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Finch, Jeffrey William. "Selective mass spectrometry by single-photon ionization from a molecular hydrogen laser source". Diss., The University of Arizona, 1992. http://hdl.handle.net/10150/185895.
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A molecular hydrogen laser, with an output of 7.8 eV photons in the vacuum ultraviolet, is evaluated as a selective source for photoionization mass spectrometry. Types of compounds ionized by the laser include a variety of amines, nitrogen heterocycles, drugs of abuse, pharmaceuticals, and polynuclear aromatic hydrocarbons (PAHS). The laser is coupled to a time-of-flight mass analyzer, which allows a spectrum to be recorded with each laser pulse. The laser is a "soft" ionization source and mass spectra of nearly all of the compounds studied yield single ion peaks due to the parent molecule with no fragments. This results in simplified mass spectra with a one-to-one correspondence of photoactive molecules with molecular ion peaks. Since the photoionization threshold of the laser is relatively low, selectivity of the photoactive species is high in the presence of a complex sample matrix. The performance of the laser source is improved with a few changes in the original design. In addition, the previous method of recording mass spectra with a photographic emulsion is replaced with a digital oscilloscope, which averages spectra over many laser pulses. As a result, a true assessment of the technique's sensitivity is finally achieved. The time-of-flight mass spectrometer is modified with a new microchannel plate ion detector and preamplifier. As a result, detection limits for PAH's improve by nearly three orders of magnitude, from the 100 ng range to the 100 pg range. Selectivity of the laser photoionization source in complex mixture analysis is demonstrated with the ability to detect PAH's in a drinking water sample at concentrations below 100 parts-per-trillion, using a simple solid-phase extraction technique. Application of the technique for rapid screening of drugs of abuse in urine is demonstrated where solid-phase extraction columns are utilized for sample pretreatment. Urine samples spiked with drugs such as cocaine, codeine, morphine, phencyclidine, and methadone, yield photoionization mass spectra consisting of parent molecular ions for the drugs with a few noninterfering ion signals from the matrix. The technique is evaluated and compared to other drug screening techniques such as enzyme-multiplied immunoassay.
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Chen, Yanfeng. "Analysis of Biological Molecules Using Stimulated Desorption Photoionization Mass Spectrometry". Diss., Georgia Institute of Technology, 2006. http://hdl.handle.net/1853/14620.
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Surface-assisted laser desorption/ionization mass spectrometry (SALDI MS) is a novel technique for direct analysis of organic and biological molecules. Amino acids, dipeptides, and organoselenium compounds were successfully detected by SALDI on carbon and silicon surfaces. Surface effects, solvent effects, temperature effects and pH effects were studied. A possible mechanism of SALDI is proposed based on observed results.
In general, stimulated desorption results in neutral yields that are much larger than ion yields. Thus, we have exploited and further developed laser desorption single photon ionization mass spectrometry (LD/SPI MS) as a means of examining biomolecules. The experimental results clearly demonstrate that LD/SPI MS is a very useful and fast analysis method with uniform selectivity and high sensitivity.
Selenium (Se) is an essential ultra-trace element in the human body. In efforts to obtain more useful information of selenium metabolites in human urine, mass determination of unknown organoselenium compounds in biological matrices using SALDI MS was investigated. In another approach, several selenium metabolites in human urine were successfully detected by LD/SPI MS. A HPLC-MS/MS method was also developed for a quantitative case study of selenium metabolites in human urine after ingestion of selenomethionine.
Low-energy electrons (LEE, 3-20 eV) have been shown to induce single and double strand breaks (SSB and DSB) in plasmid DNA. To understand the genotoxic effects due to secondary species of high-energy radiation, we investigate the role of transient negative ions and the specificity in LEE-DNA damage by examining the neutral product yields using low electron stimulated dissociation SPI MS. The neutral yields as a function of incident electron energy are also correlated with the SSBs and DSBs measured using post-irradiation gel electrophoresis. The results provide further insight concerning the mechanisms of LEE-induced damage to DNA.
Overall, this research provided an in-depth understanding of non-thermal surface processes and the development of new mass spectrometric techniques for the analysis of biomolecules.
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Burns, Kimberly Ann. "Coupled multi-group neutron photon transport for the simulation of high-resolution gamma-ray spectroscopy applications". Diss., Atlanta, Ga. : Georgia Institute of Technology, 2009. http://hdl.handle.net/1853/29737.
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Thesis (Ph.D)--Mechanical Engineering, Georgia Institute of Technology, 2010.Committee Chair: Hertel, Nolan; Committee Member: Kulp, William David; Committee Member: Lee, Eva; Committee Member: Pagh, Richard; Committee Member: Petrovic, Bojan; Committee Member: Rahnema, Farzad; Committee Member: Smith, Eric; Committee Member: Wang, Chris. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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Knie, André [Verfasser]. "Photon induced inner-shell excitation processes of nitrous oxide probed by angle resolved fluorescence and Auger-Electron spectrometry / André Knie". Kassel : Kassel University Press, 2013. http://d-nb.info/1056946180/34.
