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1
Newsome, G. Asher Glish Gary L. "Novel instrumentation and method development for a quadrupole ion trap mass spectrometer". Chapel Hill, N.C. : University of North Carolina at Chapel Hill, 2009. http://dc.lib.unc.edu/u?/etd,2747.
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Thesis (Ph. D.)--University of North Carolina at Chapel Hill, 2009.Title from electronic title page (viewed Mar. 10, 2010). "... in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department Chemistry." Discipline: Chemistry; Department/School: Chemistry.
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Laskay, Ünige A. "Dynamic collision induced dissociation : a novel fragmentation method in the quadrupole ion trap /". View abstract, 2009. http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&res_dat=xri:pqdiss&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&rft_dat=xri:pqdiss:3353544.
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Laskay, Ünige A. "Dynamic Collision Induced Dissociation - A Novel Fragmentation Method in the Quadrupole Ion Trap". Ohio University / OhioLINK, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1230577624.
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Kliewer, Marcus. "Método de Espectroscopia de Mistura de Níveis para Medida de Momentos de Quadrupolo Nucleares". Universidade de São Paulo, 1999. http://www.teses.usp.br/teses/disponiveis/43/43131/tde-16022011-194341/.
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Momentos de quadrupólo elétricos de estados isoméricos nucleares com vidas médias entre 10 nanosegundos e 100 milisegundos podem ser medidos com o método Espectroscopia de Mistura de Níveis (Level Mixing Spectroscopy- LEMS), utilizando campos magnéticos variáveis aplicados em núcleos implantados em materiais hospedeiros que possuam gradientes de campo elétrico. O Campo magnético externo pode ser substituido pelo campo hiperfino de materiais ferromagnéticos e sua variação poderia ser controlada variando a temperatura. O objetivo deste trabalho é verificar a viabilidade desta substituição. Implementamos o método LEMS no Laboratório Pelletron usando como caso teste o estado isomérico de 398 KeV do 69Ge que possui todas as suas propriedades nucleares conhecidas (meia vida, spin, momento magnético, momento de quadrupolo elétrico). Ele foi produzido pela reação 56Fe(16O, 2pn)69Ge com o feixe de 16O à 53 MeV (LAB) de energia, e depois implantado em Gadolínio que é ferromagnético abaixo de Tc = 289K. Medimos a anisotropia da radiação gama emitida por esse núcleo em função da temperatura. A comparação entre as medidas da anisotropia em função da temperatura, com medidas da anisotropia em função do campo magnético externo, feita pelo grupo de Leuven/Bélgica, nos levou a duas interpretações possíveis. Na primeira, supondo a interação elétrica constante e independente da temperatura, obtemos um campo magnético hiperfino anômalo para o Gd. Na segunda análise, obtivemos o campo hiperfino variando linearmente com a magnetização, admitindo gradientes de campo elétrico dependentes da temperatura. Medidas futuras usando monocristal de Gd poderão resolver esta ambiguidade, bem como medidas TDPAD (Time Diferencial Perturbed Angular Distribuition) em função da temperatura, na qual se mede diretamente o campo hiperfino.The Level Mixing Spectroscopy method allows to measure the eletric quadrupole moments of high spin isomeric nuclear states (10ns < t < 100ms) produced in nuclear reactions. The magnetic interaction is usualy created by an intense external magnetic field. The eletric quadrupole interaction can be created by recoi-implantation of the nuclei in non-cub crystals, used as hosts. The external magnetic field can then be replaced by the hiperfine fields of ferromagnetic materials, controling its intensity by temperature variation. The purpose of the research performed for this work is to verify the viability of this replacement. We adapt the LEMS method to be used in the Pelletron Laboratory. We choose the isomeric state at 398 KeV exitation energy in the 69Ge nucleus as a test case, because it has all nuclear properties well known (half-life, spin, magnetic moment, eletric quadrupole moment). It was produced by the 56Fe(16O, 2pn)69Ge reaction, with a 16O beam at 53 MeV, and implanted and stopped in a Gadolinium host, which is a ferromagnet from low temperatures up to Tc=289 K. We measure the anisotropy of the emitted gama ray as a function of the temperature of the host. The comparison of this measurement with another of the anisotropy as a function of an external magnetic field strength, done by the Leuven/Belgium group, show us two possibilities. In the first, we suppose that the eletric interaction is cosntant and independent of temprature and we obtain an anomalous magnetic hyperfine field for Gd. In the second one, we obtain a hyperfine field that follows the magnetization if we assume eletric field gradientes that are temperature dependent. New measurements by using Gd monocrystal and the TDPAD (Time Diferencial Perturbed Angular Distribution) method may solve this ambiguity.
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Cook, Shannon L. "Metastable Atom-Activated Dissociation (MAD): A Novel Dissociation Method Employed within a Quadrupole Ion Trap Mass Spectrometer". Ohio University / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1331325173.
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Borazjani, Ehsan. "Inverse Heat Conduction Approach for Infrared Non-destructive Testing of Single and Multi-layer Materials". Thèse, Université d'Ottawa / University of Ottawa, 2012. http://hdl.handle.net/10393/22919.
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The focus of this thesis is to derive analytical tools for the design of infrared nondestructive tests in single and multi layer material bodies. This requires the predetermination of the parameters of the experiment such that the infrared image has the required resolution for defect detection. Inverse heat conduction in single and multi-layer materials is investigated to determine the required frequency of excitation in order to obtain a desired temperature at the observation point. We use analytical quadrupole representation to derive a polynomial relation to estimate the frequency of the periodic excitation as a function of the temperature amplitude at a given observation point within the body. The formula includes characteristic geometric and material parameters of the system. The polynomial formula can be an e ective design tool for quick frequency predetermination in the design of non-destructive testing experiments with infrared thermography. The convergence and accuracy of the formula is assessed by comparison with the analytical thermal quadrupole solution and experimental results. We also investigate the e ect of the nite length of the material domain in order to establish the range of applicability of a simpli ed formula based on semi-in nite domain assumption. The e ect of nite length is investigated analytically by using (i) Fourier series which accounts for transients and (ii) Time varying solution associated to the steady state solution when a purely periodic excitation is applied. These results are also compared with numerical solution obtained with commercial nite element software ANSYSTM.
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Shepherd, Sarah Louise. "Lifetime measurement of '1'5'8Er using the recoil distance method". Thesis, University of Liverpool, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.366949.
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Dronov, Michail [Verfasser] y Torsten Claus [Akademischer Betreuer] Schmidt. "Concentration-Gradient-Method for improvement of precision and accuracy of isotope ratio analysis using quadrupole based inductively coupled plasma-mass spectrometry / Michail Dronov ; Betreuer: Torsten Claus Schmidt". Duisburg, 2018. http://d-nb.info/1173616012/34.
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Moradian, Annie. "New methods of mass analysis with quadrupoles with added octopole fields". Thesis, University of British Columbia, 2007. http://hdl.handle.net/2429/367.
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Mass selective axial ejection of ions and mass analysis with a stability island with linear quadrupoles with added octopole fields are described. With mass selective axial ejection, quadrupoles with 2.0% and 2.6% added octopole fields have been tested and compared to a conventional quadrupole. The effects of trapping ions at different q values,
excitation voltage, scan direction, balanced and unbalanced rf voltages on the rods, and dc applied between the rods have been investigated. The highest scan speeds and highest resolution are obtained with resonant excitation and ejection at high q (q = 0.8). With axial ejection, the quadrupole with a 2.0% added octopole field provides mass resolution and ejection efficiencies similar to a conventional rod set. Quadrupole, dipole and simultaneous dipole-dipole excitation between the x and y rod pairs were compared and
no advantage was found with quadrupole or dipole-dipole excitation. The effects of scan speed were investigated and a resolution at half height of about 1600 is possible at scan speeds up to 5000 Th/s.
Mass analysis using islands of stability was investigated with a quadrupole with2.0% added octopole field. The island of stability is formed with auxiliary excitation. The experiments confirm the predictions of the simulations. With the resolving dc applied to the quadrupole so that the Mathieu parameter a>0, conventional mass analysis with applied rf and dc and no auxiliary excitation is possible. In this case use of an island of stability yields similar peak shape and resolution. However with the polarity of the resolving dc reversed so that a<0, only very low resolution can be obtained; the added octopole prevents conventional mass analysis. By using a stability island when a<0, the resolution is substantially improved.
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Saba, Elias. "Detection and Quantification of PCB insoil using GC/MS : - method development and education for users". Thesis, KTH, Skolan för teknikvetenskap (SCI), 2013. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-126489.
