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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
121

A Radio Frequency Quadrupole Instrument for use with Accelerator Mass Spectrometry: Application to Low Kinetic Energy Reactive Isobar Suppression and Gas–phase Anion Reaction Studies

Eliades, John Alexander 21 August 2012 (has links)
A radio frequency (rf) quadrupole instrument, currently known as an Isobar Separator for Anions (ISA), has been integrated into an Accelerator Mass Spectrometry (AMS) system to facilitate anion–gas reactions before the tandem accelerator. An AMS Cs+ sputter source provided > 15 keV ions that were decelerated in the prototype ISA to < 20 eV for reaction in a single collision cell and re-accelerated for AMS analysis. Reaction based isobar suppression capabilities were assessed for smaller AMS systems and a new technique for gas–phase reaction studies was developed. Isobar suppression of 36S– and 12C3– for 36Cl analysis, and YF3– and ZrF3– for 90Sr analysis were studied in NO2 with deceleration to < 12 eV. Observed attenuation cross sections, σ [x 10^–15 cm^2], were σ(S– + NO2) = 6.6, σ(C3– + NO2) = 4.2, σ(YF3– + NO2) = 7.6, σ(ZrF3– + NO2) = 19. With 8 mTorr NO2, relative attenuations of S–/Cl– ~ 10^–6, C3–/Cl– ~ 10^–7, YF3–/SrF3– ~ 5 x 10^–5 and ZrF3–/SrF3– ~ 4 x 10^–6 were observed with Cl– ~ 30% and SrF3– > 90% transmission. Current isobar attenuation limits with < 1.75 MV accelerator terminal voltage and ppm impurity levels were calculated to be 36S–/Cl– ~ 4 x 10^–16, 12C3–/Cl– ~ 1.2 x 10^–16, 90YF3–/SrF3– ~ 10^–15 and 90ZrF3–/SrF3– ~ 10^–16. Using 1.75 MV, four 36Cl reference standards in the range 4 x 10^–13 < 36Cl/Cl < 4 x 10^–11 were analyzed with 8 mTorr NO2. The measured 36Cl/Cl ratios plotted very well against the accepted values. A sample impurity content S/Cl < 6 x 10^–5 was measured and a background level of 36S–/Cl < 9 x 10^–15 was determined. Useful currents of a wide variety of anions are produced in AMS sputter sources and molecules can be identified relatively unambiguously by stripping fragments from tandem accelerators. Reactions involving YF3–, ZrF3–, S– and SO– + NO2 in the ISA analyzed by AMS are described, and some interesting reactants are identified.
122

Etude microscopique de systèmes fermioniques finis : corrélations dans les noyaux atomiques et gaz d'électrons confinés par un potentiel harmonique en présence d'un champ magnétique

Naïdja, Houda 09 January 2009 (has links)
Dans le cadre d'une approche Higher Tamm Dancoff Approximation notée HTDA, nous avons étudié les corrélations vibrationnelles de type quadrupole, avec et sans appariement. Le champ moyen a été déterminé dans le cadre d'une approche microscopique utilisant l'interaction effective de Skyrme. Une interaction résiduelle schématique de type delta plus quadrupole-quadrupole, tenant compte en particulier de l'appariement neutron-proton T=0 et T=1 a été utilisé. Les résultats obtenus pour la résonance géante quadrupolaire isoscalaire du noyau Ca40 ont été comparés aux données expérimentales et à d'autres résultats théoriques. Nous avons également étudié un gaz de fermions piégés dans un potentiel d'oscillateur harmonique à 2D, et à température nulle, en présence d'un champ magnétique uniforme. Les expressions exactes des quelques grandeurs thermodynamiques ont été dérivées à partir de la matrice densité de Bloch. / Within the framework of the so-called Higher Tamm Dancoff Approxiamtion (HTDA), we have studied the quadrupole vibrational correlations with and without pairing correlations. The mean field has been determined within a microscopic approach using the Skyrme effective interaction. A schematic residual interaction of the delta plus quadrupole-quadrupole type, allowing in particular neutron-proton T=0 and T=1 pairing, has been used. The results which have been obtained for the isoscalar quadrupole giant resonance of the Ca40 have been compared with the experimental data. A fermion gaz trapped in a 2D harmonic oscillator well at zero temperature and in the presence of a uniform magnetic field has been investigated. Exact expressions of some thermodynamic quantities have been derived from the Bloch density matrix.
123

