Proton magnetic resonance with parahydrogen induced polarization : Imaging strategies and continuous generation

A major challenge in imaging is the detection of small amounts of molecules of interest. In the case of magnetic resonance imaging (MRI) their signals are typically concealed by the large background signal of e.g. the tissue of the body. This problem can be tackled by hyperpolarization which increases the NMR signals up to several orders of magnitude. However, this strategy is limited for 1H, the most widely used nucleus in NMR andrnMRI, because the enormous number of protons in the body screen the small amount of hyperpolarized ones.Here, I describe a method giving rise to high 1H MRI contrast for hyperpolarized molecules against a large background signal. The contrast is based on the J-coupling induced rephasing of the NMR signal of molecules hyperpolarized via parahydrogen induce polarization (PHIP) and it can easily be implemented in common pulse sequences.rnrnHyperpolarization methods typically require expensive technical equipment (e.g. lasers or microwaves) and most techniques work only in batch mode, thus the limited lifetime of the hyperpolarization is limiting its applications. Therefore, the second part of my thesis deals with the simple and efficient generation of an hyperpolarization.These two achievements open up alternative opportunities to use the standard MRI nucleus 1H for e.g. metabolic imaging in the future.

Beyond simple proton transfer processes: domino reactions between 4-substituted indoles and nitroethene as a new gateway to ergot alkaloids

The multimodal biology activity of ergot alkaloids is known by humankind since middle ages. Synthetically modified ergot alkaloids are used for the treatment of various medical conditions. Despite the great progress in organic syntheses, the total synthesis of ergot alkaloids remains a great challenge due to the complexity of their polycyclic structure with multiple stereogenic centres. This project has developed a new domino reaction between indoles bearing a Michael acceptor at the 4 position and nitroethene, leading to potential ergot alkaloid precursors in highly enantioenriched form. The reaction was optimised and applied to a large variety of substrate with good results. Even if unfortunately all attempts to further modify the obtained polycyclic structure failed, it was found a reaction able to produce the diastereoisomer of the polycyclic product in excellent yields. The compounds synthetized were characterized by NMR and ESIMS analysis confirming the structure and their enantiomeric excess was determined by chiral stationary phase HPLC. The mechanism of the reaction was evaluated by DFT calculations, showing the formation of a key bicoordinated nitronate intermediate, and fully accounting for the results observed with all substrates. The relative and absolute configuration of the adducts were determined by a combination of NMR, ECD and computational methods.

Detection of individual spin transitions of a single proton confined in a cryogenic Penning trap

Das in dieser Arbeit vorgestellte Experiment zur Messung des magnetischen Moments des Protons basiert auf der Messung des Verhältnisses von Zyklotronfrequenz und Larmorfrequenz eines einzelnen, in einer kryogenen Doppel-Penning Falle gespeicherten Protons. In dieser Arbeit konnten erstmalig zwei der drei Bewegungsfrequenzen des Protons gleichzeitig im thermischen Gleichgewicht mit entsprechenden hochsensitiven Nachweissystemen nicht-destruktiv detektiert werden, wodurch die Messzeit zur Bestimmung der Zyklotronfrequenz halbiert werden konnte. Ferner wurden im Rahmen dieser Arbeit erstmalig einzelne Spin-Übergänge eines einzelnen Protons detektiert, wodurch die Bestimmung der Larmorfrequenz ermöglicht wird. Mithilfe des kontinuierlichen Stern-Gerlach Effekts wird durch eine sogenannte magnetische Flasche das magnetische Moment an die axiale Bewegungsmode des Protons gekoppelt. Eine Änderung des Spinzustands verursacht folglich einen Frequenzsprung der axialen Bewegungsfrequenz, welche nicht-destruktiv gemessen werden kann. Erschwert wird die Detektion des Spinzustands dadurch, dass die axiale Frequenz nicht nur vom Spinmoment, sondern auch vom Bahnmoment abhängt. Die große experimentelle Herausforderung besteht also in der Verhinderung von Energieschwankungen in den radialen Bewegungsmoden, um die Detektierbarkeit von Spin-Übergängen zu gewährleisten. Durch systematische Studien zur Stabilität der axialen Frequenz sowie einer kompletten Überarbeitung des experimentellen Aufbaus, konnte dieses Ziel erreicht werden. Erstmalig kann der Spinzustand eines einzelnen Protons mit hoher Zuverlässigkeit bestimmt werden. Somit stellt diese Arbeit einen entscheidenden Schritt auf dem Weg zu einer hochpräzisen Messung des magnetischen Moments des Protons dar.