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The aim of this paper is to document the development of a method for detectionand quantification of Polychlorinated biphenyls (PCB) in soil using GasChromatography (GC) connected to a Quadrupole Mass Spectrometer (MS) via aninternal standard (CB189). The method developed is performed in conjunction withthe information provided by the Swedish environmental agency (Svenskanaturvårdsverket, SNV) in regards to PCB limits for sensitive land usage. The steps ofthe method and maintenance of the GC/MS are used to create a user manual andan attempt at transformative learning is done in an effort to teach the staff atLjungaLab AB so that at the very least, independent analysis can be run and at best,new methods and application are independently developed for the GC/MS. Anevaluation of the teaching efforts is also done to assess what grade of learning isachieved.Syftet med denna uppsats är att dokumentera utvecklingen av en metod fördetektion och kvantifiering av polyklorerade bifenyler (PCB) i jord med hjälp avgaskromatografi (GC) ansluten till en masspektrometer (MS) och med användningav en intern standard (CB189). Metoden som utvecklats skapades med hjälp avuppgifter från det svenska naturvårdsverket (SNV) angående PCB-gränser för känsligmarkanvändning. Därefter skapades en användarmanual som beskriver stegen imetoden och även underhåll av GC/MS. Personalen på LjungaLab AB undervisadesi hur man använder och underhåller instrumenten för att, åtminstone, kunna köraoberoende analyser, och i bästa fall, utveckla nya metoder och tillämpningarsjälvständigt. Det sistnämda är ett försök till transformativ lärande. En utvärdering avlärarinsatser sker också för att bedöma vilken grad av lärande som uppnås.
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Arvidsson, Björn. "Quantitative Bioanalysis : Liquid separations coupled to targeted mass spectrometric measurements of bioactive compounds". Doctoral thesis, Uppsala universitet, Analytisk kemi, 2008. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-8581.
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Performing quantitative analysis of targeted bioactive compounds in biological samples, such as blood plasma, cerebrospinal fluid or extracts from pig liver, put high demands on the ruggedness of the method acquiring the results. In addition to the complexity of the sample matrix, the bioactive compounds targeted for analysis usually have low levels of natural abundance, further increasing the demand on the analytical method sensitivity. Furthermore, quantitation of analytes at trace levels in the presence of large amounts of interfering species in biofluids must aim for repeatable precision, high accuracy ensuring the closeness to the true values, a linear response spanning over several orders of magnitude and low limits of quantitation to be valid for monitoring disease states in clinical analysis. An analytical method most commonly follow a certain order of events, called the analytical chain, which includes; experimental planning, sampling, sample pre-treatment, separation of species, detection, evaluation, interpretation and validation, all equally important for the outcome of the results. In this thesis, the scope has been to create novel methods, or to refine already existing methods, in order to achieve even better performances of the different events in the analytical chain. One of the aspects has been to sample and enrich analytes in vivo by the use of solid supported microdialysis, giving the advantage of almost real-time monitoring of analyte levels within a living host with targeted selectivity due to the analyte affinity for solid particles. Another aspect to selectively clean and enrich analytes in a complex matrix has been developed and automated on-line by the use of a column-switching technique before the analytical separation. By using several steps of extraction and separation coupled on-line to selected detection by the use of a triple quadrupole mass spectrometer facilitates great selectivity of species. The mass spectrometer also gives the ability to distinguish between isotopically labelled analogues coeluting with the analytes yielding the necessary accuracy for quantitative evaluation. Both development of analytical methods and clinical applications has been performed, as well as improvements of existing techniques, all to improve the quantitation of trace levels of targeted analytes in biofluids.
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Xiong, Hong. "Robust adaptive methods and their applications in quadrupole resonance". [Gainesville, Fla.] : University of Florida, 2006. http://purl.fcla.edu/fcla/etd/UFE0013387.
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Payne, Nicholas Roy. "Quadrupolar relaxation-based methods in fast field-cycling MRI". Thesis, University of Aberdeen, 2019. http://digitool.abdn.ac.uk:80/webclient/DeliveryManager?pid=240235.
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Quadrupolar relaxation-based methods in Fast Field-Cycling MRI Nicholas R. Payne Aberdeen Biomedical Imaging Centre, University of Aberdeen, AB25 2ZD, Scotland, UK Fast Field-Cycling MRI (FFC-MRI) can access contrast based on the dependence of a sample's relaxation rate to the applied magnetic field strength. This technique can provide signal based on interactions with local quadrupolar nuclei through cross-relaxation, however, there are other so-called Nuclear Quadrupole Double Resonance (NQDR) techniques described in the literature. This work has been centred on efforts to apply these techniques to FFC-MRI and otherwise explore how interactions between protons and quadrupolar nuclei can be further exploited. Through this work two irradiation systems were designed and built for manual tuning, in the first instance, and automatic tuning. The latter was able to quickly retune to coil, however, it was limited in RF power handling capability. A second strand of work was concerned with the reduction in receiver deadtime required to detect signal from solid-state samples such as those previously used in NQDR experiments in the literature. However, circuitry designed to dampen coil ringing by temporarily reducing the resonator's Q-factor following a pulse, along with a novel method utilising field-cycling were not able to reduce the deadtime enough to detect signal from relevant samples. This, coupled with a lack of evidence of NQDR effects in gel-like samples, proved the ultimate stumbling block for NQDR in FFC-MRI. Success was seen in a third strand of work in which simulations were used to design custom experiments which could be used to provide large increases to the signal-to-noise ratio in some experiments. The simulated environment also allowed for fast testing and development of new post-process algorithms which could more accurately calculate relaxation rates. The work concluded that NQDR is unlikely to be useful in FFC-MRI due to the constraints on both the sample and the technique. However the information from quadrupolar nuclei can be improved with better post-processing and tailored pulse sequence parameters.
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Madur, Arnaud. "Contribution à la métrologie magnétique des multipôles d'accélérateurs : les quadrupôles du Synchroton SOLEIL". Thesis, Vandoeuvre-les-Nancy, INPL, 2006. http://www.theses.fr/2006INPL060N/document.
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Dans les accélérateurs de particules de type synchrotron tels que SOLEIL, le faisceau de particules doit répondre à des critères toujours plus exigeants afin d’améliorer les propriétés du rayonnement synchrotron émis. Le comportement du faisceau d’électrons dépend notamment des aimants multipolaires de l’anneau de stockage du synchrotron. Parmi eux, les quadrupôles, qui produisent une induction magnétique quadrupolaire, ont un rôle capital dans la focalisation des particules du faisceau. Certains défauts de fabrication peuvent introduire des décalages dans la position de leur axe magnétique et dans l’orientation transverse de l’induction magnétique, ce qui détériore la qualité de champ. Il est donc nécessaire de quantifier ces défauts et de les corriger. Pour cela, des mesures magnétiques sont mises en œuvre. Le premier chapitre de ce mémoire s’attache principalement à expliciter les tolérances imposées aux quadrupôles de l’anneau de stockage du synchrotron SOLEIL. Dans le second chapitre, les outils théoriques permettant de mettre en œuvre la méthode des bobines tournantes sont présentés. Une modélisation est proposée afin de prévoir les conséquences des défauts des bobines tournantes sur les harmoniques de l’induction magnétique. Une méthode de détection des défauts du banc de mesures est également présentée. Le troisième chapitre est dévolu aux résultats expérimentaux obtenus lors de la mesure des aimants multipolaires (quadrupôles) de l’anneau de stockage de SOLEIL. Dans un dernier chapitre, l’alignement basé sur le faisceau (BBA) des quadrupôles et des sextupôles dans l’anneau de stockage est abordé. Cette étape est indispensable car elle permet de connaître la position du faisceau par rapport à son orbite théorique qui peut être définie comme étant l’axe magnétique des quadrupôles ou l’axe magnétique des sextupôles. Une méthode de BBA est ici validée dans le cas des quadrupôles et une autre est proposée dans le cas des sextupôlesIn particle accelerators, more particularly in synchrotrons like SOLEIL, the particle beam is submitted to very strict constraints in order to improve the synchrotron radiation properties. The behaviour of the electron beam depends on the magnetic field distribution along the machine, mainly produced by the multipolar magnets of the storage ring (SR). Among them, the SOLEIL quadrupoles makes the electron beam very sensitive to their magnetic field errors due to some manufacturing defects. In that context, two main parameters are very important concerning the quadrupoles: the magnetic axis location and the magnetic field orientation in the transverse plane. These quantities are to be quantified and corrected by means of magnetic measurements. The first part of this thesis is mainly devoted to the presentation of the quadrupole constraint origin. In that context, the accelerator history and a brief review of the existing magnetic measurement method are presented. In the second chapter, theoretical tools regarding rotating coils are detailed. A model is proposed to simulate the effects of rotating coil defects on the magnetic measurements. Then, to quantify these defects, a method is detailed in order to take them into account during the measurements. A third chapter is devoted to the magnetic measurement bench set up and to the experimental results of the SR multipolar magnet measurements. Finally, the last chapter deals with the beam-based alignment (BBA) of the SR multipoles. A method is validated for quadrupoles and an innovative BBA method is proposed in the case of sextupoles
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Johnson, Clive. "The use of periodic ab initio methods in the determination of NMR quadrupole parameters". Thesis, Open University, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.270038.
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Vadlejch, Daniel. "Charakterizace mikropohybu a jeho vliv na systematické posuvy frekvence kvadrupólového přechodu iontu vápníku zachyceného v Paulově pasti". Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2020. http://www.nusl.cz/ntk/nusl-417151.
