No description available.

The main purpose of this research was to develop improved methods for RF coil characterisation, and for non-invasive spatio-temporal mapping of temperature in the living body, in order to utilise the full potential of magnetic resonance imaging (MRI) at high magnetic fields by ensuring radiofrequency (RF) safety. Current RF power limits are often overly conservative, unnecessarily limiting the full potential of MRI, especially at high field. Thus it is useful to monitor tissue temperature while running MR imaging sequences which may deposit high RF power. Proton resonance frequency (PRF) MR thermometry can employ the phase of the complex MR signal to estimate temperature change over time. However, the shift of the water PRF with temperature is relatively small, making phase-based MR thermometry inherently sensitive to any extraneously caused changes of local frequency or MR phase. A potential source of error to PRF MR thermometry is a change in surround air susceptibility. The considerable impact of air susceptibility changes on PRF MR thermometry was demonstrated and quantified in experiments and magnetic field simulations. One way of correcting MR thermometry is to use a chemically shifted reference substance, in combination with a phase-sensitive chemical shift-selective MR thermometry sequence. The requirement of having a reliable separation of substances based on their resonance frequency was met by a novel frequency-selective phase-sensitive spin-echo (SE) MR thermometry sequence. This sequence was thoroughly tested in phantom and in-vivo experiments as well as in extensive Bloch simulations. The sequence limitations and advantages are discussed in detail. This technique acquires unsaturated water and fat images in rapid succession at the same position in space. The acquisition of a water and fat slice in less than 100 ms allows the correction of rapid field fluctuations in the brain caused by breathing and heartbeat, while still ensuring the correction of long term drift. With no assumptions required regarding temperature distribution in the tissue, this novel MR thermometry technique can measure brain temperature within a single (1.5 mm)3 voxel with a very low standard deviation (SD) of 0.3 K. Using an MRI phantom with a dimethyl sulfoxide reference, heating experiments achieved a MR temperature measurement with an SD of approximately 0.1 K in a single (1.5 mm)3 voxel. In conclusion, the work presented in this thesis assists the development of a real-time in-vivo temperature monitoring system that guarantees patient RF safety at high field.

No description available.

Yes / Small-angle neutron scattering (SANS) and neutron spin-echo (NSE) have been used to investigate the temperature-dependent solution behaviour of highly-branched poly(N-isopropylacrylamide) (HB-PNIPAM). SANS experiments have shown that water is a good solvent for both HB-PNIPAM and a linear PNIPAM control at low temperatures where the small angle scattering is described by a single correlation length model. Increasing the temperature leads to a gradual collapse of HB-PNIPAM until above the lower critical solution temperature (LCST), at which point aggregation occurs, forming disperse spherical particles of up to 60 nm in diameter, independent of the degree of branching. However, SANS from linear PNIPAM above the LCST is described by a model that combines particulate structure and a contribution from solvated chains. NSE was used to study the internal and translational solution dynamics of HB-PNIPAM chains below the LCST. Internal HB-PNIPAM dynamics is described well by the Rouse model for non-entangled chains.

Helium-3 surface spin echo spectroscopy (HeSE) has been used to measure the diffusive dynamics of adsorbates on close-packed metal surfaces, namely hydrogen on Cu(111), Pd(111) and Ru(0001), carbon and oxygen on Ru(0001), and oxygen on Cu(111). Chapter 2 reviews the HeSE technique and describes the relevant dynamical models and statistical methods used to interpret data in later chapters. The performance of the ionizing detector is analysed, with a focus on the signal-to-noise ratio. In Chapter 3 expressions for the classical intermediate scattering function (ISF) are introduced for open and closed systems. The effects of corrugation and surface-perpendicular motion on the amplitude of different components in the ISF are modelled analytically and compared with simulation. The exact ISF for a particle on a flat surface, obeying the Generalized Langevin Equation with exponential memory friction, is calculated analytically. In Chapter 4 the analytical ISF is calculated for quantum Brownian motion and for coherent tunneling dynamics in a tight binding system. The bounce method for calculating quantum mechanical hopping rates in dissipative systems is applied to model diffusion of hydrogen on Ru(0001). Chapter 5 presents the first HeSE measurements of carbon and oxygen diffusion. C/Ru(0001) diffusion is assigned to a small carbon cluster. The jump rate has an activation energy $E_{A}=292\pm7\,$meV in the temperature range $550\,\textrm{K}\leq T \leq 1300\,$K. Oxygen diffusion is significantly slower. By comparison of literature data with the new HeSE results, the activation energy for oxygen diffusion at low coverage is estimated as $650\pm10$meV. Oxygen measurements at high coverage $\theta\approx0.22\,$ML are consistent with strong mutual O-O interactions. Surface diffusion is also observed after exposing Cu(111) to oxygen. Chapter 6 presents low-coverage measurements of protium (H) and deuterium (D) diffusion on Ru(0001), Pd(111) and Cu(111). In the quantum activated regime there is evidence for multiple jumps in all three systems, suggesting a low dynamical friction. The measurements on Ru(0001) indicate that the deep tunneling rate is much slower for D than for H.

