To optimize contrast agent in MRI scan region, e.g. to enhance paramagnetic relaxation in the MRI scan fields(0.1T-3T), one possible way is to slow down the tumbling of the paramagnetic complex. The effect of slowing down the reorientational motion of the complex to increase relaxivity is obvious and this strategy has already been employed in producing MRI contrast agent that can bind to specific proteins. An example is MS-325 binds to human serum albumin(HSA). The slow down effects on the ligands around paramagnetic ion, and on the zero field splitting(ZFS) interaction are under studies and the physics behind is still not clear. In this thesis, a generalized Solomon-Bloembergen-Morgan(GSBM) theory together with stochastic Liouville approach(SLA), is applied to investigate the mechanism behind the slow down effects. Two gadolinium complexes, MS-325+HSA and Gd(H2O)83++glycerol are studied by means of NMRD and ESR experiments. GSBM is a second order perturbation theory with closed analytical form. The computation based on this theory is fast, but it has its limitation and in the case of Gd(S=7/2) the ZFS strength times its correlation time(Δt.τƒ) should be less than 0.1. In comparison, the SLA is an "exact" theory that can evaluate the validity of GSBM calculation. However, the calculation in SLA is time consuming due to the large matrix it constructed. The major model used in GSBM is a two dynamic model, characterized by transient ZFS Δt and static ZFS Δs and their corresponding correlation time τƒ and τR, while in SLA the model is only described by Δt and τƒ. A combined NMRD and ESR analysis is used to understand the details of ZFS interaction. Both models can reproduce experimental NMRD profiles and model parameters are similar; for ESR linewidths the model parameters are quite different. The fitting results indicate the NMRD profiles are less sensitive to the detail expression of ZFS correlation function. In order to interpret both NMRD and ESR experiments with identical parameters, a more complex ZFS interaction model should be developed.

Macromolecular transitions such as conformational changes and protein-protein association underlie many biological processes. Conformational changes in the N-terminal domain of the transmembrane protein DsbD (nDsbD) were studied by NMR and molecular dynamics (MD) simulations. nDsbD supplies reductant to biosynthetic pathways in the oxidising periplasm of Gram-negative bacteria after receiving reductant from the C-terminal domain of DsbD (cDsbD). Reductant transfer in the DsbD pathway happens via protein-protein association and subsequent thiol-disulphide exchange reactions. The cap loop shields the active-site cysteines in nDsbD from non-cognate oxidation, but needs to open when nDsbD bind its interaction partners. The loop was rigid in MD simulations of reduced nDsbD. More complicated dynamics were observed for oxidised nDsbD, as the disulphide bond introduces frustration which led to loop opening in some trajectories. The simulations of oxidised and reduced nDsbD agreed well with previous NMR spin-relaxation and residual dipolar coupling measurements as well as chemical shift-based torsion angle predictions. NMR relaxation dispersion experiments revealed that the cap loop of oxidised nDsbD exchanges between a major and a minor conformation. The differences in their conformational dynamics may explain why oxidised nDsbD binds its physiological partner cDsbD much tighter than reduced nDsbD. The redox-state dependent interaction between cDsbD and nDsbD is thought to enhance turnover. NMR relaxation dispersion experiments gave insight into the kinetics of the redox-state dependent interaction. MD simulations identified dynamic encounter complexes in the association of nDsbD with cDsbD. The mechanism of the conformational changes in the transport cycle of LacY were also investigated. LacY switches between periplasmic open and cytoplasmic open conformations to transport sugars across the cell membrane. Two mechanisms have been proposed for the conformational change, a rocker-switch mechanism based on rigid body motions and an “airlock” like mechanism in which the transporter would switch conformation via a fully occluded structure. In MD simulations using the novel dynamics importance sampling approach such a fully occluded structure was found. The simulations argued against a strict “rocker-switch” mechanism.