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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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Widdifield, Cory. "Multinuclear Solid-State Magnetic Resonance Studies on ‘Exotic’ Quadrupolar Nuclei: Acquisition Methods, High-Order Effects, Quantum Chemical Computations, and NMR Crystallography". Thèse, Université d'Ottawa / University of Ottawa, 2012. http://hdl.handle.net/10393/20722.
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This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.
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Cunningham, Connell Glish Gary L. "Improved methods of tandem mass spectrometry for proteomics applications in a quadrupole ion trap mass spectrometer". Chapel Hill, N.C. : University of North Carolina at Chapel Hill, 2006. http://dc.lib.unc.edu/u?/etd,217.
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Thesis (Ph. D.)--University of North Carolina at Chapel Hill, 2006.Title from electronic title page (viewed Oct. 10, 2007). " ... in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Department of Chemistry. Chapel Hill 2006." Discipline: Chemistry; Department/School: Chemistry.
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BELLAMY, PASCAL. "Methode d'analyse des systemes de locomotion de robots, et application a un quadrupede". Paris 6, 1988. http://www.theses.fr/1988PA066057.
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Determination et optimisation d'un systeme de locomotion de robot a partir des conditions de fonctionnement imposees a ce vehicule. L'ebauche d'une methode d'analyse cinematique parametree est proposee. Les equations cinematiques sont obtenues par analogie entre le probleme de la prehension et la manipulation d'objets et celui de la locomotion
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Colaux, Henri. "Investigating sensitivity improvement methods for quadrupolar nuclei in solid-state nuclear magnetic resonance". Thesis, University of St Andrews, 2016. http://hdl.handle.net/10023/9628.
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The study of quadrupolar nuclei using NMR spectroscopy in the solid state significantly increased in popularity from the end of the 20th century, with the introduction of specific methods to acquire spectra free from the effects of the quadrupolar interaction, that results in broadened lineshapes that cannot be completely removed by spinning the sample at the magic angle (MAS), unlike most of the other interactions present in the solid state. The first technique which allows, without any specific hardware, the removal of this broadening has been the Multiple-Quantum MQMAS experiment. The method quickly gained a popularity within the NMR community, with numerous successful applications published. However, the multiple-quantum filtration step in this experiment relies on severely limits sensitivity, restricting application to the most sensitive nuclei. Extending the applicability of MQMAS to less receptive nuclei requires the use of signal improvement techniques. There are multiple examples of such approaches in the literature, but most of these require additional optimisation that may be time-consuming, or simply impossible, on less receptive nuclei. This work introduces a novel signal improvement technique for MQMAS, called FAM-N. Its optimisation is solely based on density matrix simulations using SIMPSON, implying no additional experimental optimisation is required, while improving the signal in MQMAS spectra by equivalent or higher amounts than other common methods. In order to prove the applicability of this method on virtually any system, FAM-N has been investigated by simulation, and tested experimentally using a number of model samples, as well as samples known to be challenging to study by NMR. This work also explores other aspects of NMR spectroscopy on quadrupolar nuclei. Adiabatic inversion of the satellite populations can be performed to improve the central transition signal in static or MAS spectra. A range of methods has been tested and compared, with particular attention given to hyperbolic secant-shaped pulses, for which its performance have been described. Finally, cross-polarisation from a spin I = 1/2 nucleus to a quadrupolar nucleus has been investigated. After reviewing the theory for the static case, simulations have been performed under MAS in order to identify the conditions for efficient magnetisation transfer, with applications in spectral editing or for the combination with MQMAS.
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Wirnsberger, Peter. "Computer simulation and theoretical prediction of thermally induced polarisation". Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/282988.
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In this thesis, we study the phenomenon of thermally induced polarisation using a combination of theory and computer simulation. Molecules of sufficiently low symmetry exhibit thermo-molecular orientation when subjected to a temperature gradient, leading to considerable electrostatic fields in polar liquids. Here, we first use non-equilibrium molecular dynamics simulations to study this interesting effect numerically. To this end, we propose an integration algorithm to impose a constant heat flux in simulations and show that it greatly improves energy conservation compared to a previous algorithm. We next investigate the thermal polarisation of water and find that truncation of electrostatic interactions can lead to severe artefacts, such as the wrong sign of polarisation and an overestimation of the electric field. We further show that the quadrupole-moment contribution to the electric field is significant and responsible for an inversion of its sign. To facilitate the theoretical description of electrostatic interactions, we propose a new dipolar model fluid as a perturbation of a Stockmayer fluid. Using this modified Stockmayer model, we provide numerical evidence for the recently proposed phenomenon of thermally induced monopoles. We show that the electrostatic field generated by a pair of heated/cooled colloidal particles immersed in such a solvent can be trivially described by two Coulomb charges. Finally, we propose a mean-field theory to predict the thermo-polarisation effect exhibited by our model fluid theoretically, and demonstrate near quantitative agreement with simulation results.
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Ageev, Sergei Z. "Application of density matrix methods to quadrupolar spins in solid state NMR and NQR". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1997. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp04/nq29870.pdf.
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Cotta, Aloísio José Bueno. "Determinação de elementos-traço em águas e rochas por ICP-MS quadrupolar com cela de colisão". [s.n.], 2010. http://repositorio.unicamp.br/jspui/handle/REPOSIP/286784.
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Orientador: Jacinta EnzweilerTese (doutorado) - Universidade Estadual de Campinas, Instituto de Geociências
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Resumo: A espectrometria de massas com plasma indutivamente acoplado (ICP-MS) possibilita determinações multielementares rápidas e com baixos limites de detecção numa variedade de matrizes, dentre elas as geológicas. Neste estudo, métodos comparativos utilizando um ICP-MS quadrupolar equipado com cela de colisão (CC) foram estabelecidos para determinar amplos conjuntos de elementos-traços em águas e em rochas. A aplicabilidade e as limitações da CC para atenuar interferências poliatômicas sobre os isótopos empregados foram amplamente investigadas. Em condições ótimas, muitas interferências puderam ser eliminadas ou significativamente atenuadas, o que tornou os métodos menos dependentes de correções matemáticas. Para a análise de rochas, técnicas clássicas de dissolução envolvendo misturas ácidas, como HF/HNO3, foram utilizadas e um novo procedimento com equipamento que possibilita efetuar a digestão sob pressão de até 13 MPa é proposto. Nesse caso, a precipitação de AlF3, o qual retém alguns elementos-traço, principalmente Co, Sr, Ba e Pb, foi o maior obstáculo à recuperação quantitativa dos analitos. A formação de AlF3 foi evitada com a adição de Mg à porção teste e com o controle da temperatura de digestão. A decomposição por sinterização com peróxido de sódio foi também investigada e verificou-se que a inclusão de uma etapa de aquecimento da dispersão resultante da dissolução do sinterizado em água, antes da separação do precipitado de hidróxidos de Fe e Ti, o qual retém os elementos-traço, auxilia na coprecipitação de Ni, Zr, Nb, Cd, Sn, Sb, Hf, Pb e Th e permite acrescentá-los à lista de elementos determináveis. Os métodos foram validados pela análise de um conjunto de materiais de referência (MR), alguns deles certificados. Os resultados obtidos demonstraram que os métodos desenvolvidos para águas e rochas apresentaram tendência e coeficientes de variação menores que 5% para a maior parte dos mensurandos. Os resultados obtidos para os MR certificados de rochas, BRP-1 e OU-6, foram utilizados para calcular a incerteza do método ao nível aproximado de confiança de 95%. A técnica de diluição isotópica foi aplicada para determinar Cr, Ni, Cu, Zn, Sr e Sn em alguns MR de rochas em uso e em candidatos a MR, com o objetivo de estabelecer o método e contribuir com novos valores para esses MR. As incertezas de todas as etapas do procedimento foram estimadas. Os resultados obtidos evidenciam que o valor certificado de Cr em BRP-1 deveria ser revisto e confirmam a necessidade do estabelecimento da rastreabilidade metrológica durante a certificação de MR.