Epitaxial growth of Ge-Sb-Te based phase change materials

Perumal, Karthick 05 August 2013 (has links)
Ge-Sb-Te basierte Phasenwechselmaterialen sind vielersprechende Kandidaten für die Anwendung in optischen und elektrischen nicht-flüchtigen Speicheranwendungen. Diese Materialien können mit Hilfe von elektrischen oder optischen Pulsen reversibel zwischen der kristallinen und amorphen Struktur geschaltet werden. Diese stukturellen Phasen zeigen einen großen Unterschied in ihren elektronischen Eigenschaften, der sich in einer starken Änderung der optischen Reflektivität und des elektrischen Widerstands zeigt.Diese Studie befasst sich mit epitaktischem Wachstum und Analyse der epitaktischen Schichten. Der erste Teil der Arbiet befasst sich mir dem epitaktischen Wachstum von GeTe. Dünne GeTe Schichten wurden auf Si(111) und Si(001) Substraten mit einer Gitterfehlanpassung von 10.8% präpariert. Auf beiden Substraten bildet sich in der GeTe Schicht die [111] Oberflächenfacette parallel zur Si(001) und Si(111) Oberfläche aus. Während des inertialen Wachstums findet eine Phasentransformation von amorph zu kristallin statt. Diese Phasentransformation wurde mittels azimuthaler in-situ Beugung hochenergetischer Elektronen sowie in-situ Röntgenbeugung unter streifendem Einfall untersucht. Der zweite Teil der Arbeit wird die Epitaxie sowie die strukturelle Charakterisierung dünner Sb2Te3 Schichten dargestellt. Der dritte Teil umfasst die Epitaxie terniärer Ge-Sb-Te Schichten . Zum Wachstum wurden sowohl die Substrattemperatur als auch die Ge, Sb und Te Flüsse variiert. Es wird gezeigt, dass die Komposition der Schicht stark von der Wachtumstemperatur abhängt und nur entlang der pseudibinären Verbindungslinie von GeTe-Sb2Te3 variiert. Zur Kontrolle des Wachstums wurde dabei die in-situ Quadrupol Massenspektroskopie verwendet. Es zeigen sich diverse inkommensurate Beugungsmaxima entlang der [111] Oberflächennormalen der Schichten, anhand derer die Ausbildung einer Lehrstellen Ordnung in Form einer Überstruktur diskutiert wird. / Ge-Sb-Te based phase change materials are considered as a prime candidate for optical and electrical data storage applications. With the application of an optical or electrical pulse, they can be reversibly switched between amorphous and crystalline state, thereby exhibiting large optical and electrical contrast between the two phases, which are then stored as information in the form of binary digits. Single crystalline growth is interesting from both the academic and industrial perspective, as ordered Ge-Sb-Te based metamaterials are known to exhibit switching at reduced energies. The present study deals with the epitaxial growth and analysis of Ge-Sb-Te based thin films. The first part of the thesis deals with the epitaxial growth of GeTe. Thin films of GeTe were grown on highly mismatched Si(111) and (001) substrates. On both the substrate orientations the film grows along [111] direction with an amorphous-to-crystalline transition observed during the initial stages of growth. The amorphous-to-crystalline transition was studied in-vivo using azimuthal reflection high-energy electron diffraction scans and grazing incidence x-ray diffraction. In the second part of the thesis epitaxy and characterization of Sb2Te3 thin films are presented. The third part of the thesis deals with the epitaxy of ternary Ge-Sb-Te alloys. The composition of the films are shown to be highly dependent on growth temperatures and vary along the pseudobinary line from Sb2Te3 to GeTe with increase in growth temperatures. A line-of-sight quadrupole mass spectrometer was used to reliably control the GeSbTe growth temperature. Growth was performed at different Ge, Sb, Te fluxes to study the compositional variation of the films. Incommensurate peaks are observed along the [111] direction by x-ray diffraction. The possibility of superstructural vacancy ordering along the [111] direction is discussed.
124

Etude microscopique de systèmes fermioniques finis : corrélations dans les noyaux atomiques et gaz d'électrons confinés par un potentiel harmonique en présence d'un champ magnétique