Spintronics or electronics that utilizes the spin degree of freedom of a single charge carrier (or an ensemble of charge carriers) to store, process, sense or communicate data and information is a rapidly burgeoning field in electronics. In spintronic devices, information is encoded in the spin polarization of a single carrier (or multiple carriers) and the spin(s) of these carrier(s) are manipulated for device operation. This strategy could lead to devices with low power consumption. This dissertation investigates spin transport in one dimensional and two dimensional semiconductors, with a view to applications in spintronic devices.

Since a decade, spintronics and related physics have attracted considerable attention due to the massive research conducted in these areas. The main reason for growing interest in these fields is the expectation to use the electrons spin instead of or in addition to the charge for the applications in spin-based electronics, quantum information, and quantum computation. A prime concern for these spins to be possible candidates for carrying information is the ability to coherently control them on the time scales much faster than the decoherence times. This thesis reports on the spin dynamics in two-dimensional electron gases hosted in artificially grown III-V semiconductor quantum wells. Here we present a series of experiments utilizing the techniques to optically control the spin polarization triggered by either optical or electrical methods i.e. well known pump-probe technique and current-induced spin polarization. We investigated the spin coherence in high mobility dense two-dimensional electron gas confined in GaAs/AlGaAs double and triple quantum wells, and, it\'s dephasing on the experimental parameters like applied magnetic field, optical power, pump-probe delay and excitation wavelength. We have also studied the large spin relaxation anisotropy and the influence of sample temperature on the long-lived spin coherence in triple quantum well structure. The anisotropy was studied as a function sample temperature, pump-probe delay time, and excitation power, where, the coherent spin dynamics was measured in a broad range of temperature from 5 K up to 250 K using time-resolved Kerr rotation and resonant spin amplification. Additionally, the influence of Al concentration on the spin dynamics of AlGaAs/AlAs QWs was studied. Where, the composition engineering in the studied structures allows tuning of the spin dephasing time and electron g-factor. Finally, we studied the macroscopic transverse drift of long current-induced spin coherence using non-local Kerr rotation measurements, based on the optical resonant amplification of the electrically-induced polarization. Significant spatial variation of the electron g-factor and the coherence times in the nanosecond scale transported away half-millimeter distances in a direction transverse to the applied electric field was observed. / Há uma década, a spintrônica e outras áreas relacionadas vêm atraindo considerável atenção, devido a enorme quantidade de pesquisa conduzidas por elas. A principal razão para o crescente interesse neste campo é a expectativa da aplicação do controle do spin do elétron no lugar ou em adição à carga, em dispositivos eletrônicos e informação e computação quânticas. A possibilidade destes spins carregarem informação depende, primeiramente, da habilidade de controlá-los coerentemente, em uma escala de tempo muito mais rápida do que o tempo de decoerência. Esta tese trata da dinâmica de spins em gases de elétrons bidimensionais, em poços quânticos de semicondutores III-V, crescidos artificialmente. Nós apresentamos uma série de experimentos, utilizando técnicas para o controle ótico da polarização de spin, desencadeadas por métodos óticos ou eletrônicos, ou seja, técnicas conhecidas de bombeio e prova e polarização de spin induzida por corrente. Nós investigamos a coerência de spin em gases bidimensionais, confinados em poços quânticos duplos e triplos de GaAs/AlGaAs e a dependência da defasagem com parâmetros experimentais, como campo magnético externo, potência ótica, tempo entre os pulsos de bombeio e prova e comprimento de onda da excitação. Também estudamos a grande anisotropia de relaxação de spin como função da temperatura da amostra, potência de excitação e defasagem entre bombeio e prova, medidos para uma vasta gama de temperatura, entre 5K e 250K, usando Rotação de Kerr com Resolução Temporal (TRKR) e Amplificação Ressonante de Spin (RSA). Além disso estudamos a influência da concentração de Al na dinâmica dos poços de AlGaAs/AlAs, para o qual a engenharia da composição da estrutura permite sintonizar o tempo de defasagem de spin e o fator $ g $ do elétron. Por fim, estudamos a deriva transversal macroscópica da longa coerência de spin induzida por corrente, através de medidas de Rotação de Kerr não-locais, baseadas na amplificação ressonante ótica da polarização eletricamente induzida. Observamos uma variação espacial significante do fator $ g $ e do tempo de vida da coerência, na escala de nanosegundos, deslocada distâncias de meio milímetro na direção transversa ao campo magnético aplicado.