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Ben, Ltaief Ltaief [Verfasser]. "Interatomic Coulombic decay in noble gas clusters of varying sizes investigated by photon-induced (dispersed) fluorescence spectrometry / Ltaief Ben Ltaief". Kassel : Universitätsbibliothek Kassel, 2018. http://d-nb.info/1162155019/34.
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Habib, Amr. "Détecteurs radiologiques grande surface, multi-énergie". Thesis, Grenoble, 2014. http://www.theses.fr/2014GRENT055.
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L'objectif de la thèse est de proposer une solution pour un circuit intégré matriciel pour l'imagerie de rayons X fonctionnant, soit en mode spectrométrique où l'énergie de chaque photon X est mesurée, soit en mode d'intégration de charges où l'énergie totale déposée par les rayons X pendant une image est mesurée, la solution devant être à terme compatible avec un détecteur de grande surface typiquement de 20 cm x 20 cm. Un circuit de test (ASIC), ‘Sphinx' de 20 x 20 pixels au pas de 200 µm x 200 µm, en technologie CMOS 0.13 µm a été conçu pour servir de preuve du concept proposé. L'architecture de pixel retenue permet la quantification de la charge incidente par des paquets de contre-charges aussi bas que 100 électrons, ces contre-charges étant comptabilisées, soit pour chaque photon X (mode spectrométrique), soit pour la totalité des photons détectés pendant une image (mode intégration). Les premières mesures de caractérisation prouvent la validité du concept avec de bonnes performances en termes de consommation, bruit et linéarité. Une partie des pixels est dédiée à la détection directe des rayons X, ceux-ci étant alors convertis en charges électriques dans un semi-conducteur, tel que CdZnTe par exemple, lequel semiconducteur est couplé pixel à pixel à l'ASIC. Une autre partie des pixels est dédiée à la détection indirecte des rayons X, ceux-ci étant alors convertis en photons visibles dans une couche scintillatrice, telle CsI : Tl par exemple, et chaque pixel de l'ASIC possédant alors une photodiode. Pour ce dernier mode, de nouvelles formes de photodiodes rapides et peu capacitives ont de plus été conçues, simulées, et fabriquées en technologie CMOS 0.13 µm sur un autre ASIC. Enfin, la thèse se conclut en proposant des idées d'amélioration de performances à réaliser potentiellement dans un futur prototypeThe objective of the thesis is to propose a solution for a 2D integrated circuit X-ray imager working, either in spectrometric mode where each X photon energy is measured, or in charge integration mode where the total energy deposited by X-ray during an image is measured, the solution being compatible with large area detectors typically of 20 cm x 20 cm. A proof of concept prototype ASIC 'Sphinx' was designed and fabricated in CMOS 0.13 µm technology; the ASIC being formed of a matrix of 20 x 20 pixels with a 200 µm pixel pitch. The designed architecture allows the quantification of the incoming charge through the use of counter-charge packets as low as 100 electrons. The injected packets are counted for each X photon (in the spectrometric photon counting mode), or for all charges integrated during the image period (in charge integration mode). First characterization measurements prove the validity of the concept with good performance in terms of power consumption, noise, and linearity. A first part of the ASIC is dedicated to X-ray direct detection where a semiconductor, e.g. CdZnTe, hybridized to the ASIC's pixels converts X-photons to electrical charge. Another part of the ASIC is dedicated indirect X-ray detection where a scintillator, e.g. CsI:Tl, is used to convert X-photons to visible photons which are then detected by in-pixel photodiodes. For the latter mode, new forms of photodiodes characterized by fast detection and low capacity were designed, simulated, and fabricated in CMOS 0.13 µm technology on a different ASIC. Finally, the thesis concludes with proposing performance enhancing ideas to be potentially implemented in a future prototype
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Varga, János [Verfasser], e Armin [Akademischer Betreuer] Reller. "Application of Thermal Analysis: Single Photon Ionization Time-of-Flight Mass Spectrometry for Studies of Inorganic Clusters and Ionic Liquids / János Varga ; Betreuer: Armin Reller". Augsburg : Universität Augsburg, 2017. http://d-nb.info/114105390X/34.
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Nazih, Abdelhamid. "Applications de la spectroscopie par corrélation de photons à : 1) la granulométrie des imbrûlés : 2) la vélocimétrie". Rouen, 1989. http://www.theses.fr/1989ROUES030.
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Mesure de la distribution granulométrique de particules de suies dans un tunnel de dilution. Application d'une méthode vélocimétrique basée sur l'annulation de la fonction de corrélation de l'intensité à des temps finis. Bon accord des résultats expérimentaux et des prévisions théoriques
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Zahir, Mostafa Lokman. "Nouvelles références en énergie X et gamma inférieures à 100 keV établies à l'aide de calorimètres magnétiques ultra haute résolution". Electronic Thesis or Diss., université Paris-Saclay, 2024. http://www.theses.fr/2024UPASP125.