Search for high mass resonances decaying into electron-positron pairs in proton-proton collisions at sqrt(s) = 7 TeV with the ATLAS detector

The Standard Model of particle physics was developed to describe the fundamental particles, which form matter, and their interactions via the strong, electromagnetic and weak force. Although most measurements are described with high accuracy, some observations indicate that the Standard Model is incomplete. Numerous extensions were developed to solve these limitations. Several of these extensions predict heavy resonances, so-called Z' bosons, that can decay into an electron positron pair. The particle accelerator Large Hadron Collider (LHC) at CERN in Switzerland was built to collide protons at unprecedented center-of-mass energies, namely 7 TeV in 2011. With the data set recorded in 2011 by the ATLAS detector, a large multi-purpose detector located at the LHC, the electron positron pair mass spectrum was measured up to high masses in the TeV range. The properties of electrons and the probability that other particles are mis-identified as electrons were studied in detail. Using the obtained information, a sophisticated Standard Model expectation was derived with data-driven methods and Monte Carlo simulations. In the comparison of the measurement with the expectation, no significant deviations from the Standard Model expectations were observed. Therefore exclusion limits for several Standard Model extensions were calculated. For example, Sequential Standard Model (SSM) Z' bosons with masses below 2.10 TeV were excluded with 95% Confidence Level (C.L.).

Spins, moments and radii of cd isotopes

The complex nature of the nucleon-nucleon interaction and the wide range of systems covered by the roughly 3000 known nuclides leads to a multitude of effects observed in nuclear structure. Among the most prominent ones is the occurence of shell closures at so-called ”magic numbers”, which are explained by the nuclear shell model. Although the shell model already is on duty for several decades, it is still constantly extended and improved. For this process of extension, fine adjustment and verification, it is important to have experimental data of nuclear properties, especially at crucial points like in the vicinity of shell closures. This is the motivation for the work performed in this thesis: the measurement and analysis of nuclear ground state properties of the isotopic chain of 100−130Cd by collinear laser spectroscopy.rnrnThe experiment was conducted at ISOLDE/CERN using the collinear laser spectroscopy apparatus COLLAPS. This experiment is the continuation of a run on neutral atomic cadmium from A = 106 to A = 126 and extends the measured isotopes to even more exotic species. The required gain in sensitivity is mainly achieved by using a radiofrequency cooler and buncher for background reduction and by using the strong 5s 2S1/2 → 5p 2P3/2 transition in singly ionized Cd. The latter requires a continuous wave laser system with a wavelength of 214.6 nm, which has been developed during this thesis. Fourth harmonic generation of an infrared titanium sapphire laser is achieved by two subsequent cavity-enhanced second harmonic generations, leading to the production of deep-UV laser light up to about 100 mW.rnrnThe acquired data of the Z = 48 Cd isotopes, having one proton pair less than the Z = 50 shell closure at tin, covers the isotopes from N = 52 up to N = 82 and therefore almost the complete region between the neutron shell closures N = 50 and N = 82. The isotope shifts and the hyperfine structures of these isotopes have been recorded and the magnetic dipole moments, the electric quadrupole moments, spins and changes in mean square charge radii are extracted. The obtained data reveal among other features an extremely linear behaviour of the quadrupole moments of the I = 11/2− isomeric states and a parabolic development in differences in mean square nuclear charge radii between ground and isomeric state. The development of charge radii between the shell closures is smooth, exposes a regular odd-even staggering and can be described and interpreted in the model of Zamick and Thalmi.