<p>To optimize contrast agent in MRI scan region, e.g. to enhance paramagnetic relaxation in the MRI scan fields(0.1T-3T), one possible way is to slow down the tumbling of the paramagnetic complex. The effect of slowing down the reorientational motion of the complex to increase relaxivity is obvious and this strategy has already been employed in producing MRI contrast agent that can bind to specific proteins. An example is MS-325 binds to human serum albumin(HSA). The slow down effects on the ligands around paramagnetic ion, and on the zero field splitting(ZFS) interaction are under studies and the physics behind is still not clear. In this thesis, a generalized Solomon-Bloembergen-Morgan(GSBM) theory together with stochastic Liouville approach(SLA), is applied to investigate the mechanism behind the slow down effects. Two gadolinium complexes, MS-325+HSA and Gd(H₂O)₈³⁺+glycerol are studied by means of NMRD and ESR experiments.</p><p>GSBM is a second order perturbation theory with closed analytical form. The computation based on this theory is fast, but it has its limitation and in the case of Gd(S=7/2) the ZFS strength times its correlation time(Δ<i>t</i>.<i>τ</i>_ƒ) should be less than 0.1. In comparison, the SLA is an "exact" theory that can evaluate the validity of GSBM calculation. However, the calculation in SLA is time consuming due to the large matrix it constructed. The major model used in GSBM is a two dynamic model, characterized by transient ZFS Δ<i>t</i> and static ZFS Δ<i>s</i> and their corresponding correlation time <i>τ</i>_ƒ and <i>τR</i>, while in SLA the model is only described by Δ<i>t</i> and <i>τ</i>_ƒ. A combined NMRD and ESR analysis is used to understand the details of ZFS interaction. Both models can reproduce experimental NMRD profiles and model parameters are similar; for ESR linewidths the model parameters are quite different. The fitting results indicate the NMRD profiles are less sensitive to the detail expression of ZFS correlation function. In order to interpret both NMRD and ESR experiments with identical parameters, a more complex ZFS interaction model should be developed.</p>

Lobtention dun bon contraste en imagerie médicale est un pré-requis à un examen de qualité. Limagerie médicale basée sur la résonance nucléaire magnétique utilise diverses substances magnétiques comme agent de contraste. Le développement dagents de contraste à la fois plus performants et plus économiques sappuie fortement sur létude fondamentale des propriétés magnétiques de divers matériaux potentiellement utilisables. Dans ce travail, deux voies ont été poursuivies. La première partie est consacrée à des matériaux à transition de spin, qui pourraient être utilisés comme agents de contraste en résonance magnétique, pour autant que leur température de transition soit voisine de celle du corps humain. En effet, ces matériaux ont la particularité de posséder deux états magnétiques différents et, sous linfluence dune perturbation telle que la pression ou la température, peuvent passer dun état à lautre, à savoir létat paramagnétique ou diamagnétique. Les complexes de fer(II) étudiés sont basés sur des ligands tri-pyrazolyl borate et méthane. Une autre voie suivie pour améliorer le diagnostic médical est le développement et lutilisation de nanoparticules magnétiques fonctionnelles pour la détection et/ou le traitement des cellules cancéreuses. Dans la deuxième partie de ce travail, les propriétés magnétiques de nanoparticules ferriques préparées par deux méthodes différentes sont investiguées. La spectroscopie Mössbauer est largement utilisée dans cette thèse et les résultats obtenus par cette technique constituent la contribution principale de lauteur au travail. Cette technique, basée sur la fluorescence résonnante sans recul des rayons gamma, permet létude des interactions hyperfines de matériaux solides contenant du fer. Appliquée aux matériaux à transition de spin et aux nanoparticules, deux champs dapplication bien distincts, la spectroscopie Mössbauer fournit des informations structurelles et magnétiques. Elle complémente admirablement dautres techniques macroscopiques et microscopiques, comme la magnétométrie, la microscopie électronique et la diffraction des rayons X. Les autres techniques qui ont été utilisées par lauteur sont la magnétométrie et la relaxation des muons. Cest la première fois, que cette dernière technique est introduite dans léventail des techniques exploitées à lUniversité de Liège.