Abstract: Inductively coupled plasma mass spectrometry (ICP-MS) is suited for fast multi-trace element determinations with low detection limits in a variety of matrices, including geological samples. In this study we established comparative analytical methods for the determination of an expressive number of trace elements in water and rock samples using an ICP-MS equipped with collision cell (CC). The applicability and limitations of CC for polyatomic interference attenuation over the isotopes used were widely investigated. Under optimized conditions, many interferences were eliminated or significantly attenuated, so these methods depend less on mathematical corrections. For rock analyses, classical multi-acid decomposition techniques, with mixtures like HF/HNO3, were used, and a new procedure with equipment that allows digestion at 13 MPa is proposed. In this case, the precipitation of AlF3, which retains some trace elements like Co, Sr, Ba and Pb preferentially, was the major drawback in achieving quantitative recoveries. The formation of AlF3 was inhibited by adding Mg to the test portion and controlling the temperature of digestion. Sample decomposition by sintering with sodium peroxide was also tested and was demonstrated that including a heating step of the sinter dispersion obtained after dissolution in water and before the separation of the precipitated Fe and Ti hydroxides, which retain many trace elements, helps to achieve a quantitative co-precipiation of Ni, Zr, Nb, Cd, Sn, Sb, Hf, Pb and Th and allows to include them to the list of determinable elements. The methods were validated by analysis of a set of reference materials (RM) some of them certified. Relative standard deviations and bias of the results were less than 5% for most of the measurands. The results obtained for the certified RM BRP-1 and OU-6 were used to calculate the measurement uncertainty at the approximate 95% confidence interval. The isotope dilution technique was applied to determine Cr, Ni, Cu, Zn, Sr and Sn in some geochemical RM in use and in candidate RM, with the objective of establishing the method to contribute with new values for the analysed RM. The uncertainties of the whole analytical procedure were estimated. The results obtained show that the certified value of Cr in BRP-1 should be reviewed and confirm the need of establishing the metrological traceability during the certification of RM.
Doutorado
Geologia e Recursos Naturais
Doutor em Ciências
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Ghimire, Chiran. "FUSION OF LIPID DROPLETS AND SUBMOLECULAR DISSECTION OF DNA G-QUADRUPLEX USING OPTICAL TWEEZERS". Kent State University / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=kent1501231695038118.
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Procházka, Michal. "NQR spektroskopie - návrh metod měření". Master's thesis, Vysoké učení technické v Brně. Fakulta elektrotechniky a komunikačních technologií, 2013. http://www.nusl.cz/ntk/nusl-219990.
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Nuclear quadropole spectroscopy is a modern analytical method for detecting specific solid state materials, e.g. explosives, drugs etc. It uses phenomenon of atomic nucleus called nuclear quadrupole moment. NQR method is very similar to common nuclear magnetic resonance (NMR) that is why major principles are explained using NMR. The thesis deals with basic principle of NQR, its usage for explosives detection and also detection of other chemical compounds and many other useful applications. The thesis deals with specific circuit design, techniques for sufficient sensitivity, impedance matching and circuit isolation. Practical part consists of simulations as well as designs of a few impedance transformers, pi-networks, and coils. Also experimental probe was created. In the last part, NQR workplace was assembled and a few chemical compounds were detected. These were KClO3, NaClO3 and NaNO2 . Finally minimum detectable amount of potassium chlorate as the strongest signal of these was determined.
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Takamiya, Patrick Toyoki. "Approximation of the fast bottom reflection coefficient in the quadruplet expansion of the method of images in a wedge shaped ocean". Thesis, Monterey, Calif. : Springfield, Va. : Naval Postgraduate School ; Available from National Technical Information Service, 1994. http://handle.dtic.mil/100.2/ADA281644.
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Borin, Antonio Carlos. "Aplicações do método interação de configuraçäes ao estudo de espectroscopia eletrônica, fotoeletrônica e ressonância quadrupolar nuclear". Universidade de São Paulo, 1993. http://www.teses.usp.br/teses/disponiveis/46/46132/tde-04072012-090245/.
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Esta tese tem como objetivo central a descrição teórica rigorosa da estrutura, de propriedades e da espectroscopia de alguns sistemas diatômicos. Como abordagem de cálculo ela se serve da metodologia interação de configurações na sua forma conhecida como excitações simples e duplas a partir de um conjunto de múltiplas referências (MRSD-CI), além de conjuntos base relativamente extensos de funções Gaussianas Cartesianas contraídas. Ela propõe a existência de duas novas espécies moleculares, BeC e BeC+, para as quais um total de 20 estados eletrônicos (13 para o BeC e 7 para o BeC+) foram caracterizados através de suas curvas de potencial e de seus respectivos estados vibro-rotacionais. Constantes espectroscópicas para cada estado foram calculadas e os momentos elétricos das transições eletrônicas mais relevantes foram também estudados. Essas transições foram analisadas tanto em termos de probabilidades de transição calculadas via momento de transição como por meio de fatores de Franck-Condon. Transições vibro-rotacionais dentro de um mesmo estado eletrônico foram ainda examinadas. Para esses vários estados, tempos de vida radiativa foram também calculados. Complementando essa descrição espectroscópica, uma discussão sobre a natureza da ligação química nesses sistemas foi ainda apresentada. Conjugando os resultados obtidos para essas duas espécies, o espectro fotoeletrônico da molécula BeC foi simulado servindo-se da aproximação de Franck-Condon para estimar as intensidades das linhas de cada banda. Além de propriedades eletrônicas como o momento de dipolo, cálculos de gradiente de campo elétrico no átomo de berílio em função da distância internuclear foram também realizados com o propósito de fornecer dados teóricos confiáveis que permitam a determinação experimental do momento quadrupolar do núcleo de 9Be sobre o qual existe certa controvérsia na literatura. Tais cálculos, realizados para os sitemas BeH+ e BeC, além de incluirem o efeito da vibração molecular no gradiente de campo elétrico na forma de uma média vibracional, mostraram que a aproximação de Buckingham usada por alguns grupos não é apropriada para descrever tal efeito.The aim of this thesis is to describe theoretically the structure, properties, and the spectroscopy of some diatomic species using the multirefence single and double excitations configuration interaction approach, and an extensive atomic basis set of contracted Cartesian Gaussian orbitals. Two new diatomic species are proposed, BeC and BeC+, for which twenty electronic states have been characterized (13 for BeC, and 7 for BeC+) by means of their potential energy curves and vibro-rotational states. Spectroscopic constants for both of them have been computed, as well as electric moments of the most relevant electronic transitions. The transitions have been described by using either transitions probabilities computed with the aid of the theoretical transition moment functions, or by Franck-Condon factors. Vibro-rotational transitions within the same electronic state have also been described. Radiative lifetimes have been computed for several states. Complementing the spectroscopic description, a descussion on the nature of the chemical bonding has also been presented. A combination of the results for the neutral and ionic species allowed the calculation of the vertical and adiabatic ionization potentials and the Franck-Condon distribution spectrum for transitions from the ground state of BeC to selected bound states of BeC+. Besides the electronic properties, as dipole moment, the electric field gradient at the 9Be nucleus has also been computed as a function of the internuclear distance with the purpose of providing reliable theoretical results to help in the spectroscopic determination of the nuclear quadrupole moment of 9Be, since the data reported to date do not seem to be so conclusive. This kind of analysis has been carried out for the species BeH+ and BeC. By taking into account the nuclear motion effects on the electric field gradient as an average over the vibrational wavefunction, it was possible to show that the commom practice of using the Buckingham\'s expression to compute such correction is not recornrnended.
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Silva, Marcos Antonio da. "Estudo de compostos LiMePO4 (Me=Mg, Co, Ni) através de Ressonância Magnética Nuclear". Universidade de São Paulo, 2000. http://www.teses.usp.br/teses/disponiveis/88/88131/tde-13032014-112117/.
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Nesta dissertação é apresentado um estudo dos compostos Li1-3xMgFexPO4 através de Ressonância Magnética Nuclear (7Li e 31P), no intervalo de temperatura de 150 a 410 K. Estudos desses compostos através de técnicas de difração de elétrons e efeito Mossbauer confirmam que os íons Fe entram na rede cristalina na forma Fe3+, substituindo os íons Li+. O comportamento dos espectros de RMN, dos tempos de relaxação spin-rede e da susceptibilidade magnética dos núcleos 7Li e 31P em função da temperatura, em conjunto com medidas de condutividade iônica, indicam que, mesmo com a adição de impurezas Fe3+ na rede, os íons Li+ pouca mobilidade dentro do intervalo de temperatura utilizado.This work reports a 7Li and 31P nuclear magnetic resonance study in the Li1-3xMgFexPO4 phases between 150 and 410 K. This study, complementary to those made using Mössbauer and magnetic neutron diffraction experiments, confirms that the Fe3+ ions enter as in the lattice, and that they enter substituting Li ions. The behavior of the 7Li e 31P nuclear magnetic resonance spectra, together with ionic conductivity measurements, show that no Li mobility occurs in temperature range studied even with the addition of the Fe impurity.
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El, Rassy Elissa. "Development of Methods to Identify Thermophysical Properties of Complex Media". Thesis, Chasseneuil-du-Poitou, Ecole nationale supérieure de mécanique et d'aérotechnique, 2019. http://www.theses.fr/2019ESMA0013.