Naidja, Houda 09 January 2009 (has links) (PDF)
Dans le cadre d'une approche Higher Tamm Dancoff Approximation notée HTDA, nous avons étudié les corrélations vibrationnelles de type quadrupole, avec et sans appariement. Le champ moyen a été déterminé dans le cadre d'une approche microscopique utilisant l'interaction effective de Skyrme. Une interaction résiduelle schématique de type delta plus quadrupole-quadrupole, tenant compte en particulier de l'appariement neutron-proton T=0 et T=1 a été utilisé. Les résultats obtenus pour la résonance géante quadrupolaire isoscalaire du noyau Ca40 ont été comparés aux données expérimentales et à d'autres résultats théoriques. Nous avons également étudié un gaz de fermions piégés dans un potentiel d'oscillateur harmonique à 2D, et à température nulle, en présence d'un champ magnétique uniforme. Les expressions exactes des quelques grandeurs thermodynamiques ont été dérivées à partir de la matrice densité de Bloch.
125

Characterization of Molecular Glycerophospholipids by Quadrupole Time-of-Flight Mass Spectrometry

Ekroos, Kim 10 November 2003 (has links) (PDF)
The physical properties of glycerophospholipids (GPLs) are not only determined by the head group (HG), but also by their fatty acid (FA) chains, which affect their distribution and function within membranes in the cell. Understanding the microheterogenity of lipid membranes on a molecular level requires qualitative and quantitative characterization of individual lipids and identification of their FA moieties. The aim of my study was to introduce the new technology of multiple precursor ion scanning (MPIS) on a QSTAR Pulsar time-of-flight mass spectrometer (QqTOF) to analyze lipids. Detailed information on fatty acid composition of individual GPL molecules could be obtained in parallel with conventional profiling of lipid classes, and this could be done by direct analysis of total lipid extracts. This method was termed Fatty Acid Scanning (FAS) and Head Group Scanning HGS, respectively. In this way the molecular GPL composition of total lipid extracts could be charted in a single analysis accurately and rapidly at a low picomole concentration level. Furthermore, combining FAS and HGS together with ion trap MS3 analysis allowed complete charting of the molecular composition of PCs, including quantification of their positional isomers, thus providing a detailed and comprehensive characterization of molecular composition of the pool of PCs. Development of the Lipid Profiler software allowed full automation and rapid processing of complex data, including identification and quantification of molecular GPLs. This approach was evaluated by preliminary applications. First, the molecular composition of PCs of total lipid extracts of MDCK cells and of human red blood cells (RBC) could accurately be charted. Significant presence of positional isomers was observed increasing the total number of individual PC species close to one hundred. Secondly, the molecular PC and SM species distribution in detergent resistant membranes (DRMs) prepared by Triton X-100 DRMs were analyzed and were found to be enriched in distinct GPLs. The distribution in PCs and SMs of Triton X-100 DRMs of RBC were compared with those of the DRMs of MDCK cells. Finally, combining the use of a 96 well plate and a robotic system demonstrated that these analyses can be automated and analyzed with high throughput. This system we termed Shotgun Lipidomics. Taken together, this mass spectrometric methodology provides rapid and detailed insight into the distribution of the molecular GPLs of membranes and membrane sub-fractions.
126

Numerical Studies of Axially Symmetric Ion Trap Mass Analysers

Kotana, Appala Naidu January 2017 (has links) (PDF)
In this thesis we have focussed on two types of axially symmetric ion trap mass analysers viz., the quadrupole ion trap mass analyser and the toroidal ion trap mass analyser. We have undertaken three numerical studies in this thesis, one study is on the quadrupole ion trap mass analysers and two studies are on the toroidal ion trap mass analysers. The first study is related to improvement of the sensitivity of quadrupole ion trap mass analysers operated in the resonance ejection mode. In the second study we have discussed methods to determine the multipole coefficients in the toroidal ion trap mass analysers. The third study investigates the stability of ions in the toroidal ion trap mass analysers. The first study presents a technique to cause unidirectional ion ejection in a quadrupole ion trap mass spectrometer operated in the resonance ejection mode. In this technique a modified auxiliary dipolar excitation signal is applied to the endcap electrodes. This modified signal is a linear combination of two signals. The first signal is the nominal dipolar excitation signal which is applied across the endcap electrodes and the second signal is the second harmonic of the first signal, the amplitude of the second harmonic being larger than that of the fundamental. We have investigated the effect of the following parameters on achieving unidirectional ion ejection: primary signal amplitude, ratio of amplitude of second harmonic to that of primary signal amplitude, different operating points, different scan rates, different mass to charge ratios and different damping constants. In all these simulations unidirectional ejection of destabilized ions has been successfully achieved. The second study presents methods to determine multipole coefficients for describing the potential in toroidal ion trap mass analysers. Three different methods have been presented to compute the toroidal multipole coefficients. The first method uses a least square fit and is useful when we have ability to compute potential at a set of points in the trapping region. In the second method we use the Discrete Fourier Transform of potentials on a circle in the trapping region. The third method uses surface charge distribution obtained from the Boundary Element Method to compute these coefficients. Using these multipole coefficients we have presented (1) equations of ion motion in toroidal ion traps (2) the Mathieu parameters in terms of multipole coefficients and (3) the secular frequency of ion motion in these traps. It has been shown that the secular frequency obtained from our method has a good match with that obtained from numerical trajectory simulation. The third study presents stability of ions in practical toroidal ion trap mass analysers. Here we have taken up for investigation four geometries with apertures and truncation of electrodes. The stability is obtained in UDC-VRF plane and later this is converted into A-Q plane on the Mathieu stability plot. Though the plots in terms of Mathieu parameters for these structures are qualitatively similar to the corresponding plot of linear ion trap mass analysers, there is a significant difference. The stability plots of these have regions of nonlinear resonances where ion motion is unstable. These resonances have been briefly investigated and it is proposed that they occur on account of hexapole and octopole contributions to the field in these toroidal ion traps.
127