Nuclear magnetic resonance (NMR) spectroscopy was used to determine the structure of transmembrane (TM) segment IX of the Na+/H+ exchanger isoform 1 (NHE1) in dodecylphosphocholine micelles. Studying isolated TM segments in this fashion constitutes a well-established "divide and conquer" approach to the study of membrane proteins, which are often extremely difficult to produce, purify, and reconstitute in full-length polytopic form. A similar approach was combined with NMR spin relaxation experiments to determine the peptide backbone flexibility of NHE1 TM VII. The combined NMR structural and dynamics studies are consistent with an important role for TM segment flexibility in the function of NHE1, a protein involved in apoptosis and myocardial disease. The study of the rhomboid protease system is also described from two perspectives: 1) I attempted to produce several TM constructs of the substrate spitz or a related construct and the production and purification are described in detail; and 2) I present coarse-grained molecular dynamics simulation results for the E. coli rhomboid ecGlpG and a spitz TM construct. Spitz appears to preferentially associate with rhomboid near TMs 1 and 3 rather than the proposed substrate gate at TM 5. The two proteins primarily interact at the termini of helices rather than within the hydrocarbon core of the bilayer. Finally, I present a detailed analysis of coarse-grained molecular dynamics simulations of the fibroblast growth factor receptor 3 TM domain dimerization. Specifically, algorithms are described for analyzing critical features of wild-type and G380R mutant constructs. The G380R mutation is the cause of achondroplasia, the most common form of human dwarfism. The results suggest that the proximity of a residue to the dimer interface may impact the severity of the mutant phenotype. Strikingly, heterodimer and mutant homodimer constructs exhibit a secondary dimer interface which may explain the increased signaling activity previously reported for the G380R mutation--the helices may rotate with the introduction of G380R. The unifying theme of this work is the 'study of membrane proteins' using complementary techniques from structural biology and computational biochemistry.

Since a decade, spintronics and related physics have attracted considerable attention due to the massive research conducted in these areas. The main reason for growing interest in these fields is the expectation to use the electrons spin instead of or in addition to the charge for the applications in spin-based electronics, quantum information, and quantum computation. A prime concern for these spins to be possible candidates for carrying information is the ability to coherently control them on the time scales much faster than the decoherence times. This thesis reports on the spin dynamics in two-dimensional electron gases hosted in artificially grown III-V semiconductor quantum wells. Here we present a series of experiments utilizing the techniques to optically control the spin polarization triggered by either optical or electrical methods i.e. well known pump-probe technique and current-induced spin polarization. We investigated the spin coherence in high mobility dense two-dimensional electron gas confined in GaAs/AlGaAs double and triple quantum wells, and, it\'s dephasing on the experimental parameters like applied magnetic field, optical power, pump-probe delay and excitation wavelength. We have also studied the large spin relaxation anisotropy and the influence of sample temperature on the long-lived spin coherence in triple quantum well structure. The anisotropy was studied as a function sample temperature, pump-probe delay time, and excitation power, where, the coherent spin dynamics was measured in a broad range of temperature from 5 K up to 250 K using time-resolved Kerr rotation and resonant spin amplification. Additionally, the influence of Al concentration on the spin dynamics of AlGaAs/AlAs QWs was studied. Where, the composition engineering in the studied structures allows tuning of the spin dephasing time and electron g-factor. Finally, we studied the macroscopic transverse drift of long current-induced spin coherence