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Les matériaux à structures complexes (anisotropes, multicouches et hétérogènes comme poreux) sont de plus en plus utilisés dans de nombreuses applications (ex. automobile,aéronautique, industrie chimique, génie civil et biomédical), notamment en raison de leur amélioration des propriétés mécaniques et physiques. L’identification des propriétés thermophysiques de ces matériaux devient un enjeu incontournable dans plusieurs applications afin de prédire correctement l’évolution de la température au sein de ces structures et d’assurer le contrôle et la modélisation des transferts de chaleur au cours des processus. Dans ce contexte,l’identification des propriétés thermophysiques de tels matériaux, suscitent depuis de nombreuses années une préoccupation importante et croissante. La principale caractéristique de cette thèse concerne la mise en œuvre d’une méthode d’identification directe et simultanée des diffusivités thermiques de matériaux monocouches ou multicouches à l’aide d’un modèle3D transitoire analytique et d’une expérience unique et non intrusive. La méthode proposée est d’abord validée sur un matériau monocouche opaque et isotrope, puis appliquée et vérifiée sur un matériau orthotrope. La méthode d’identification est basée sur l’expérience bien connue de la méthode flash, qui utilise l’évolution de la température sur la face avant ou arrière de l’échantillon, enregistrée via une caméra infrarouge, pour identifier les paramètres inconnus. Compte tenu de la complexité et de la non-linéarité du problème inverse, un algorithme d’optimisation hybride couplant un algorithme stochastique (Optimisation par essaims particulaires) et un déterministe (de type gradient), a été choisi. L’estimation repose sur la minimisation de l’écart entre les mesures et la réponse d’un modèle semi-analytique inspiré de l’approche des quadripôles thermiques qui prédit l’évolution de la température sur la face avant ou la face arrière. L’excitation thermique, générée par un laser CO2, est représentée par un flux de chaleur localisé imposé qui peut être de type Dirac ou créneau. Les estimations sont comparées aux valeurs trouvées dans la littérature et aux résultats obtenus en utilisant d’autres méthodes bien établies. Enfin, quelques améliorations de la méthode sont étudiées, en termes de temps de calcul et de précision, avec une optimisation des conditions expérimentales241RÉSUMÉ(durée et intensité des créneaux, face de mesure. . . ). La méthode est ensuite généralisée aux matériaux multicouches, puis appliquée expérimentalement à un matériau bicouche. Cette stratégie, qui peut être considérée comme une tâche difficile, est motivée par l’impossibilité,dans certains cas, de séparer les 2 couches, en particulier pour les revêtements déposés sur des substrats, qui sera la dernière application investiguée dans ce travail. Une analyse de sensibilité est souvent effectuée afin de tester la faisabilité de l’estimation et de la comparaison,pour les matériaux à deux couches et multicouches, de plusieurs configurations possibles en termes de faces d’excitation/de mesures. La pré-évaluation des méthodes d’identification et les études paramétriques sont effectuées à l’aide de données synthétiques bruitées et obtenues à l’aide du modèle ou d’un code numérique d’éléments finis (pseudo-expérience) afin de vérifier la faisabilité et la robustesse des approches. L’une des caractéristiques les plus distinctes de cette approche est que l’estimation peut être réalisée, et avec succès, sans aucune connaissance préalable de la forme ou de l’intensité de l’excitation. En effet, outre l’estimation simultanée des diffusivités thermiques, la méthode peut prédire la quantité de chaleur absorbée parle matériau ainsi que la distribution spatiale de l’excitation thermiqueAdvanced materials with complex structures (anisotropic, multilayers and heterogeneous like porous) are increasingly used in many applications, (e.g. automotive, aeronautics, chemical industry, civil and biomedical engineering) due to their advantages, in terms of mechanical and physical properties enhancements. Estimating thermophysical properties of such materials becomes a crucial issue in several applications in order to correctly predict temperature evolution inside these structures and to ensure the control and the modelling of heat transfers through the processes. In this context, the identification of such materials thermophysical properties, has taken from many years, a significant and increasing concern. The main feature of this thesis relies on the devolvement of a direct and simultaneous identification method of the thermal diffusivities of monolayer or multilayer materials using an analytical 3D transient model and a unique and non-intrusive experiment. The proposed method is firstly validated on an isotropic opaque monolayermaterial, then applied and verified on an orthotropic one. The identificationmethod is based on the well-known flash-method experiment whose temperature evolution on the front or rear face on the sample, recorded via an IR camera, is used to identify the unknown parameters. Considering the complexity, and the non-linearity of the inverse problem, a hybrid optimization algorithm combining a stochastic algorithm (Particles Swarm Optimization) and a deterministic one (gradient based), has been chosen. This minimization procedure is applied to fit the observation to the output of a pseudo- analytical model inspired from the thermal quadrupoles approach that predicts the temperature evolution on the front or rear face. The thermal excitation, generated by a CO2 laser, is mimicked by an imposed localized heat flux that may be of Dirac or pulse type. The estimations are compared with values from literature and results obtain from well-established methods. Finally, some improvement of the method are investigated, in terms of time consumption and accuracy, with an optimization of the experiment design (pulse time and intensity, measurement face). The method is then generalised to multi-layer materials, then applied experimentally to a two-layer material. This strategy, which can be considered as a challenging task, is motivated by the impossibility, in some cases, to separate the 2 layers, especially for coatings deposited on substrates which is the last application investigated in this work. A sensitivity analysis is often conducted in order to test the feasibility of the estimation and compare, for two-layer and multilayers materials, several possible configurations in terms of excitation/measurements faces. Pre-evaluation of the overall identification methods and parametric studies are performed using synthetic noisy data generated using the model or a numerical finite element code(pseudo-experiment) to verify the approaches feasibility and robustness. One of the most distinctive features of our approach is that the estimation may be successfully achieved without any a priori knowledge about the shape or the intensity of the excitation. Indeed, besides the simultaneous estimation of the thermal diffusivities, the method predicts the total amount of heat absorbed by the material as well as the space shape of the thermal excitation
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Futh, Susanne [Verfasser], Leane [Gutachter] Lehmann y Sabine [Gutachter] Kulling. "Entwicklung einer Methode mittels Gaschromatographie und gekoppeltem Triple-Quadrupol-Massenspektrometer zur Quantifizierung von Estrogen-Metaboliten in humanem Brustgewebe / Susanne Futh. Gutachter: Leane Lehmann ; Sabine Kulling". Würzburg : Universität Würzburg, 2015. http://d-nb.info/1111509042/34.
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Broecker, Sebastian. "Aufbau und Anwendung einer Methode zur Identifizierung und Quantifizierung von Giften und deren Metaboliten in Blut und Haaren in der Systematischen Toxikologischen Analyse mittels Flüssigchromatographie-Quadrupol-Flugzeitmassenspektrometrie-Kopplung (LC-QTOF-MS)". Doctoral thesis, Humboldt-Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2012. http://dx.doi.org/10.18452/16461.
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Die Systematische Toxikologische Analyse (STA) stellt auf Grund der großen Vielfalt und der ständigen Zunahme an toxikologisch relevanten Substanzen eine der größten Herausforderungen in der chemischen Analyse dar. In der vorliegenden Arbeit wurde daher die Eignung der Flüssigchromatographie in Kombination mit der Hybrid-Quadrupol-Flugzeitmassenspektrometrie (LC-QTOF-MS) für diesen Zweck untersucht. Dazu wurden eine Datenbank mit über 7360 und eine CID-Spektrenbibliothek mit mehr als 2720 toxikologisch relevanten Substanzen erstellt und geeignete Probenvorbereitungsmethoden entwickelt. Die Erprobung der Methoden erfolgte an dotierten Blut- und Haarproben. Hierbei zeigte sich, dass die Analyse im Auto-MS/MS-Modus (Messzyklen von MS- und MS/MS-Spektren) eine Identifizierung basischer Substanzen mittels CID-Spektren zwischen 0,5 und 2 ng/ml im Blut ermöglichte. Die Nachweisgrenzen der für 24 Wirkstoffe validierten Methode in Haaren lagen bei 3 bis 15 pg/mg. Die Eignung der LC-QTOF-MS zur STA von Haarproben wurde an 30 Drogentodesfällen und 60 Todesfällen mit bekannter chronischer Medikamenteneinnahme zu Lebzeiten sowie an 77 Blutproben nachgewiesen. Für die Suche nach Metaboliten wurde ein Metaboliten-Tool entwickelt. In der praktischen Anwendung auf Datenfiles von Blut- und Haarproben erwies sich das Tool als wertvolles Hilfsmittel zur Identifizierung unbekannter Peaks und zur Bestätigung von Suchergebnissen in der Datenbank. Zur automatischen Konzentrationsabschätzung identifizierter Substanzen wurde ein Tool „Estimate Concentration“ geschaffen. Die Überprüfung des Verfahrens an realen Blut- und Haarproben durch Vergleich mit HPLC-DAD- und GC-MS-Ergebnissen wies eine gute Übereinstimmung der Konzentrationen auf. Insgesamt zeigten die Untersuchungen, dass die LC-QTOF-MS zurzeit die am besten geeignete Methode für die STA darstellt. Auch bei einem erst später aufkommenden Verdacht kann eine gezielte Suche in dem bereits gemessenen Datenfile durchgeführt werden.Due to the large variety and the steady increase of toxicologically relevant substances, systematic toxicological analysis (STA) is one of the most difficult tasks in analytical chemistry and, therefore, a steady topic of research and methodical improvement. For this reason, the suitability of liquid chromatography in combination with hybrid quadrupole time-of-flight mass spectrometry (LC-QTOF-MS) for STA was investigated. For this purpose, a database of more than 7360 and a CID spectra library of more than 2720 toxicologically relevant substances and suitable methods for sample preparation were developed. The application was evaluated at spiked blood and hair samples. It was found that the analysis in Auto-MS/MS mode (alternating measurement cycles of MS and MS/MS spectra) allowed substance identification in blood using CID spectra between 0.5 and 2 ng/ml for basic substances. The detection limits of the validated method in hair ranged from 3 to 15 pg/mg for 24 drugs. The suitability of LC-QTOF-MS for STA was tested for hair samples from 30 drug-related death cases and from 60 death cases with known chronic medication as well as for 77 blood samples. For the search of metabolites, a metabolite tool was developed. In the practical application to data files from blood and hair samples, the tool proved to be very helpful for identification of unknown peaks and for confirmation of results obtained only from the database without CID spectra. A tool "Estimate Concentration" was created for automatic estimation of concentrations of identified substances. The application to real blood and hair samples and the comparison of the concentrations with results from HPLC-DAD and GC-MS showed good agreement. Overall, these investigations showed that LC-QTOF-MS is currently the most favorable method for STA. Because of the comprehensive registration of all substances in a sample, the data files can be checked for the presence of certain poisons even later without new measurements.