Measurement of the forward-backward asymmetry of Z boson decays in electron-positron pairs with the ATLAS detector in proton-proton collisions at root out s = 7TeV at the LHC

In this thesis the measurement of the effective weak mixing angle wma in proton-proton collisions is described. The results are extracted from the forward-backward asymmetry (AFB) in electron-positron final states at the ATLAS experiment at the LHC. The AFB is defined upon the distribution of the polar angle between the incoming quark and outgoing lepton. The signal process used in this study is the reaction pp to zgamma + X to ee + X taking a total integrated luminosity of 4.8\,fb^(-1) of data into account. The data was recorded at a proton-proton center-of-mass energy of sqrt(s)=7TeV. The weak mixing angle is a central parameter of the electroweak theory of the Standard Model (SM) and relates the neutral current interactions of electromagnetism and weak force. The higher order corrections on wma are related to other SM parameters like the mass of the Higgs boson.rnrnBecause of the symmetric initial state constellation of colliding protons, there is no favoured forward or backward direction in the experimental setup. The reference axis used in the definition of the polar angle is therefore chosen with respect to the longitudinal boost of the electron-positron final state. This leads to events with low absolute rapidity have a higher chance of being assigned to the opposite direction of the reference axis. This effect called dilution is reduced when events at higher rapidities are used. It can be studied including electrons and positrons in the forward regions of the ATLAS calorimeters. Electrons and positrons are further referred to as electrons. To include the electrons from the forward region, the energy calibration for the forward calorimeters had to be redone. This calibration is performed by inter-calibrating the forward electron energy scale using pairs of a central and a forward electron and the previously derived central electron energy calibration. The uncertainty is shown to be dominated by the systematic variations.rnrnThe extraction of wma is performed using chi^2 tests, comparing the measured distribution of AFB in data to a set of template distributions with varied values of wma. The templates are built in a forward folding technique using modified generator level samples and the official fully simulated signal sample with full detector simulation and particle reconstruction and identification. The analysis is performed in two different channels: pairs of central electrons or one central and one forward electron. The results of the two channels are in good agreement and are the first measurements of wma at the Z resonance using electron final states at proton-proton collisions at sqrt(s)=7TeV. The precision of the measurement is already systematically limited mostly by the uncertainties resulting from the knowledge of the parton distribution functions (PDF) and the systematic uncertainties of the energy calibration.rnrnThe extracted results of wma are combined and yield a value of wma_comb = 0.2288 +- 0.0004 (stat.) +- 0.0009 (syst.) = 0.2288 +- 0.0010 (tot.). The measurements are compared to the results of previous measurements at the Z boson resonance. The deviation with respect to the combined result provided by the LEP and SLC experiments is up to 2.7 standard deviations.

Erste Messung der Pi-0-Photoproduktion an transversal polarisierten Protonen nahe der Schwelle