using non-local Kerr rotation measurements, based on the optical resonant amplification of the electrically-induced polarization. Significant spatial variation of the electron g-factor and the coherence times in the nanosecond scale transported away half-millimeter distances in a direction transverse to the applied electric field was observed. / Há uma década, a spintrônica e outras áreas relacionadas vêm atraindo considerável atenção, devido a enorme quantidade de pesquisa conduzidas por elas. A principal razão para o crescente interesse neste campo é a expectativa da aplicação do controle do spin do elétron no lugar ou em adição à carga, em dispositivos eletrônicos e informação e computação quânticas. A possibilidade destes spins carregarem informação depende, primeiramente, da habilidade de controlá-los coerentemente, em uma escala de tempo muito mais rápida do que o tempo de decoerência. Esta tese trata da dinâmica de spins em gases de elétrons bidimensionais, em poços quânticos de semicondutores III-V, crescidos artificialmente. Nós apresentamos uma série de experimentos, utilizando técnicas para o controle ótico da polarização de spin, desencadeadas por métodos óticos ou eletrônicos, ou seja, técnicas conhecidas de bombeio e prova e polarização de spin induzida por corrente. Nós investigamos a coerência de spin em gases bidimensionais, confinados em poços quânticos duplos e triplos de GaAs/AlGaAs e a dependência da defasagem com parâmetros experimentais, como campo magnético externo, potência ótica, tempo entre os pulsos de bombeio e prova e comprimento de onda da excitação. Também estudamos a grande anisotropia de relaxação de spin como função da temperatura da amostra, potência de excitação e defasagem entre bombeio e prova, medidos para uma vasta gama de temperatura, entre 5K e 250K, usando Rotação de Kerr com Resolução Temporal (TRKR) e Amplificação Ressonante de Spin (RSA). Além disso estudamos a influência da concentração de Al na dinâmica dos poços de AlGaAs/AlAs, para o qual a engenharia da composição da estrutura permite sintonizar o tempo de defasagem de spin e o fator $ g $ do elétron. Por fim, estudamos a deriva transversal macroscópica da longa coerência de spin induzida por corrente, através de medidas de Rotação de Kerr não-locais, baseadas na amplificação ressonante ótica da polarização eletricamente induzida. Observamos uma variação espacial significante do fator $ g $ e do tempo de vida da coerência, na escala de nanosegundos, deslocada distâncias de meio milímetro na direção transversa ao campo magnético aplicado.

We present the detailed study of the spin kinetics of the nitrogen (N) donor electrons in 6H SiC wafers grown by the Lely method and by the sublimation “sandwich method” (SSM) with a donor concentration of about 10 17cm-3 at T=10–40K. The donor electrons of the N donors substituting quasi-cubic “k1” and “k2” sites (Nk1,k2) in both types of the samples revealed the similar temperature dependence of the spin-lattice relaxation rate (T1 -1), which was described by the direct one-phonon and two-phonon processes induced by the acoustic phonons proportional to T and to T9, respectively. The character of the temperature dependence of the T1 -1 for the donor electrons of N substituting hexagonal (“h”) site (Nh) in both types of 6H SiC samples indicates that the donor electrons relax through the fast-relaxing centers by means of the cross-relaxation process. The observed enhancement of the phase memory relaxation rate (Tm -1) with the temperature increase for the Nh donors in both types of the samples, as well as for the Nk1,k2 donors in Lely grown 6H SiC, was explained by the growth of the free electron concentration with the temperature increase and their exchange scattering at the N donor centers. The observed significant shortening of the phase memory relaxation time Tm for the Nk1,k2 donors in the SSM grown sample with the temperature lowering is caused by hopping motion of the electrons between the occupied and unoccupied states of the N donors at Nh and Nk1,k2 sites. The impact of the N donor pairs, triads, distant donor pairs formed in n-type 6H SiC wafers on the spin relaxation times was discussed.