Techniques based on principle of nuclear magnetic resonance (NMR) belong to the most modern methods for studying physical, chemical and biological properties of materials [1]. Their universality predestinates them for application in a wide range of scientific disciplines, e.g. in medicine to study properties of tissues. Advantages of techniques utilizing principle of NMR consist in their noninvasiveness and thoughtfulness to human health or studied material. In addition, no undesirable effects of magnetic force field have been so far proved by research. Objectives of this Diploma Thesis are evaluation of MR images of tissue cultures and determination of protons amount included in them. Theoretic part of the Thesis is devoted to the bases of NMR and provides basic overview of MR methods. The spin echo method (SE) is described in more details, including the process of assessment of technique’s parameters, e.g. general magnetization. Practical part of Diploma Thesis is focused on determination of integral of image intensity of clusters of early somatic embryos. Intensity integrals characterizing number of protons in growing cluster were calculated from MR images of spruce embryos contaminated by lead. The intensity of an image weighted by spin density is proportionate to the number of proton nuclei in the chosen slice. The Thesis describes further evaluation of relaxation time T2 from MR images weighted by spin density. Following part is dealing with determination of diffusion from MR images with application of compensation methods, three-measurement arrangement and presentation of obtained results. Images were processed by use of MATLAB and MAREVISI programs.

Preklinické magneticko-rezonanční (MR) zobrazování na malých zvířatech je velmi aktuální a vyžaduje, vzhledem k rozměrům těchto zvířat, vyšší citlivost. Vyšší citlivosti lze dosáhnout použitím MR systému s vysokým základním magnetickým polem (např. 4,7 T a výše). Vyšší citlivost přináší výhody v podobě možnosti vyššího rozlišení, lepší poměr signál-šum, větší chemický posuv, prodloužení longitudinální relaxace (T1), atd. Na druhou stranu vyšší magnetické pole znamená větší deformace základního magnetického pole na rozhraních tkání s rozdílnou susceptibilitou a zkrácení transverzální relaxace (T2). Tuková tkáň je významně zastoupena v lidském těle a primárně sloužící pro uchovávání energie ve formě tuků. Tukovou tkáň lze rozdělit na hnědou a bílou tukovou tkáň. Hnědá tuková tkáň se vyskytuje hlavně u novorozenců, ale může být ve velmi malém množství také u dospělých jedinců. Bílá tuková tkáň je určena pro ukládání tuků, které slouží jako zdroj energie. Kromě toho bílá tuková tkáň produkuje adipokiny, hormony a mnoho dalších látek důležitých pro náš metabolizmus. Tuk lze obecně považovat jako biomarker při určitých nemocech (obezita, steatóza jater, a další). Z tohoto důvodu je kvantifikace tuku velmi důležitá pro správnou diagnózu. V MR zobrazování je speciální skupina metod pro separaci vody a tuku. Tyto metody se nazývají Dixonovy metody a jejich princip je založen na chemickém posuvu. V této práci je popsána nová T2-váhovaná sekvence pro Dixonovu akvizici (Kapitola 5.3). Navržená sekvence je z hlediska akviziční doby velmi efektivní a řadí se mezi tříbodové Dixonovy (3PD) techniky. Nově navržená sekvence fast triple spin echo Dixon (FTSED) vychází z původní sekvence rychlého spinového echa (FSE). Modifikací původní sekvence FSE vedla ke vzniku nové sekvence FTSED, která umožňuje získat tři obrazy během jediné akvizice, bez toho aniž bychom prodloužili celkovou dobu měření. Sekvence byla úspěšně implementována na 9,4 T MRI systém na Ústavu přístrojové techniky v Brně. Získaná data byla pak zpracována iterativně pomocí algoritmu IDEAL (iterative decomposition of water and fat with echo asymmetry and least-squares estimation). Výsledkem jsou separátní obrazy vody a tuků, z kterých lze vypočítat mapy frakce tuku (FF-mapy). Sekvence byla ověřena na fantomech a poté byla odzkoušena potkanovi. Úspěšná implementace této metody na 9,4 T MRI systému znamená, že může být použita také na MR zobrazovacích systémech s nižšími magnetickými poli.