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Gurusinghe, Ranil Malaka. "Methyl Internal Rotation Probed by Rotational Spectroscopy". Kent State University / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=kent1476282624055414.
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Chen, Sih-Yu. "Computational studies of biomolecules". Thesis, University of St Andrews, 2017. http://hdl.handle.net/10023/11064.
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In modern drug discovery, lead discovery is a term used to describe the overall process from hit discovery to lead optimisation, with the goal being to identify drug candidates. This can be greatly facilitated by the use of computer-aided (or in silico) techniques, which can reduce experimentation costs along the drug discovery pipeline. The range of relevant techniques include: molecular modelling to obtain structural information, molecular dynamics (which will be covered in Chapter 2), activity or property prediction by means of quantitative structure activity/property models (QSAR/QSPR), where machine learning techniques are introduced (to be covered in Chapter 1) and quantum chemistry, used to explain chemical structure, properties and reactivity. This thesis is divided into five parts. Chapter 1 starts with an outline of the early stages of drug discovery; introducing the use of virtual screening for hit and lead identification. Such approaches may roughly be divided into structure-based (docking, by far the most often referred to) and ligand-based, leading to a set of promising compounds for further evaluation. Then, the use of machine learning techniques, the issue of which will be frequently encountered, followed by a brief review of the "no free lunch" theorem, that describes how no learning algorithm can perform optimally on all problems. This implies that validation of predictive accuracy in multiple models is required for optimal model selection. As the dimensionality of the feature space increases, the issue referred to as "the curse of dimensionality" becomes a challenge. In closing, the last sections focus on supervised classification Random Forests. Computer-based analyses are an integral part of drug discovery. Chapter 2 begins with discussions of molecular docking; including strategies incorporating protein flexibility at global and local levels, then a specific focus on an automated docking program – AutoDock, which uses a Lamarckian genetic algorithm and empirical binding free energy function. In the second part of the chapter, a brief introduction of molecular dynamics will be given. Chapter 3 describes how we constructed a dataset of known binding sites with co-crystallised ligands, used to extract features characterising the structural and chemical properties of the binding pocket. A machine learning algorithm was adopted to create a three-way predictive model, capable of assigning each case to one of the classes (regular, orthosteric and allosteric) for in silico selection of allosteric sites, and by a feature selection algorithm (Gini) to rationalize the selection of important descriptors, most influential in classifying the binding pockets. In Chapter 4, we made use of structure-based virtual screening, and we focused on docking a fluorescent sensor to a non-canonical DNA quadruplex structure. The preferred binding poses, binding site, and the interactions are scored, followed by application of an ONIOM model to re-score the binding poses of some DNA-ligand complexes, focusing on only the best pose (with the lowest binding energy) from AutoDock. The use of a pre-generated conformational ensemble using MD to account for the receptors' flexibility followed by docking methods are termed “relaxed complex” schemes. Chapter 5 concerns the BLUF domain photocycle. We will be focused on conformational preference of some critical residues in the flavin binding site after a charge redistribution has been introduced. This work provides another activation model to address controversial features of the BLUF domain.
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Broecker, Sebastian [Verfasser], Fritz [Akademischer Betreuer] Pragst y Michael W. [Akademischer Betreuer] Linscheid. "Aufbau und Anwendung einer Methode zur Identifizierung und Quantifizierung von Giften und deren Metaboliten in Blut und Haaren in der Systematischen Toxikologischen Analyse mittels Flüssigchromatographie-Quadrupol-Flugzeitmassenspektrometrie-Kopplung (LC-QTOF-MS) / Sebastian Broecker. Gutachter: Fritz Pragst ; Michael W. Linscheid". Berlin : Humboldt Universität zu Berlin, Mathematisch-Naturwissenschaftliche Fakultät I, 2012. http://d-nb.info/1020016477/34.
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Ranwez, Vincent. "Méthodes efficaces pour reconstruire de grandes phylogénies suivant le principe du maximum de vraisemblance". Phd thesis, Université Montpellier II - Sciences et Techniques du Languedoc, 2002. http://tel.archives-ouvertes.fr/tel-00843175.
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La reconstruction de phylogénies moléculaires consiste à retrouver l'arbre évolutif (ou phylogénie) d'un ensemble de séquences homologues. La méthode de reconstruction la plus fiable actuellement, semble être la méthode du maximum de vraisemblance. Les méthodes classiques pour rechercher la phylogénie de vraisemblance maximale deviennent, rapidement, très coûteuses en temps de calcul lorsque le nombre de séquences augmente. Elles ne peuvent donc pas traiter de grandes phylogénies. Actuellement, les deux types de méthodes qui permettent de reconstruire de grandes phylogénies suivant le principe du maximum de vraisemblance sont : les méthodes de distances et les méthodes de quadruplets. Toutes deux divisent le problème initial en sous-problèmes contenant peu de séquences. Elles peuvent alors résoudre rapidement (suivant le principe du maximum de vraisemblance) chacun de ces sous-problèmes, puis combiner les solutions obtenues pour proposer une phylogénie de l'ensemble des séquences. Après avoir présenté les principales méthodes de reconstruction phylogenetique, nous décrivons une nouvelle méthode de quadruplets (Weight Optimization) qui possède de bonnes propriétés théoriques et reconstruit des arbres plus fiables que Quartet Puzzling (une méthode de quadruplets très populaire). Nous expliquons ensuite en quoi les méthodes de quadruplets sont mal adaptées pour reconstruire de grandes phylogénies suivant le principe du maximum de vraisemblance, et comment ces méthodes peuvent résoudre efficacement d'autres problèmes. Puis, nous proposons une approche qui combine de manière originale les méthodes de distances et du maximum de vraisemblance. Cette approche que nous appelons TripleML permet d'améliorer la fiabilité de différentes méthodes de distances en remplaçant les distances qu'elles utilisent par des distances qui sont estimées en optimisant localement la vraisemblance de triplets de séquences (ou de groupes de séquences).
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Yang, Yingying. "Innovative non-destructive methodology for energy diagnosis of building envelope". Thesis, Bordeaux, 2017. http://www.theses.fr/2017BORD0913/document.