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Les raies X et gamma émis par des radionucléides peuvent être utilisées pour étalonner l'échelle en énergie des détecteurs à dispersion d'énergie. C'est le cas notamment pour les détecteurs cryogéniques qui offrent une excellente résolution, mais présentent des non-linéarités qu'il faut corriger. Afin d'étalonner ces détecteurs avec précision en dessous de 200 keV, il est nécessaire de disposer de rayons X et gamma ayant une incertitude de l'ordre de 0,1 eV. Or, les énergies des photons gamma recommandées respectant ce critère sont rares ou basées sur une seule mesure expérimentale. L'objectif principal de cette thèse est de mesurer avec une excellente résolution des photons gamma en dessous de 200 keV pour améliorer les incertitudes sur leurs énergies à environ 0,1eV. Pour répondre à cet objectif, un nouveau détecteur cryogénique a été conçu. C'est un calorimètre métallique magnétique (Metallic Magnetic Calorimeter, MMC) doté de huit absorbeurs en or de 50 µm d'épaisseur sur une surface totale de 8,4 mm². Un montage a été réalisé pour accueillir quatre puces MMC, deux puces SQUID assurant la lecture des MMC et les circuits imprimés pour les connecter aux câbles du réfrigérateur à dilution qui sert à les refroidir à leur température de fonctionnement autour de 15 mK. De plus, le montage comporte un passeur cryogénique de sources radioactives, spécialement réalisé pour fonctionner à très basse température et pouvoir mesurer jusqu'à quatre sources séquentiellement. Les sources mesurées sont des mélanges de plusieurs radionucléides : trois radionucléides étalon utilisés pour corriger la non-linéarité du MMC (169Yb, 57Co et 153Gd) et sept radionucléides pour mesurer leurs énergies X et gamma avec une très faible incertitude (109Cd, 133Ba 155Eu, 210Pb, 239Np, 241Am et 243Am). Les mélanges entre radionucléides ont été choisis par simulations Monte Carlo pour minimiser les interférences spectrales. L'169Yb a été produit par irradiation d'une feuille de thulium avec des deutérons auprès du cyclotron Arronax.Deux sessions de mesure indépendantes sur deux lots de quatre sources ont été effectuées à environ 16 mK, avec des conditions de régulation de température différentes. La résolution en énergie du détecteur est de 15 eV à 36 eV entre 0 keV et 200 keV. La non-linéarité de chaque absorbeur a été corrigée avec les raies des radionucléides étalons et un polynôme de second degré. Les énergies X et gamma mesurées ont été analysées et combinées par différentes méthodes. Quelle que soit la session de mesure et la méthode d'analyse utilisée, les énergies obtenues sont cohérentes entre elles, seules les incertitudes diffèrent. Au final, les énergies de 15 raies gamma ont été mesurées et pour 14 d'entre elles, l'incertitude obtenue, environ 0,2 eV, est plus faible que celle des valeurs recommandées. Huit énergies de photons X Kα ont également été mesurées ; pour ces raies mieux connues, un très bon accord est observé avec les valeurs recommandées, validant ainsi la méthodologie utiliséeThe X and gamma rays emitted by radionuclides can be used to calibrate the energy scale of energy-dispersive detectors. This is particularly the case for cryogenic detectors, which offer excellent resolution but have non-linearities that need to be corrected. In order to calibrate these detectors accurately below 200 keV, it is necessary to have X-rays and gamma rays with an uncertainty of the order of 0.1 eV. However, recommended gamma-ray photon energies meeting this criterion are rare or based on a single experimental measurement. The main objective of this thesis is to measure gamma photons below 200 keV with excellent resolution in order to improve the uncertainties on their energies to around 0.1 eV. To meet this objective, a new cryogenic detector has been designed. It is a Metallic Magnetic Calorimeter (MMC) with eight 50 µm-thick gold absorbers covering a total surface area of 8.4 mm². An assembly was built to house: four MMC chips, two SQUID chips for reading-out the MMCs, and the printed circuits to connect them to the cables of the dilution refrigerator. The set-up also includes a cryogenic radioactive source sampler, specially designed to operate at very low temperatures and to measure up to four sources sequentially. The sources measured are mixtures of several radionuclides: three standard radionuclides used to correct the non-linearity of the MMC (169Yb, 57Co and 153Gd) and seven radionuclides used to measure their X and gamma energies with very low uncertainty (109Cd, 133Ba, 155Eu, 210Pb, 239Np, 241Am and 243Am). Mixtures of radionuclides in the sources were chosen by Monte Carlo simulations to minimise spectral interference. Ytterbium-169 was produced by irradiating a thulium foil with deuterons at the Arronax cyclotron.Two independent measurement sessions on two set of four sources were carried out at around 16 mK during two weeks, with different temperature control conditions. The energy resolution of the