Diese Arbeit befasst sich mit der photoinduzierten Erzeugung neutraler Pionen, sehr nahe an der Schwellenenergie. Dabei werden zwei Ziele verfolgt: Zum einen die Überprüfung von Vorhersagen dieser effektiven Theorien und Modelle, zum anderen werden hier erstmals alle relevanten Partialwellenamplituden modellunabhängig aus gemessenen Observablen bestimmt. Diese Methode soll in Zukunft auch bei höheren Energien im Bereich der Nukleonresonanzen Anwendung finden. rnrnKonkret wird die Durchführung und Analyse eines Experiments vorgestellt, welches am Mainzer Mikrotron (MAMI) in den Jahren 2010 bis 2013 mit zirkular polarisiertem Photonenstrahl stattfand. Der Photonenstrahl wurde an einer Anlage zur Erzeugung energiemarkierter Bremsstrahlung aus dem Elektronenstrahl von MAMI gewonnen. Zum Nachweis der Reaktionsprodukte diente das hermetische 4pi CB/TAPS-Detektorsystem. Erstmalig standen bei derartigen Messungen auch transversal polarisierte Protonen zur Verfügung. Dazu wird Butanol in einer speziellen Apparatur dynamisch polarisiert. Molekularer Wasserstoff lässt sich aufgrund der para-Konfiguration nicht polarisieren. Wegen der Verwendung von Butanol als Targetmaterial, bei dem weniger als 5% aller erzeugten Pionen an polarisierten Protonen produziert wurden, ist die Behandlung des Untergrunds eine zentrale Aufgabe. rnrnEs werden zwei Methoden der Untergrundseparation vorgestellt, wovon die bessere in der Analyse angewendet wurde. Abschließend findet eine ausführliche Bewertung systematischer Fehler statt.rnrnDie erstmalige Verwendung transversal polarisierter Protonen ermöglicht den Zugang zu bisher nicht gemessenen Spin"=Freiheitsgraden. In Kombination mit einem komplementären Vorläufer-Experiment aus dem Jahr 2008 mit linear polarisiertem Photonenstrahl konnten aus den gewonnenen Daten erstmals alle komplexen s- und p-Partialwellenamplituden modellunabhängig bestimmt werden. rnrnDarüber hinaus wurden im Rahmen dieser Arbeit wesentliche Verbesserungen am apparativen Aufbau erzielt. Beispiele sind ein Elektronenstrahl-Polarimeter, ein zellularer CB-Multiplizitätstrigger, sowie signifikante Verbesserungen der Datennahmeelektronik und des Triggersystems, die teilweise in dieser Arbeit vorgestellt werden.

Search for Dark Matter in events with a highly energetic jet and missing transverse momentum in proton-proton collisions at root out s = 8 TeV with the ATLAS detector

The experiments at the Large Hadron Collider at the European Centre for Particle Physics, CERN, rely on efficient and reliable trigger systems for singling out interesting events. This thesis documents two online timing monitoring tools for the central trigger of the ATLAS experiment as well as the adaption of the central trigger simulation as part of the upgrade for the second LHC run. Moreover, a search for candidates for so-called Dark Matter, for which there is ample cosmological evidence, is presented. This search for generic weakly interacting massive particles (WIMPs) is based on the roughly 20/fb of proton-proton collisions at a centre-of-mass-energy of sqrt{s}=8 TeV recorded with the ATLAS detector in 2012. The considered signature are events with a highly energetic jet and large missing transverse energy. No significant deviation from the theory prediction is observed. Exclusion limits are derived on parameters of different signal models and compared to the results of other experiments. Finally, the results of a simulation study on the potential of the analysis at sqrt{s}=14 TeV are presented.

Single meson production in proton diffraction at 190 GeV/c at COMPASS

The quark model successfully describes all ground state bary-ons as members of $SU(N)$ flavour multiplets. For excited baryon states the situation is totally different. There are much less states found in the experiment than predicted in most theoretical calculations. This fact has been known for a long time as the 'missing resonance problem'. In addition, many states found in experiments are only poorly measured up to now. Therefore, further experimental efforts are needed to clarify the situation.rnrnAt mbox{COMPASS}, reactions of a $190uskgigaeVperclight$ hadron beam impinging on a liquid hydrogen target are investigated.rnThe hadron beam contains different species of particles ($pi$, $K$, $p$). To distinguish these particles, two Cherenkov detectors are used. In this thesis, a new method for the identification of particles from the detector information is developed. This method is based on statistical approaches and allows a better kaon identification efficiency with a similar purity compared to the method, which was used before.rnrnThe reaction $pprightarrow ppX$ with $X=(pi^0,~eta,~omega,~phi)$ is used to study different production mechanisms. A previous analysis of $omega$ and $phi$ mesons is extended to pseudoscalar mesons. As the resonance contributions in $peta$ are smaller than in $ppi^0$ a different behaviour of these two final states is expected as a function of kinematic variables. The investigation of these differences allows to study different production mechanisms and to estimate the size of the resonant contribution in the different channels.rnrnIn addition, the channel $pprightarrow ppX$ allows to study baryon resonances in the $pX$ system.rnIn the mbox{COMPASS} energy regime, the reaction is dominated by Pomeron exchange. As a Pomeron carries vacuum quantum numbers, no isospin is transferred between the target proton and the beam proton. Therefore, the $pX$ final state has isospin $textstylefrac{1}{2}$ and all baryon resonances in this channel are $N^ast$ baryons. This offers the opportunity to do spectroscopy without taking $Delta$ resonances into account. rnrnTo disentangle the contributions of different resonances a partial wave analysis (PWA) is used. Different resonances have different spin and parity $J^parity$, which results in different angular distributions of the decay particles. These angular distributions can be calculated from models and then be fitted to the data. From the fit the contributions of the single resonances as well as resonance parameters -- namely the mass and the width -- can be extracted. In this thesis, two different approaches for a partial wave analysis of the reaction $pprightarrow pppi^0$ are developed and tested.