Charakterizace glykoforem haptoglobinu v lidském séru / Characterization of hapt oglobin glycoforms in human serum

Darebná, Petra January 2015 (has links)
Characterization of haptoglobin glycoforms in human serum Petra Darebná (Katedra biochemie, Přírodovědecká fakulta, Univerzita Karlova v Praze, Česká republika) Changes in glycosylation of proteins are associated with several types of cancer, including hepatocelular carcinoma and colorectal carcinoma. This project deals with data independent analysis using ion cyclotron resonance with Fourier transform and tandem mass spectrometry with liquid chromatogramy and multiple reaction monitoring to quantify these changes in hepatocelular cancinoma and colorectal carcinoma with liver metastases. In the first part of the project the haptoglobin was enriched from pooled serum samples of pacients with hepatocellular carcinoma, colorectal cancer and colorectal carcinoma with metastases using hemoglobin immobilized on CNBr-activated Sepharose 4B and then purified by high pressure liquid chromatography. Individual haptoglobin glycopeptides were analyzed using ion cyclotron resonance with Fourier transform. In the second part of the project we analyzed changes in glycosylation depending on diferent tumor diseases in partially depleted serum of individual patients using ethanol precipitation. Individual fucosylated glycoforms of N-glycopeptides of serum proteins were compared with their nonfucosylated forms. In...
128

Escape Of High Mass Ions Due To Initial Thermal Energy And Its Implications For RF Trap Design

Subramanyan, E K Ganapathy 09 1900 (has links) (PDF)
This thesis investigates the loss of high mass ions due to the initial thermal energy in ion trap mass analyzers. It provides an analytical expression for estimating the percentage loss of ions of a given mass at a particular temperature, in a trap operating with a set of conditions. The investigations have been carried out on quadrupole and cylindrical ion trap geometries. The three-dimensional Maxwellian velocity distribution function has been assumed to derive an expression for the percentage of ions lost. Adopting an approximation based on the observed escape velocity profiles of ions, an expression for the percentage loss of ions of a given mass has been derived as a function of the temperature for an ensemble of ions, its mass and its escape velocity. An analytical expression for the escape velocity has also been developed. It is seen that the escape velocity is a function of the trapping field, drive frequency and ion mass. Because the trapping field is determined by trap design parameters and operating conditions, it has been possible to study the influence of these parameters on ion loss. The parameters investigated include ion temperature, magnitude of the initial potential applied to the ring electrode (which determines the low mass cut-off), trap size, dimensions of apertures in the endcap electrodes and RF drive frequency. The studies demonstrate that ion loss due to initial thermal energy increases with increase in mass and that ion escape occurs in the radial direction. Reduction in the loss of high mass ions is favoured by lower ion temperatures, increasing low mass cut-off, increasing trap size, and higher RF drive frequencies. The dimensions of the apertures in the endcap electrodes do not influence ion loss in the range of aperture sizes considered.
129

A Preliminary Investigation Of The Role Of Magnetic Fields In Axially Symmetric rf Ion Traps