detector is 15 eV to 36 eV for gamma-rays between 0 keV and 200 keV. The non-linearity of each absorber was corrected using the lines of the standard radionuclides and a second-degree polynomial. The X-ray and gamma-ray energies measured were analysed and combined using various methods. Regardless ofthe measurement session and analysis method used, the energies obtained are consistent with each other, with only the uncertainties differing. In the end, the energies of 15 gamma-ray lines were measured and for 14 of them, the uncertainty obtained, around 0.2 eV, is lower than the recommended values. Eight Kα X-ray photon energies were also measured; for these well-known lines, very good agreement was observed with the recommended values, thus validating the methodology used in the work presented
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Adam, Thomas [Verfasser], Ralf [Akademischer Betreuer] Zimmermann, Antonius [Akademischer Betreuer] Kettrup e Harun [Akademischer Betreuer] Parlar. "Investigation of Tobacco Pyrolysis Gases and Puff-by-puff Resolved Cigarette Smoke by Single Photon Ionisation (SPI) – Time-of-flight Mass Spectrometry (TOFMS) / Thomas Adam. Gutachter: Antonius Kettrup ; Harun Parlar. Betreuer: Ralf Zimmermann". München : Universitätsbibliothek der TU München, 2006. http://d-nb.info/1058140760/34.
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Pearson, Wright L. "The use of infrared multiple photon dissociation and Fourier transform ion cyclotron resonance mass spectrometry to study the thermochemical dynamics of dephosphorylation and the spectral and density functional theory determined structural characteristics of monosaccharide isomers". [Gainesville, Fla.] : University of Florida, 2009. http://purl.fcla.edu/fcla/etd/UFE0024272.
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Wang, Shih-fan. "Synthesis and Characterization of Surface Relaxations of Macrocyclic Polystyrenes and Interfacial Segregation in Blends with Linear Polystyrenes". University of Akron / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=akron1322506008.
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Sidorova, Mariia. "Timing Jitter and Electron-Phonon Interaction in Superconducting Nanowire Single-Photon Detectors (SNSPDs)". Doctoral thesis, Humboldt-Universität zu Berlin, 2021. http://dx.doi.org/10.18452/22296.
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Die vorliegende Doktorarbeit beschäftigt sich mit der experimentellen Studie zweier miteinander verbundener Phänomene: Dem intrinsischen Timing-Jitter in einem supraleitendenden Nanodraht-Einzelphotonen-Detektor (SNSPD) und der Relaxation der Elektronenenergie in supraleitenden Filmen. Supraleitende Nanodrähte auf einem dielektrischen Substrat als mikroskopische Grundbausteine jeglicher SNSPDs stellen sowohl für theoretische als auch für experimentelle Studien komplexe Objekte dar. Die Komplexität ergibt sich aus der Tatsache, dass SNSPDs in der Praxis stark ungeordnete und ultradünne supraleitende Filme verwenden, die eine akustische Fehlanpassung zu dem zugrundeliegenden Substrat aufweisen und einen Nichtgleichgewichts-Zustand implizieren. Die Arbeit untersucht die Komplexität des am weitesten in der SNSPD Technologie verbreiteten Materials, Niobnitrid (NbN), indem verschiedene experimentelle Methoden angewandt werden. Als eine mögliche Anwendung der SNSPD-Technologie wird ein Prototyp eines dispersiven Raman-Spektrometers mit Einzelphotonen-Sensitivität demonstriert.This Ph.D. thesis is based on the experimental study of two mutually interconnected phenomena: intrinsic timing jitter in superconducting nanowire single-photon detectors (SNSPDs) and relaxation of the electron energy in superconducting films. Microscopically, a building element of any SNSPD device, a superconducting nanowire on top of a dielectric substrate, represents a complex object for both experimental and theoretical studies. The complexity arises because, in practice, the SNSPD utilizes strongly disordered and ultrathin superconducting films, which acoustically mismatch with the underlying substrate, and implies a non-equilibrium state. This thesis addresses the complexity of the most conventional superconducting material used in SNSPD technology, niobium nitride (NbN), by applying several distinct experimental techniques. As an emerging application of the SNSPD technology, we demonstrate a prototype of the dispersive Raman spectrometer with single-photon sensitivity.
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Lavanchy, Nicole. "Le métabolisme énergétique du myocarde isolé de rat : la situation ischémique abordée par la spectroscopie de résonance magnétique nucléaire (RMN)". Grenoble 1, 1987. http://www.theses.fr/1987GRE10055.
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Mozharov, Sergey. "Developments in photonic systems for Raman spectrometry in microreactors". Thesis, University of Strathclyde, 2010. http://oleg.lib.strath.ac.uk:80/R/?func=dbin-jump-full&object_id=14493.
