptura celular ou solubilização de lipídios e proteínas de membrana. A capacidade lítica dos surfatantes resulta de sua estrutura química, que determina o modo de interação dos mesmos com as membranas. Em concentrações mais altas (acima da concentração micelar crítica), os surfatantes desestabilizam as bicamadas lipídicas, levando à formação de micelas-mistas. Ensaios hemolíticos são bons modelos para estudo do efeito lítico de surfatantes em biomembranas. Aplicando em eritrócitos humanos o tratamento quantitativo proposto por Lichtenberg (1985) para estudo da solubilização de bicamadas lipídicas mensurou-se, neste trabalho, as concentrações para início (Csat) e 100% de hemólise (Csol), induzidas por 25 surfatantes clássicos, pertencentes a cinco diferentes famílias. A variação dos valores de Csat, Csol determinada com diferentes hematócritos permitiu o cálculo da constante de ligação surfatante/membrana e da razão surfatante/lipídio de membrana (Re) para início e 100% de hemólise. O parâmetro Re foi usado para classificar os detergentes como fortes, médios ou fracos agentes solubilizantes, com boa correlação com dados da literatura o que nos permitiu propor seu uso para descrever o efeito lítico de surfatantes, como uma alternativa simples e aplicável as membranas biológicas. As transições durante o processo hemolítico foram acompanhadas pela técnica de Ressonância Paramagnética Eletrônica, com uso marcador de spin 5 doxil-estearato (incorporado a 1 mol% nas membranas de eritrócito) e lise induzida pelo surfatante não iônico Triton X100. Concomitante ao aparecimento de hemoglobina e fosfato livres no sobrenadante - indicadores da ruptura da membrana, medidas do parâmetro de ordem daquele marcador de spin permitiram estudar as transições que acontecem durante (membrana:membrana mista) e após (membrana mista:micela mista) a hemólise / Abstract: Surfactants or detergents are amphiphilic compounds that form micellar aggregates in the presence of excess water. Surfactants are able to induce disruption of lamellar aggregates, justifying their use for cell lysis or in the extraction of membrane constituents such as lipids and proteins. The lytic capacity of a given surfactant is determined by its chemical structure, that rules its interaction with the membranes. At high concentration (above the critic micelle concentration), surfactants destabilize lipid bilayer leading to mixed micelle formation. Hemolytic assays are a good model to study the lytic effect of surfactants on biomembranes. In this study we have applied to human erythrocytes the quantitative treatment proposed by Lichtenberg (1985) to describe the solubilization of model lipid membranes. The concentration for onset (Csat) and complete (Csol) hemolysis induced by 25 classic surfactants from five different families were measured. Changes in Csat and Csol values at different hematocrits allowed the determination of the surfactant/membrane lipid molar ratio (Re) for beginning and 100% lysis. The Re arameter was used to classify the surfactants as strong, medium or weak membrane solubilizers. The classification was in good correlation with data in the literature, allowing us to recommend the use of Re parameter to describe the lyric effect of surfactants on biomembranes. The transitions in the hemolytic process were accompanied by Electron Paramagnetic Resonance, using the 5-doxyl-stearate spin-probe (1 mol%, incorporated in the erythrocyte membrane) and the non-ionic surfactant Triton X100. Simultaneously to the appearance of hemoglobin and phosphate released in the supernatant, measurements of the order parameter of the spin probe were used to characterize the transitions that take place during (membrane :mixed membrane) and after (mixed: membrane: mixed micelle) hemolysis / Doutorado / Bioquimica / Doutor em Biologia Funcional e Molecular

Tritrpticina (TRP3) é um peptídeo antimicrobiano com 13 resíduos de amino ácidos com três Ws sequenciais. Com o objetivo de contribuir para a compreensão de seu mecanismo de ação, realizaram-se estudos funcionais e conformacionais da TRP3 e de dois análogos onde um (WLW) ou dois (LWL) W foram substituídos por L. Os peptídeos foram igualmente ativos contra bactérias Gram positivas e negativas. Sua atividade hemolítica requereu concentrações maiores, diminuindo na ordem TRP3>WLW>LWL. Os peptídeos permeabilizaram membranas modelo de E. coli ou contendo fosfolipídios carregados negativamente. Espectros de CD sugeriram que os peptídeos adquirem diferentes conformações ao se ligarem a bicamadas e micelas. Estudos de fluorescência mostraram que a ligação a membranas decresce na ordem: TRP3>WLW>LWL e que os peptídeos se localizam próximos à interface membrana-água. Espectros de RPE de marcadores de spin lipídicos indicaram que a ligação dos peptídeos altera a organização dos lipídios, aumentando o empacotamento molecular / Tritrpticin (TRP3) is a 13-residue antimicrobial peptide that contains three sequential Ws. With the aim of contributing to the understanding of its mechanism of action, functional and conformational studies were performed with TRP3 and two of its analogues where one (WLW) or two (LWL) of the W were replaced by L. The peptides were equally active against both Gram positive and Gram negative bacteria. Higher concentrations were required for hemolytic activity which varied in the order: TRP3>WLW>LWL. The peptides permeabilized membranes model membranes mimicking E. coli\'s lipid composition or containing different negatively charged phospholipids. CD spectra suggested the peptides acquired different conformations upon binding to bilayers or micelles. Fluorescence studies showed that membrane binding decreases in the order: TRP3>WLW>LWL and that the peptides are located close to the water-membrane interface. EPR spectra of lipid spin labels indicated that peptide binding alter lipid organization, increasing molecular packing