Sridhar, P 04 1900 (has links) (PDF)
Axially symmetric rf ion traps consists of a mass analyser having three electrodes, one of which is a central ring electrode and the other two are endcap electrodes. In the ideal Paul trap mass spectrometer, the electrodes have hyperboloidal shape (March and Hughes, 1989) and in mass analyser with simplified geometry, such as the cylindrical ion trap (Wu et al.,2005) the central electrode is a cylinder and the two endcap electrode and flat plates. rf-only or rf/dc potential is applied across the ring electrode and the grounded endcap electrodes for conducting the basic experiments of the mass spectrometer. In recent times, the miniaturisation of ion trap is one of the research interests in the field of mass spectrometry. The miniaturisation has the advantages of compactness, low power consumption and portability. However, this is achieved at the cost of the overall performance of the mass spectrometer with its deleterious effect on resolution. Research groups study the field distribution in the trap for better understanding of ion dynamics in the direction of achieving improved performance with the miniaturised traps. One aspect which has not received any attention in research associated with quadrupole ion traps is the possible role of the magnetic field in improving performance of these traps. Since in the quadrupole ion trap mass analyser ion is confined by an oscillating (rf) field, magnetic fields have been considered superfluous. The motivation of the thesis is to understand the dynamics of ions in axially symmetric rf ion traps, in the presence of the magnetic field. The axially symmetric rf ion trap geometries considered in this thesis are the Paul trap and the cylindrical ion trap (CIT). The changes incurred to the ion motion and Mathieu stability diagram in the presence of magnetic field is observed in this work. Also, the relation between the magnetic field and the Mathieu parameter is shown. The thesis contains 4 chapters: Chapter 1 provides the basic back ground of mass spectrometry and the operating principles. The equations of ion motion in the Paul trap is derived and also the solution to Mathieu equation is provided. The solution to the Mathieu equation are the Mathieu parameters and , when plotted with on the x-axis and on the y-axis, results in the Mathieu stability plot, the explanation of which is also given in the chapter. A brief description of the secular frequency associated with the ion dynamics is given in this chapter. The popular experiments conducted (i.e. the mass selective boundary ejection and resonance ejection) with a mass spectrometer is described here. Finally at the end of the chapter is the scope of the thesis. Chapter 2 facilitates with the preliminary study required fort he accomplishment of the task. The Paul trap and the CIT are the rf ion traps considered in this work. The geometries of these two traps are described in this chapter. The computational methods used for the analysis of various aspects of mass spectrometer is introduced. The computational methods used involve the methods used for calculating the charge distribution on the electrodes, potentials, multipole co-efficients and trajectory calculations. The boundary element method(BEM), calculation for Potentials and the Runge-Kutta method used for the trajectory calculations are introduced in this chapter. The expressions for calculating the multipole co-efficients are also specified. Chapter 3 presents the results obtained. The equations of ion motion in a quadrupole ion trap in the presence of magnetic field is derived here. Verification of numerical results with and without the magnetic field are presented at the end of this chapter. The chapter also presents various graphs showing the impact of magnetic field on the ion dynamics in the Paul trap and the CIT. The impact of the presence of magnetic field on the micro motion in -, -and -directions of the rf ion traps are shown in this chapter. Also the figures showing the variation in the Mathieu stability plots, with varying magnetic field intensity are presented in the chapter. At the end of this chapter the relation between the magnetic field and the Mathieu parameter is derived and plotted. Chapter 4 explains the various observations made from the results obtained. This chapter also highlights the future scope of the work for making this a more applicable one. References in the text have been given by quoting the author’s name and year of publication. Full references have been provide, in an alphabetic order, at the end of the thesis.
130

Charakterizace mikropohybu a jeho vliv na systematické posuvy frekvence kvadrupólového přechodu iontu vápníku zachyceného v Paulově pasti / Characterization of micro-motion and its influence on systematic frequency shifts of quadrupole transition of Calcium ion trapped in Paul trap

Vadlejch, Daniel January 2020 (has links)
This thesis deals with the analysis of micromotion of a single charged calcium ion trapped inside the linear Paul's ion trap and the influence of residual micromotion on the systematic frequency shifts of the clock transition of calcium ion. The fundamental properties of the motion of an ion confined within linear Paul's ion trap are shown in general using a theoretical description. The micromotion component of the overall motion is especially emphasized. A model expressing micromotion in the axial direction of the trap is introduced on the basis of the results of the numerical calculation of electric fields inside the trap. The model is compared to the reality experimentally. Then, the photon-correlation method of detection of micromotion is introduced and subsequently used to minimize and to estimate a measure of residual micromotion in all spacial directions. According to the achievable measure of residual micromotion, the systematic frequency shifts caused by this micromotion are estimated. It can be seen that we are able to reach uncertainties of the relative frequency shifts due to micromotion below 10^20. We expect that uncertainty of total motional systematic frequency shift is in our case limited by thermal motion.

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