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Odeneye, Michael Adetunji. "Infrared photodissociation of gas phase ions : single photon and multiphoton events". Thesis, University of Sussex, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.311414.
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Roos, Andreas. "Single photon double valence ionization of methyl monohalides". Thesis, Uppsala universitet, Molekyl- och kondenserade materiens fysik, 2014. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-239195.
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This thesis is based on experimental results from measurements on methyl halides at a photon energy corresponding to the He IIβ emission line. Double ionization processes involving the valence electrons of the molecules CH3F, CH3Cl and CH3I are studied by means of a magnetic bottle TOF-PEPECO spectrometer. Resulting double ionization data of these molecules suggest that mainly direct double photoionization is observed as a continuous energy sharing between the ejected electron pairs. As a mean to further understand the double ionization processes, a "rule of thumb", for double ionization in molecules, is applied to the data presented in the double ionization spectra. This is done in order to quantify the effective distance between the two vacancies created in the dications. It is found that the distance between the vacancies may be related to the bond distance between the carbon and halogen atoms. Further investigations call for quantum chemical calculations to scrutinize this hypothesis.Det här examensarbetet är baserat på experimentella fotojonisations studier av metyl halider vid en fotonenergi motsvarande He IIβ emissionslinjen. Valenselektronerna i dubbeljonisations processerna för CH3F, CH3Cl och CH3I har studerats under användning av en så-kallad magnetisk flask TOF-PEPECO spektrometer. Resultaten av dessa mätningar visar att mestadels direkt dubbeljonisation processer före- kommer, där elektronerna delar kontinuerligt på energin som friges vid jonisationen. Den dubbla jonisa- tions processen är ytterligare studerad genom att tillämpa en tumregel för dubbeljonisation i molekyler, vilket ger en indikation av hur stort avståndet är mellan de två vakanserna som skapades när molekylerna joniserade. Resultaten från tumregeln visar att avståndet mellan vakanserna kan vara relaterade till bind- ningsavståndet mellan kol-atomen och halogen-atomen, i respektive metyl halogen. För att ytterligare bekräfta dubbeljonisations processerna i dessa molekyler, krävs kvantmekaniska beräkningar.
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Ottewell, P. "Inclusive photoproduction of phi mesons by photons of energy 70-170 GeV at the Omega Spectrometer with a ring imaging Cerenkov detector". Thesis, University of Manchester, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233386.
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Gabrielyan, Marianna. "RELATIVE ENERGY CALIBRATION OF THE TJNAF HALL-B PHOTON TAGGER AND INVESTIGATION OF LIMITATIONS OF THE PHOTON TAGGING TECHNIQUE". UKnowledge, 2006. http://uknowledge.uky.edu/gradschool_theses/405.
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In this work we report on two sets of measurements involving the Hall-B photon tagging system of the Tomas Jefferson National Accelerator Facility. The relative energy calibration of the tagging counters was performed by using the PrimEx pair spectrometer and a series of high position resolution micro-strip detectors. The photon energies were determined by forming coincidence between the tagger and the e+ e- pairs for several values of the pair spectrometer magnetic field between 0.36T to 1.9T (total of 180 fields). The second set of measurements, collected in conjunction with the Fall 2004 PrimEx run, investigated inherent limitations on the photon tagging technique. We report for the first time an experimental signature for these effects.
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Simpson, Matthew James. "Ion-molecule reaction mass spectrometry and vacuum-ultraviolet negative photoion spectroscopy". Thesis, University of Birmingham, 2010. http://etheses.bham.ac.uk//id/eprint/1056/.
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Two separate experimental techniques have been used to investigate the fundamental properties of small polyatomic molecules in the gas phase. Selected ion flow tube mass spectrometry has been used to study the reactions of cations and anions with ethene, monofluoroethene, 1,1-difluoroethene, trifluoroethene and tetrafluoroethene. Calculated collisional reaction rate coefficients are compared to those measured by the experiment. The product ions from these reactions have been detected and their branching ratios measured. Many of these results have been explained using arrow-pushing mechanisms. Using tunable vacuum-ultraviolet radiation from a synchrotron, negative ions have been detected following photoexcitation of 24 gaseous molecules. The majority of the molecules studied are halogen-substituted methanes. Product anions resulting from unimolecular ion-pair dissociation reactions were detected, and their ion yields recorded in the range 8-35 eV. Absolute cross sections for ion-pair formation and resulting quantum yields are calculated. This vast collection of data is summarised and ion-pair formation from polyatomic molecules is reviewed.
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Rimal, Dipak. "PROTON FORM FACTOR PUZZLE AND THE CEBAF LARGE ACCEPTANCE SPECTROMETER (CLAS) TWO-PHOTON EXCHANGE EXPERIMENT". FIU Digital Commons, 2014. http://digitalcommons.fiu.edu/etd/1211.