La résonance paramagnétique électronique est une technologie permettant de localiser et de caractériser les radicaux libres, fondée sur la propriété de résonance des électrons libres lorsqu’ils sont placés dans un champ magnétique spécifique. Afin d’augmenter la qualité des reconstructions obtenues par des dispositifs d’imagerie de résonance paramagnétique électronique, ce travail propose l’utilisation de méthodes variationnelles pour inverser le modèle de formation des images, qui combine une convolution avec une transformée de Radon. La fonctionnelle proposée repose sur la norme L2 pour le terme d’attache aux données, et sur la variation totale et une seminorme de Besov pour le terme de régularisation. La seminorme de Besov est implémentée grâce à la transformée en curvelets et à la norme L1 qui permet d’appliquer un critère de parcimonie. Les propriétés de ces termes de régularisation permettent de reconstruire des images à la fois pertinentes dans les zones où l’acquisition des données est insuffisante, notamment sur les bords, et suffisamment détaillées dans les zones où l’échantillon est texturé. L’augmentation de la qualité des images reconstruites permet d’envisager des acquisitions sur des durées réduites, ouvrant la voie à des expériences in vivo ou cliniques actuellement limitées par des durées d’acquisition de l’ordre de plusieurs dizaines de minutes. Les algorithmes de minimisation primal-dual de Chambolle-Pock et FISTA sont utilisés pour résoudre les problèmes d’optimisation que pose l’utilisation de méthodes variationnelles. L’étude détaillée du modèle direct permet de mettre en évidence une structure de Toeplitz, dont les propriétés sont utilisées pour résoudre le problème inverse en évitant le recours à la rétroprojection filtrée ou aux transformées de Fourier non-uniformes. Des simulations numériques sont menées sur le fantôme de Shepp-Logan, et valident le modèle proposé qui surpasse à la fois visuellement et quantitativement les techniques de reconstruction couramment utilisées, combinant déconvolution et rétroprojection filtrée. Des reconstructions menées sur des acquisitions réelles, consistant en un échantillon papier d’une encre paramagnétique et en une phalange distale irradiée, valident par l’expérience le choix des fonctionnelles utilisées pour inverser le modèle direct. La grande souplesse de la méthode variationnelle proposée permet d’adapter la fonctionnelle au problème de la séparation de sources qui se pose lorsque deux molécules paramagnétiques différentes sont présentes au sein d’un même échantillon. La fonctionnelle proposée permet de séparer les deux molécules dans le cadre d’une acquisition classique d’imagerie de résonance paramagnétique électronique, ce qui n’était possible jusqu’alors que sur des acquisitions dites hyperspectrales beaucoup plus gourmandes en temps. / Spatial electron paramagnetic resonance imaging (EPRI) is a recent method to localize and characterize free radicals in vivo or in vitro, leading to applications in material and biomedical sciences. To improve the quality of the reconstruction obtained by EPRI, a variational method is proposed to inverse the image formation model. It is based on a least-square data-fidelity term and the total variation and Besov seminorm for the regularization term. To fully comprehend the Besov seminorm, an implementation using the curvelet transform and the L1 norm enforcing the sparsity is proposed. It allows our model to reconstruct both image where acquisition information are missing and image with details in textured areas, thus opening possibilities to reduce acquisition times. To implement the minimization problem using the algorithm developed by Chambolle and Pock, a thorough analysis of the direct model is undertaken and the latter is inverted while avoiding the use of filtered backprojection (FBP) and of non-uniform Fourier transform. Numerical experiments are carried out on simulated data, where the proposed model outperforms both visually and quantitatively the classical model using deconvolution and FBP. Improved reconstructions on real data, acquired on an irradiated distal phalanx, were successfully obtained. Due to its great versatility, the variational approach is easily extended to the source separation problem which happens when two different paramagnetic species are present in the sample. The objective function is consequently modified, and a classic EPRI acquisition yields two images, one for each species. Until now, source separation could only be applied to hyperspectral EPRI data, much more costly in acquisition time.