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Le secteur du bâtiment représente 35% des la consommations énergétiques dans les pays membres de l’agence international de l’énergie en 2010 et 39,8% aux Etats-Unis en 2015. Plus de 50% de cette consommation a été utilisée pour la production de chaleur et de froid. Néanmoins cette consommation peut être réduite par l'amélioration la performance énergétique du bâtiment. La performance thermique de l'enveloppe du bâtiment joue un rôle primordial. Par conséquent, le diagnostic thermique de l'enveloppe du bâtiment est nécessaire pour, par exemple, la réception de nouvelles constructions, l'amélioration de la performance énergétique des anciens bâtiments, ainsi que la vente et la location des logements. Pourtant, il existe très peu de méthodes quantitatives pour la caractérisation des parois épaisses. L'objectif de cette étude est d'explorer des méthodes quantitatives innovantes de diagnostic thermique de l'enveloppe du bâtiment. Des mesures expérimentales ont été réalisées en laboratoire (à l’IFSTTAR à Nantes) et in situ (à l’IUT de Bordeaux). Différents capteurs et méthodes d'instrumentation ont été étudiés pour mesurer la densité de flux et la température de surfaces des parois, afin de procurer des recommandations pour le choix des capteurs ainsi que des protocoles de traitement de données. A partir des données mesurées (température et densité de flux des surfaces de l'enveloppe), trois approches numériques ont été proposées pour estimer des paramètres thermiques des parois multicouches épaisses : par méthode inverse, par réponse à un échelon et par réponse impulsionnelle. En outre, une méthode innovante non-destructive utilisant la rayonnement térahertz a été étudiée. Les mesures ont été effectuées au sein du laboratoire I2M. Cette méthode permet de caractériser le coefficient d'absorption des matériaux constructifs ordinaires comme isolation, plâtre, béton, bois… Elle pourrait postérieurement être combinée avec une méthode thermique pour apporter des informations complémentairesBuildings represent a large share in terms of energy consumption, such as 35% in the member countries of IEA (2010) and 39.8% in U.S. (2015). Climate controlling (space heating and space cooling) occupies more than half of the consumption. While this consumption can be reduced by improving the building energy efficiency, in which the thermal performance of building envelope plays a critical role. Therefore, the thermal diagnosis of building envelope is of great important, for example, in the case of new building accreditation, retrofitting energy efficiency of old building and the building resale and renting. However, very few diagnostic methods exist for the characterization of thick walls. The present measurement standards that based on steady state heat transfer regime need a long time (several days). The classical transient technologies, such as flash method, are difficult to implement on the walls because of the large thickness of walls and the complex conditions in situ. This thesis aims to explore innovative methodologies for thermal quantitative diagnosis of building envelope. Two experimental cases were carried out: one is in laboratory (IFSTTAR, Nantes) and the other is in situ (IUT, Bordeaux). Different sensors and instruments were studied to measure the wall heat flux and surface temperature, and provided some guidelines for the choice of sensors and data processing protocols as well. Using these measured data, three estimation approaches were proposed to estimate the thermal parameters of the multilayer thick wall: pulse response curve method, step response curve method and inverse method, which can be applied for different diagnostic situations. In addition, an innovative NDE (non-destructive evaluation) method using terahertz (THz) radiation was also investigated. Measurements were carried out in I2M laboratory to characterize the absorption coefficient of standard building materials (insulation, plaster, concrete, wood ...). This THz method can be combined with a previous thermal method to provide some complementary information
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(6594134), Jeremy M. Manheim. "MASS SPECTROMETRY IONIZATION STUDIES AND METHOD DEVELOPMENT FOR THE ANALYSIS OF COMPLEX MIXTURES OF SATURATED HYDROCARBONS AND CRUDE OIL". Thesis, 2020.
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Crude oil is a mixture of hydrocarbons so complex that it is predicted to comprise as many compounds as there are genes in the human genome. Developing methods to not only recover crude oil from the ground but also to convert crude oil into desirable products is challenging due to its complex nature. Thus, the petroleum industry relies heavily on analytical techniques to characterize the oil in reservoirs prior to enhanced oil recovery efforts and to evaluate the chemical compositions of their crude oil based products. Mass spectrometry (MS) is the only analytical technique that has the potential to provide elemental composition as well as structural information for the individual compounds that comprise petroleum samples. The continuous development of ionization techniques and mass analyzers, and other instrumentation advances, have primed mass spectrometry as the go-to analytical technique for providing solutions to problems faced by the petroleum industry. The research discussed in this dissertation can be divided into three parts: developing novel mass spectrometry-based methods to characterize mixtures of saturated hydrocarbons in petroleum products (Chapters 3 and 5), exploring the cause of fragmentation of saturated hydrocarbons upon atmospheric pressure chemical ionization to improve the analysis of samples containing these compounds (Chapter 4), and developing a better understanding of the chemical composition of crude oil that tightly binds to reservoir surfaces to improve chemically enhanced oil recovery (Chapter 6).
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Subramanyan, E. K. Ganapathy. "Escape Of High Mass Ions Due To Initial Thermal Energy And Its Implications For RF Trap Design". Thesis, 2010. http://etd.iisc.ernet.in/handle/2005/2015.
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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.
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Cheng, Wen-Zhang y 鄭文章. "Measurements of Quadrupople Coupling Constants in Liquids by NMR Relaxation Methods". Thesis, 1998. http://ndltd.ncl.edu.tw/handle/12427732949010059743.
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Futh, Susanne. "Entwicklung einer Methode mittels Gaschromatographie und gekoppeltem Triple-Quadrupol-Massenspektrometer zur Quantifizierung von Estrogen-Metaboliten in humanem Brustgewebe". Doctoral thesis, 2015. https://nbn-resolving.org/urn:nbn:de:bvb:20-opus-118808.
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Im Rahmen der Arbeit wurde eine Methode für die Quantifizierung von freiem 17β-Estradiol, Estron sowie der hydroxylierten und methylierten Metabolite im Brustgewebe entwickelt. Aufgrund der geringen Probengehalte erforderte dies eine gezielte Isolierung der Analyte aus der Probenmatrix sowie eine effektive Aufreinigung und Aufkonzentrierung, so dass eine Extraktion mit anschließender Festphasenextraktion durchgeführt wurde. Zudem wurde eine empfindliche Mess-Methode etabliert, welche auf Grundlage einer multi-reaction-monitoring-Methode, mittels Gaschromatographie und gekoppelten Triple-Quadrupol-Massenspektrometer, entwickelt wurde. Die Anwendbarkeit der Aufarbeitungs- und Mess-Methode wurde überprüft, indem diese auf 30 Realproben übertragen wurde. Dabei sind die ermittelten Gehalte mit den publizierten Daten der Gewebekonzentrationen von 17β-Estradiol, Estron und deren Metaboliten verglichen und Korrelationen mit ausgewählten Brustkrebs-begünstigenden Risikofaktoren betrachtet worden. Um ein quantitatives Metabolitenprofil von 17β-Estradiol, Estron und deren Metaboliten im Gewebe zu erstellen, wurden mit Hilfe einer multi-reaction-monitoring-Methode für alle Metabolite ein spezifischer Quanti- und Qualifier-Übergang etabliert. Durch die Optimierung der Ionisierungs- und Kollisionsenergien sowie der Initial-, Transferline- und Ionenquell-Temperatur beziehungsweise der dwell-time wurden Methoden- und Geräte-bedingte Empfindlichkeitsverluste so weit wie möglich reduziert, so dass maximale Signalintensitäten aller Quantifier-Übergänge gewährleistet waren. Zur gezielten Isolation sowie Aufreinigung und Anreicherung der Analyten,... ...so dass trotz der geringen Anzahl analysierter Gewebe-spenden der Einfluss des Body-Mass-Index und die Einnahme oraler Kontrazeptiva auf die Gehalte von 17β-Estradiol in der prämenopausalen Frau deutlich wurden. Die entwickelte Mess-Methode ermöglicht den routinemäßigen Einsatz für die Quantifizierung von freiem 17β-Estradiol, Estron und deren Methyl-Catecholen in humanem Brustgewebe. Beim Vergleich der berechneten Nachweisgrenzen von Catechol-Estrogenen mit Literaturangaben wurde herausgestellt, dass empfindlichere flüssigchromatographische Methoden als Methode der Wahl bei deren Analytik heranzuziehen sind. Die Übertragung der in Standardlösungen durchgeführten Versuche zur enzymatischen Hydrolyse von Glucuronid-und Sulfat-Konjugaten auf Gewebematrix stellt für weiterführende Arbeiten den entscheidenden Ansatzpunkt dar, um ein quantitatives Metabolitenprofil von freiem und gebundenem 17β-Estradiol, Estron und den Metaboliten in Brustgewebe erstellen zu könnenThe aim of the present work was to develop a method for the quantification of free estradiol, estrone, catechol estrogens and methylation products in breast tissue. Due to trace amounts in the samples it was necessary to isolate the analytes from the sample matrix, purify and concentrate them prior to tissue extraction and solid phase extraction. Additionally, a sensitive method of measurement based on multi reaction monitoring using gas chromatography and triple quadrupole mass spectrometry was developed. The applicability of the sample preparation and measurement method was tested in 30 tissue samples by comparing the measured levels with published data concerning concentrations of estradiol, estrone and their metabolites in breast tissue. Also it was necessary to find possible correlations between the analytes concentrations and selected risk factors for breast cancer. In order to develop a quantitative profile of estradiol, estrone and metabolites in tissue, qualifier and quantifier transitions were established using the multi reaction monitoring mode. By optimising the ionisation and collision energy, the initial, transferline and ion source temperatures and the dwell-time, it was possible to reduce the loss of sensitivity caused by both method and equipment and maximize the signal intensity of all quantifier transitions. For the isolation, purification and concentration of the analytes... ...have some influence on the levels of estradiol in premenopausal women. The developed measurement method enabled a routine usage for the quantification of free estradiol, estrone and methylcatechols in human breast tissue. The comparison between the calculated detection levels of catechol estrogens and the published data led to the conclusion that liquid chromatographic methods are more sensitive. The transference of these methods and experiments conducted, such as for the enzymatic hydrolysis of glucuronide- and sulfate-conjugates on tissue matrix in standard solution, seem to offer a starting point for future research projects. Especially, for the purpose of establishing a quantitative metabolite profile of free and conjugated estradiol, estrone and their metabolites
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(8054564), Katherine Elisabeth Wehde. "THE DEVELOPMENT OF MASS SPECTROMETRIC METHODS FOR THE DETERMINATION OF THE CHEMICAL COMPOSITION OF COMPLEX MIXTURES RELEVANT TO THE ENERGY SECTOR AND THE DEVELOPMENT OF A NEW DEVICE FOR CHEMICALLY ENHANCED OIL RECOVERY FORMULATION EVALUATION". Thesis, 2019.