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Bindel, Richard Thomas. "Elliptic flow measured with the PHOBOS spectrometer at RHIC". College Park, Md. : University of Maryland, 2008. http://hdl.handle.net/1903/8546.
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Thesis (Ph. D.)--University of Maryland, College Park, 2008.Thesis research directed by: Dept. of Chemistry and Biochemistry. Title from t.p. of PDF. Includes bibliographical references. Published by UMI Dissertation Services, Ann Arbor, Mich. Also available in paper.
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Simon, Anne-Laure. "Couplage de la spectrométrie de mobilité ionique et de la spectroscopie optique : études conformationnelles en phase gazeuse". Thesis, Lyon, 2016. http://www.theses.fr/2016LYSE1128/document.
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Cette thèse porte sur le développement d'un appareil couplant la spectrométrie de masse avec la spectrométrie de mobilité ionique et la spectroscopie laser, dans le but d'effectuer des analyses conformationnelles sur des édifices biomoléculaires. La construction, la mise au point et l'optimisation de l'appareil font l'objet de la première partie de ce mémoire. En particulier, il s'est agi de déterminer les caractéristiques de l'appareil (résolution, fréquence de fonctionnement…) par une série de tests sur des systèmes modèles. Dans un deuxième temps, nous avons effectué des mesures de spectroscopie d'action sur des conformères sélectionnés en mobilité. Nous avons étudié la relation entre la conformation et les propriétés optiques d'un système en mesurant le photo-détachement d'électron de divers conformères sélectionnés. Dans le cadre de la spectroscopie d'action, nous avons utilisé les possibilités nouvelles offertes par l'appareil pour réaliser des expériences de photo-isomérisation cis-trans sur des complexes non-covalents. Sur cet exemple, nous avons montré l'intérêt de cet appareil pour mesurer des spectres d'action de photo-isomérisation. Et enfin, nous avons montré la possibilité de réaliser des mesures de spectroscopie d'action basée sur le Transfert d'Energie par Résonance de Förster (FRET), en phase gazeuse, résolu en conformationThis thesis deals with the development of a new instrument coupling mass spectrometry, ion mobility spectrometry and laser spectroscopy. The aim is to perform structural analysis on biomolecular systems.The first part of this thesis focuses on the construction, the development and the optimization of the set-up. The main point was to determine the features of the set-up (resolution, working frequency) by series of tests with model systems.In a second phase, we did conformer resolved action spectroscopy. We studied the relation between the conformation and the optical properties of one system by measuring photo- electron detachment on different selected conformers. In the framework of action spectroscopy we used the new capacity of the set-up to perform cis-trans photo-isomerization on non-covalent complexes. We showed with this example interest of the use of this instrument to measure photo-isomerization action spectra. We finally showed the possibility to perform conformer resolved action spectroscopy measurements based on Förster Resonance Energy Transfer (FRET) in the gas phase
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Niccolai, Silvia. "Three-body Forces in Photoreactions on 3He". Washington, D.C : Oak Ridge, Tenn. : United States. Dept. of Energy. Office of Energy Research ; distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2003. http://www.osti.gov/servlets/purl/824932-PJ4Kr6/native/.
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Thesis; Thesis information not provided; 1 Feb 2003.Published through the Information Bridge: DOE Scientific and Technical Information. "JLAB-PHY-03-39" "DOE/ER/40150-2763" Silvia Niccolai. 02/01/2003. Report is also available in paper and microfiche from NTIS.
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Nottingham, Mark. "Resonance photo-ionisation mass spectrometry techniques for the analysis of heavy noble gas isotopes in extra-terrestrial samples". Thesis, University of Manchester, 2017. https://www.research.manchester.ac.uk/portal/en/theses/resonance-photoionisation-mass-spectrometry-techniques-for-the-analysis-of-heavy-noble-gas-isotopes-in-extraterrestrial-samples(93bc14bd-d13f-4d91-ad16-e264754a6e79).html.
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The field of noble gas mass spectrometry is a rapidly developing one. There is a sustained requirement for continuous development of instrumentation in order to allow researchers to answer critical questions facing their respective fields. Within planetary science, the question of whether our solar system is 'typical', has been a driving force behind many lines of research. This project sought to build upon the strong instrumental base of the Isotope Geochemistry and Cosmochemistry group of the University of Manchester, in order to develop the Resonance Ionisation Mass Spectrometer for Krypton Isotopes. From that basis, it then sought to develop techniques and protocols for the analysis of extra-terrestrial samples, particularly those of very low mass. The thesis is broken down into three studies. The first involved the development of the mechanisms used to fill the Xe-Ar four-wave mixing cell. This section covers the development, implementation, and characterisation of the newly installed mass flow controllers. The additional control over the mixing ratio granted allowed an eightfold increase to the sensitivity of the instrument. The reproducibility of the gas ratio is consistently shown throughout, and has ultimately reduced the tuning time of the instrument from a number of weeks to a day. The second section details the required procedures involved in data reduction, and the development of protocols and software for the RIMSKI instrument. A range of approaches are assessed, including a novel approach to cosmic ray exposure age calculations. The methods are discussed and implemented on extra-terrestrial samples, the Stannern eucrite and the Bereba eucrite. Finally, the analytical limits of the RIMSKI instrument are expanded via the measurement of the krypton systems of individual calcium-aluminium-rich inclusions. It is observed that Allende CAIs show a trapped component, Br-derived Kr, as well as an anomalous 'heavy Kr' component (one that is enriched in 86Kr). It is additionally noted that there is a lack of cosmogenic krypton to be found in all but one of the measured inclusions. The implications of these findings are discussed.