Quantum computers can theoretically perform certain tasks which classical computers at realistic times could not. Operating a quantum computer requires precise control over the system, for instance achieved by adiabatic evolution, and isolation from the environment to retain coherence. This report combines these two, somewhat contradicting, error preventing techniques. To reduce the run-time a transitionless quantum driving algorithm, or, adiabatic shortcut, is employed. The notion of Noiseless Subsystems (NS), a generalization of decoherence free subspaces, are used for robustness against environmental decoupling, by creating logical qubits which act as a noiseless code. Furthermore, the adiabatic shortcut for the NS code is applied to a refocusing scheme (spin-echo) in order to remove the dynamical phase, sensitive to error propagation, so that only the Berry phase is effectively picked up. The corresponding Hamiltonian is explicitly derived for the only two cases of two-dimensional NS: N=3,4 qubits with total spin of j=1/2,0, respectively. This constitutes geometric quantum computation (GQC) enacting a universal single-qubit gate, which is also explicitly derived. / Kvantdatorer kan teoretiskt utföra vissa uppgifter som klassiska datorer vid realistiska tider inte kan. Att köra en kvantdator kräver exakt kontroll över systemet, till exempel genom adiabatisk utvecking, och isolering från omgiviningen för att behålla koherens. Denna rapport kombinerar dessa två, något motsägelsefulla, tekniker för felhantering. För att minska körtiden används en övergångsfri kvantkörningsalgoritm, också kallad adiabatisk genväg. Konceptet brusfria delsystem, en generalisering av dekoherensfria underrum, används för robusthet mot sammanflätning med omgivningen genom att skapa logiska kvantbitar som fungerar som en brusfri kod. Vidare tillämpas den adiabatiska genvägen för den brusfria koden på ett spinn-eko för att eliminera den dynamiska fasen, som är känslig för felpropagering, så att endast Berrys fas, som är okänslig för felpropagering, effektivt plockas upp. Motsvarande Hamiltonian härleds uttryckligen för de enda två fallen av tvådimensionella brusfria delsystem: 3 eller 4 kvantbitar med respektive totalspinn j = 1/2 och 0. Detta möjliggör beräkning med en geometrisk kvantdator baserad på en universell en-kvantbitsgrind, som också härleds explicit.

No description available.

Ces travaux de thèse sont consacrés à l’étude, par RMN et spectrométrie de masse, de la caractérisation structurale et la quantification en mélange, de polymères synthétiques à architectures complexes. La caractérisation structurale de copolymères à blocs amphiphiles POE-b-PS a été abordée dans un premier temps par la mise au point d’une nouvelle stratégie, rapide et sans prétraitement, pour la détermination de la masse moyenne en masse par RMN PGSE. La problématique des groupements terminaux fragiles en MALDI-MS, particulièrement cruciale dans le cas de polymères fonctionnalisés par des nitroxydes, a également été traitée. Une approche multidisciplinaire impliquant la RMN, la spectrométrie de masse et la chimie théorique a conduit au développement d’une stratégie de dérivation du groupement terminal labile qui permet la production d’adduits moléculaires intacts MALDI. Par ailleurs, la nécessité de quantifier les impuretés issues de la synthèse de ces macromolécules a conduit au développement d’une stratégie originale, rapide et efficace, basée sur la RMN PGSE. Cette stratégie, qui s’appuie sur la détermination des temps de relaxation magnétique des signaux au cours des expériences, suivie de la renormalisation des intégrales, a notamment soulevé la difficulté de mesurer le temps de relaxation transversale dans le cas de systèmes de spins magnétiquement couplés. Une nouvelle séquence d’impulsions a donc été proposée pour permettre une mesure précise de ce temps de relaxation dans un système de deux spins couplés. / This thesis work deals with two main analytical aspects of PEO-b-PS amphiphilic block copolymers, their structural characterization and their quantitation in mixture, using NMR and mass spectrometry. In a first part, a novel approach was developed for the determination of copolymer weight average molecular weight by PGSE NMR. The issue of MALDI mass analysis of PEO homopolymers functionalized with a labile nitroxide end-group for the purpose of nitroxide mediated polymerization of the PS block was also addressed. A multidisciplinary approach involving NMR, mass spectrometry and theoretical calculation gave rise to an efficient derivatization strategy aimed at allowing intact PEO adducts to be generated by MALDI. In addition, requirement for impurity quantitation in polymer samples led to the development of a rapid and accurate method using PGSE NMR. This approach, based on the measurement of magnetic relaxation times during PGSE experiments to enable signal intensity renormalization, evidenced the issue of transverse relaxation time estimation in the case of coupled spin systems. A novel NMR pulse sequence was hence proposed and successfully applied for accurate measurement of transverse relaxation times in a model case of a two-spin coupled system.