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This dissertation focused on the development of mass spectrometric methodologies, separation techniques, and engineered devices for the optimal analysis of complex mixtures relevant to the energy sector, such as alternative fuels, petroleum-based fuels, crude oils, and processed base oils. Mass spectrometry (MS) has been widely recognized as a powerful tool for the analysis of complex mixtures. In complex energy samples, such as petroleum-based fuels, alternative fuels, and oils, high-resolution MS alone may not be sufficient to elucidate chemical composition information. Separation before MS analysis is often necessary for such highly complex energy samples. For volatile samples, in-line two-dimensional gas chromatography (GC×GC) can be used to separate complex mixtures prior to ionization. This technique allows for a more accurate determination of the compounds in a mixture, by simplifying the mixture into its components prior to ionization, separation based on mass-to-charge ratio (m/z), and detection. A GC×GC coupled to a high-resolution time-of-flight MS was utilized in this research to determine the chemical composition of alternative aviation fuels, a petroleum-based aviation fuel, and alternative aviation fuel candidates and blending components as well as processed base oils.
Additionally, as the cutting edge of science and technology evolve, methods and equipment must be updated and adapted for new samples or new sector demands. One such case, explored in this dissertation, was the validation of an updated standardized method, ASTM D2425 2019. This updated standardized method was investigated for a new instrument and new sample type for a quadrupole MS to analyze a renewable aviation fuel. Lastly, the development and evaluation of a miniaturized coreflood device for analyzing candidate chemically enhanced oil recovery (cEOR) formulations of brine, surfactant(s), and polymer(s) was conducted. The miniaturized device was used in the evaluation of two different cEOR formulations to determine if the components of the recovered oil changed.
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Gardner, Myles Winston. "Development of chromogenic cross-linkers and selective gas-phase dissociation methods to assess protein macromolecular structures by mass spectrometry". Thesis, 2009. http://hdl.handle.net/2152/ETD-UT-2009-12-513.
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Selective gas-phase dissociation strategies have been developed for the characterization of cross-linked peptides and proteins in quadrupole ion trap mass spectrometers. An infrared chromogenic cross-linker (IRCX) containing a phosphotriester afforded rapid differentiation of cross-linked peptides from unmodified ones in proteolytic digests of cross-linked proteins by selective infrared multiphoton dissociation (IRMPD). Only the cross-linked peptides containing the chromogenic phosphate underwent IRMPD and unmodified peptides were not affected by IR irradiation. IRMPD of IRCX-cross-linked peptides yielded uncross-linked y-ion sequence tags of the constituent peptides due to secondary dissociation of all primary product ions which contained the chromophore, thus allowing successful de novo sequencing of the cross-linked peptides.
Peptides cross-linked via a two-step conjugation strategy through the formation of a bis-arylhydrazone (BAH) bond were selectively dissociated by ultraviolet radiation at 355 nm. The BAH-cross-linked peptides could be distinguished from not only unmodified peptides but also dead-end modified peptides based on the selectivity of ultraviolet photodissociation. In a complementary approach, electron transfer dissociation of BAH-cross-linked peptides resulted in preferential cleavage of the hydrazone bond which produced two modified peptides. These modified peptides were subsequently interrogated by CID which allowed for the original site of cross-linking to be pinpointed.
IRMPD was implemented in a dual pressure linear ion trap to demonstrate successful photodissociation of peptides having modest absorptivities. Peptides were observed to efficiently dissociation by IR irradiation exclusively in the low pressure cell whereas no dissociation was observed in the high pressure cell due to extensive collisional cooling. IRMPD provided greater sequence coverage of the peptides than CID and yielded product ion mass spectra which were predominantly composed of singly charged product ions which simplified spectral interpretation. IRMPD was further applied for the sequencing of small-interfering RNA. Complete sequence coverage was obtained and the results were compared to CID.text
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Sonalikar, Hrishikesh Shashikant. "Numerical Investigation of Segmented Electrode Designs for the Cylindrical Ion Trap and the Orbitrap Mass Analyzers". Thesis, 2016. http://hdl.handle.net/2005/3075.
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This thesis is a numerical study of fields within ion traps having segmented electrodes1. The focus is on two cylindrical ion trap structures, two Orbit rap structures and one planar structure which mimics the field of the Orbit rap. In all these geometries, the segments which comprise the electrodes are easily Machin able rings and plates. By applying suitable potential to the different segments, the fields within these geometries are made to mimic the fields in the respective ideal structures.
This thesis is divided into 6 chapters.
Chapter 1 presents introduction and background information relevant to this work. A brief description of the Quadrupole Ion Trap (QIT) and the Orbit rap is given. The role of numerical simulations in the design of an ion trap geometry is briefly outlined. The motivation of this thesis is presented. The chapter ends by describing the scope of the thesis.
Chapter 2 presents a general description of computational methods used throughout this work. The Boundary Element Methods (BEM) is first described. Both 2D and 3D BEM are used in this work. The software for 3D BEM is newly developed and hence 3D BEM is described in more detail. A verification of 3D BEM is presented with a few examples. The Runge-Kutta method used to compute the trajectory of ion is presented. A brief overview of the Nelder-Mead method of function minimization is given. The computational techniques specifically used to obtain the results in Chapter 3, 4 and 5 are presented in the respective chapters.
Chapter 3 presents segmented electrode geometries of the Cylindrical Ion Trap (CIT). In these geometries, the electrodes of the CIT are split into number of mini-electrodes and different voltages are applied to these segmented electrodes to achieve the desired field. Two geometries of the segmented electrode CIT will be investigated. In the first, we retain the flat end cap electrodes of the CIT but split the ring electrode into five mini-rings. In the second configuration, we split the ring electrode of the CIT into three mini-rings and
1The term ‘segmented electrode’ used in this thesis has the same connotation as the term ‘split-electrode’ used in Sonalikar and Mohanty (2013). also divide the end caps into two mini-discs. By applying different potentials to the mini-rings and mini-discs of these geometries we will show that the field within the trap can be optimized to desired values. Two different types of fields will be targeted. In the first, potentials are adjusted to obtain a linear electric field and, in the second, a controlled higher order even multipole field are obtained by adjusting the potential. It will be shown that the different potentials to the segmented electrodes can be derived from a single RF generator by connecting appropriate capacitor terminations to segmented electrodes. The field within the trap can be modified by changing the value of the external capacitors.
Chapter 4 presents segmented electrode geometries which are possible alternatives for the Orbitrap. Two segmented-electrode structures, ORB1 and ORB2, to mimic the electric field of the Orbitrap, will be investigated. In the ORB1, the inner spindle-like electrode and the outer barrel-like electrode of the Orbitrap are replaced by rings and discs of fixed radii, respectively. In this structure two segmented end cap electrodes are added. In this geometry, different potentials are applied to the different electrodes keeping top-bottom symmetry intact. In the second geometry, ORB2, the inner and outer electrodes of the Orbitrap are replaced by an approximate step structure which follows the profile of the Orbitrap electrodes. For the purpose of comparing the performance of ORB1 and ORB2 with that of the Orbitrap, the following studies will be undertaken:
(1) variation of electric potential, (2) computation of ion trajectories, (3) measurement of image currents. These studies will be carried out using both 2D and 3D Boundary Element Method (BEM), the 3D BEM is developed specifically for this study. It will be seen in these investigations that ORB1 and ORB2 have performance similar to that of the Orbitrap, with the performance of the ORB1 being seen to be marginally superior to that of the ORB2. It will be shown that with proper optimization, geometries containing far fewer electrodes can be used as mass analysers. A novel technique of optimization of the electric field is proposed with the objective of minimizing the dependence of axial frequency of ion motion on the initial position of an ion. The results on the optimization of 9 and 15 segmented-electrode trap having the same design as ORB1 show that it can provide accurate mass analysis.
Chapter 5 presents a segmented electrode planar geometry named as PORB used to mimic the electric field of the Orbit rap. This geometry has two planes, each plane consisting of 30 concentric ring electrodes. Although the geometry of PORB does not have conventional inner and outer electrodes of the Orbit rap, it will be shown that by selecting appropriate geometry parameters and suitable potentials for the ring electrodes, this geometry can trap the ions into an orbital motion similar to that in the Orbit rap. The performance of the planar geometry is studied by comparing the variation of potential, ion trajectories and image current in this geometry with that in the Orbit rap. The optimization of applied potentials is performed to correct the errors in the electric field so that the variation of axial frequency of ions with their initial position is minimized.
Chapter 6 presents the summary and a few concluding remarks
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Kotana, Appala Naidu. "Numerical Studies of Axially Symmetric Ion Trap Mass Analysers". Thesis, 2017. http://etd.iisc.ernet.in/2005/3630.
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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.