26
Langot, Pierre. "Etude femtoseconde de la thermalisation des porteurs libres dans l'arseniure de gallium". Palaiseau, Ecole polytechnique, 1996. http://www.theses.fr/1996EPXX0021.
Texto completo da fonteResumo:
Ce travail porte sur l'etude des interactions porteur-porteur et porteur-phonon dans l'arseniure de gallium par des techniques pompe-sonde de saturation d'absorption femtoseconde a haute sensibilite. Pour cela, une source femtoseconde a deux couleurs a ete developpee par conversion de frequence non-lineaire des impulsions fournies par un oscillateur femtoseconde a saphir dope titane. Nous avons tout d'abord etudie les mecanismes d'interaction des trous libres dans l'asga. Les mesures realisees sur l'echauffement de trous froids en fonction de la densite de porteurs photo-generes, de leur exces d'energie initial et de la temperature du reseau nous ont permis de mesurer directement le temps d'interaction trou-phonon et d'en deduire le potentiel de deformation optique. Une etude sur le ralentissement de la thermalisation electron-reseau du a la creation d'une population de phonons hors equilibre en centre de zone de brillouin est ensuite presentee. Les differentes mesures que nous avons realisees nous ont permis de demontrer que la thermalisation electrons-reseau aux temps longs est gouvernee par la duree de vie des phonons optiques, en accord avec un modele de simulations numeriques
27
Kosev, Krasimir. "A High-Resolution Time-of-Flight Spectrometer for Fission Fragments and Ion Beams". Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2008. http://nbn-resolving.de/urn:nbn:de:bsz:14-ds-1224498377426-87820.
Texto completo da fonteResumo:
1. A quantitive understanding of the nucleosynthesis process requires the knowledge of the production rates, the masses and the ?-decay characteristics of exotic neutron-rich nu- clei. Nuclear fission is a suitable method of producing such nuclei with masses from 60 - 150. Neutron-rich nuclei close to the r-process path can be produced via photo-fission at the Rossendorf superconducting linear accelerator of high brilliance and low emittance (ELBE) or by means of nuclear reactions at relativistic energies (for example at GSI). If the fission prod- ucts are identified and also their charge numbers are obtained, it will be principally possible to investigate their structure by means of beta-gamma spectroscopy. 2. For the purpose of fission-fragment detection a double time-of-flight (TOF) spectrometer has been developed. The key component of the TOF spectrometer is a TOF detector consisting of multichannel-plate (MCP) detectors with a position-sensitive readout, a foil for secondary electron (SE) production and an electrostatic mirror. The fission fragments are detected by measuring the SEs impinging on the position-sensitive anode after emission from the foil, ac- celeration and deflection by the electrostatic mirror. 3. In the first part of the work, special attention is paid to the relevant methods of building a spectrometer of such type. The functionality of the different detector components is proven in detail. A unique method for the determination of the SE foil thickness with ?-particles is pre- sented. Values for the mirror transmission and scattering are deduced. A dedicated SIMION 3D simulation showed that introducing serpentine like wires with pitch distance of 1 mm is capable of providing transparency of more than 90% without significant impact on the time resolution. 4. Since the performance of the MCP detectors is crucial, optimised schemes for their high- voltage supplies have been implemented successfully. Further enhancement of the setup was achieved by introducing surface-mount device (SMD) elements for signal decoupling, positioned close to the detector surface. Thus, we succeeded in avoiding signal deterioration coming from the additional capacitances and inductivities caused by extra cable lengths. Because the MCP signal decoupling takes place by means of rings with not well-defined impedance, impedance- matching problems arise, causing signal ringing and distortion. An approach towards solving this problem was to build a special fast, wide-band transimpedance amplifier. Using its circuit mounted close to the detectors, a significant reduction of the signal ringing was observed while maintaining the rise time of the detector signal. In order to process the multichannel-plate de- tector signals optimally, a new state-of-the-art constant-fraction discriminator (CFD) based on the amplitude and rise time compensated (ARC) technique with very low threshold capabilities and optimised walk properties has been developed and incorporated into the setup. 5. In our first laboratory test measurements conducted with an ?-particle source, we demonstrated ability of the setup to resolve pattern images placed directly in front of the MCP detector or reflected by the electrostatic mirror. The obtained position resolution for the second case is in the order of 2 mm. We showed that the detection efficiency of the system for ions like He is less than 30 %. This is mainly due to the low number of the electrons liberated from the SE foil. In a setup consisting of two mirror MCP detectors, we could successfully observe the TOF spectrum of a mixed (226Ra, 222Rn, 210Po, 218Po, 214Po) ?