<p>This thesis details a collection of experiments performed on two condensed matter systems, Co-doped BaFe₂As₂ and URu₂Si₂. These two materials are related by their structural type (<em>ThCr₂Si₂</em>-type) serving as great examples of the diversity of material properties present in this family. They are also both superconducting materials and belong to the collection of strongly-correlated electron systems. The interest in studying the Ba(Fe,Co)₂As₂ group of materials is due to the high superconducting transition temperature in these (and related) materials, while the compound URu₂Si₂ was studied due to the presence of a poorly-understood 'hidden order' phase.</p> <p>Muon spin relaxation/rotation/resonance (µSR) was used to measure several single crystals of the series Ba(Fe_2-<em>x</em>Co<em>_x</em>)₂As₂ with Cobalt concentrations <em>x </em>= 0.038, 0.047, 0.061, 0.074, 0.107 and 0.114, and a single crystal of Sr(Fe_0.87Co_0.13)₂As₂. The two samples with the lowest doping, <em>x </em>= 0.038 and <em>x </em>= 0.047, showed strong c-axis magnetism occurring below the magnetic transition, T_SDW. The measurements suggest that the local magnetic field is increasingly disordered as the concentration of Co increases. These samples were shown to exhibit both superconductivity and magnetism, but that the entire sample contains non-zero local magnetic fields, meaning that superconductivity exists in or near regions of strong magnetic order.</p> <p>The remaining compounds (with <em>x </em>= 0.061, 0.074, 0.107, 0.114 and Sr(Fe_0.87Co_0.13)₂As₂) were measured with zero-field (ZF)-µSR and no magnetic ordering was found down to T = 1.65 K. An analytic Ginzburg-Landau model was used to fit the data and obtain absolute values for the penetration depth, λ. A model for the temperature dependence of the density of superconducting carriers, n_s ≈ λ², based on two <em>s</em>-wave gaps describes the data well. Below T_SC, a paramagnetic frequency shift was observed indicative of field-induced magnetism along the c crystallographic direction.</p> <p>Measurements of URu₂Si₂ under chemical and hydrostatic pressure have focused on measuring the spin correlations that are present in the hidden order phase. The chemical pressure that is induced by 5% Re doping perturbs, but does not destroy, the commensurate spin excitations. The spin gap that is present in the parent material is also present under this chemical doping. The hidden order phase survives at least halfway to the quantum critical point to ferromagnetism, but is weakened by the Re substitution.</p> <p>Under hydrostatic pressure of 10.1 kbar, URu₂Si₂ becomes antiferromagnetic, but the spin correlations are found to be qualitatively similar to those of the hidden order phase. The width in reciprocal space (Q-width) of the excitations and their gapped nature remains unchanged upon entering the antiferromagnetic phase. Quantitatively, there is an increase in the magnitude of the gap at Q = (1.4 0 0). This may be a result of the increase in the transition temperature preceding the entry to the antiferromagnetic phase.</p> <p>Due to the large difference in their properties, and hence the motivation for studying Ba(Fe_1-<em>x</em>Co<em>_x</em>)₂As₂ and URu₂Si₂, they will be introduced and presented separately. Chapter 1 will provide the necessary background material on Ba(Fe,Co)₂As₂, while Chapter 2 will provide the background for the work on URu₂Si₂. Chapter 3 will describe the experimental techniques that were used to study these systems.</p> <p>Original research results on Ba(Fe,Co)₂As₂ are presented in Chapter 4. This is mainly focused on µSR measurements of dopings that display superconductivity. Samples that did not order magnetically were measured in the mixed state to measure the vortex lattice to extract the various properties, including the superconducting pairing symmetry. Samples that did order magnetically were measured to analyze the amount of magnetic disorder and discover the extent of coexistence or phase separation between magnetism and superconductivity.</p> <p>Chapter 5 details the original research results on URu₂Si₂. This involved crystal growth of these compounds, and two neutron scattering experiments to measure the spin correlations while perturbing the hidden order state. The first experiment was done on a Re-doped crystal, URu_1.9Re_0.1Si₂. Doping with Re suppresses the hidden order, eventually leading to ferromagnetism at higher dopings. This work showed that the spin correlations are also suppressed, but not as quickly as the hidden order. The second experiment was on pure URu₂Si₂ under hydrostatic pressure. Applied pressure increases the hidden order transition, but eventually leads to antiferromagnetism, the phase in which the experiment was performed.</p> / Doctor of Philosophy (PhD)