Luminosity determination for the measurement of the proton-proton total cross section at 8 TeV in the Atlas experiment

La sezione d’urto totale adronica gioca un ruolo fondamentale nel programma di fisica di LHC. Un calcolo di questo parametro, fondamentale nell’ambito della teoria delle interazioni forti, non é possibile a causa dell’inapplicabilità dell’approccio perturbativo. Nonostante ciò, la sezione d’urto può essere stimata, o quanto meno le può essere dato un limite, grazie ad un certo numero di relazioni, come ad esempio il Teorema Ottico. In questo contesto, il detector ALFA (An Absolute Luminosity For ATLAS) sfrutta il Teorema Ottico per determinare la sezione d’urto totale misurando il rate di eventi elastici nella direzione forward. Un tale approccio richiede un metodo accurato di misura della luminosità in condizioni sperimentali difficoltose, caratterizzate da valori di luminosità istantanea inferiore fino a 7 ordini di grandezza rispetto alle normali condizioni di LHC. Lo scopo di questa tesi è la determinazione della luminosità integrata di due run ad alto β*, utilizzando diversi algoritmi di tipo Event-Counting dei detector BCM e LUCID. Particolare attenzione è stata riservata alla sottrazione del fondo e allo studio delle in- certezze sistematiche. I valori di luminosità integrata ottenuti sono L = 498.55 ± 0.31 (stat) ± 16.23 (sys) μb^(-1) and L = 21.93 ± 0.07 (stat) ± 0.79 (sys) μb^(-1), rispettivamente per i due run. Tali saranno forniti alla comunità di fisica che si occupa della misura delle sezioni d’urto protone-protone, elastica e totale. Nel Run II di LHC, la sezione d’urto totale protone-protone sarà stimata con un’energia nel centro di massa di 13 TeV per capire meglio la sua dipendenza dall’energia in un simile regime. Gli strumenti utilizzati e l’esperienza acquisita in questa tesi saranno fondamentali per questo scopo.

Effect of Acute Psychological Stress on Prefrontal GABA Concentration Determined by Proton Magnetic Resonance Spectroscopy

Objective Impaired function of the central gamma-aminobutyric acid (GABA) system, which provides the brain’s major inhibitory pathways, is thought to play an important role in the pathophysiology of anxiety disorders. The effect of acute psychological stress on the human GABA-ergic system is still unknown, however. The purpose of this study was to determine the effect of acute stress on prefrontal GABA levels. Method A recently developed noninvasive magnetic resonance spectroscopy method was used to measure changes in the GABA concentration of the prefrontal cortex in 10 healthy human subjects during a threat-of-shock condition and during a safe condition (two sessions on different days). The main outcome measure was the mean GABA concentration within a 3×3×2-cm3 voxel selected from the medial prefrontal cortex. Results Prefrontal GABA decreased by approximately 18% in the threat-of-shock condition relative to the safe condition. This reduction was specific to GABA, since the concentrations of N-acetyl-aspartate, choline-containing compounds, and glutamate/glutamine levels obtained in the same spectra did not change significantly. Conclusions This result appeared compatible with evidence from preclinical studies in rodents, which showed rapid presynaptic down-regulation of GABA-ergic neurotransmission in response to acute psychological stress. The molecular mechanism and functional significance of this reduced inhibitory effect of acute psychological stress in relation to impaired GABA-ergic function in anxiety disorders merit further investigation.