-source and found a good agreement with a SRIM simulation. 6. Measurements performed at the FZ Dresden-Rossendorf 5 MV tandem accelerator en- abled us to learn more about the response of the TOF detectors to various beams of heavy ions. The first in-beam experiments clearly showed that the applied setup consisting of two mirror detectors is capable of resolving different 35Cl beam charge states. In a combination with the specially designed wide-band amplifier and dedicated CFDs based on the ARC technique, we managed to achieve an in-beam time resolution of 170 ps per TOF detector. Measurements with ions of Z > 30 resulted in detection efficiencies of greater than 90%. At foil accelerating potentials approximately two times larger than the mirror deflection voltage, most of the SEs gain enough energy to pass through the electrostatic mirror without being deflected towards the MCP surface. Thus, an abrupt drop of the efficiency curve was observed - the “transparent” mode of the mirror. 7. Properties of electrons ejected from thin foils from heavy ions have been also investigated. From the MCP pulse-height-distribution spectra, a number for the forward-emitted SEs ejected by 35Cl beam was deduced. A method for obtaining widths of the SE energy distributions from the drop of the efficiency curve for various ions has been proposed. Assuming that the efficiency curve as a function of the accelerating voltage follows an error function, its standard deviation gives the standard deviation of the SE energy distribution. Another method based on the TOF technique for reconstructing the secondary electron velocity and energy distribution was also invented. It was found that the resulting mean SE velocity closely approaches the one of the beam ions. This phenomenon was attributed to the so-called “convoy” electrons. 8. The obtained position resolution for beams like 35Cl, 79Br and 107Ag at stable detection efficiency was better than 1.8 mm. It was demonstrated that with increasing the foil accelerat- ing voltage, the position resolution improves due to the minimised SE angular spread. Such a mode of operation was favoured until the mirror “semi-transparency” regime was reached, after which increasing further the accelerating potential could lead to a position resolution worsen- ing. An explanation of the fact could be the deterioration of the anode timing signals or some defocusing effects arising from the mirror wires field at high accelerating voltages. 9. Testing photo-fission experiments were performed at the bremsstrahlung facility at the ELBE accelerator. For the first time a spectrometer of this kind was successfully employed for bremsstrahlung-induced photo-fission measurements. The setup consisted of two mirror detectors (first arm) and a 80 mm diameter MCP detector (second arm) with a 238U target positioned in between. TOF measurements with two bremsstrahlung end-point energies of 12.9 and 16.0 MeV were carried out. A clear cut separation of the TOF peaks for the medium- mass and heavy fission fragments was observed. At these experimental test runs, we did not aim at one-by-one fission fragment mass resolution, since this may be the purpose of a more specific experiment utilising a much thinner fissile source than the one applied here (minimum straggling of the fragments inside the target is required) and considerably better statistics. It was possible to estimate the photo-fission production rate for the two measuring cases and to compare the obtained results with data from other measurements.
28
Narreddula, Venkateswara Reddy. "Development of novel derivatization reagents for analysis of isomeric fatty acids by liquid chromatography-mass spectrometry". Thesis, Queensland University of Technology, 2020. https://eprints.qut.edu.au/136811/1/Venkateswara%20Reddy_Narreddula_Thesis.pdf.
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This project was a step forward in 'developing next-generation derivatization reagents for photodissociation mass spectrometry', an emerging mass spectrometry activation method for structural elucidation of lipid biomolecules. The method involves synthesis of photo labile derivatization reagents, derivatization with fatty acids and photodissociation of derivatives using 266 nm laser to elucidate subtle features of fatty acids. The thesis investigated the utility of fixed charge photo labile derivatives for identifying unusual fatty acids from lipid extract of vernix caseosa, and optimization of photodissociation efficiency of photolabile derivatives under 266 nm irradiation.
29
Lalande, Mathieu. "Processus induits par l'irradiation de modèles peptidiques de la triple hélice du collagène en phase gazeuse". Thesis, Normandie, 2018. http://www.theses.fr/2018NORMC235/document.
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Le collagène est la protéine la plus abondante dans les mammifères, et le constituant principal de la matrice extracellulaire du cartilage. Les propriétés mécaniques de ce tissu sont dues à la structure particulière du collagène : la triple hélice. Lors de cette thèse, nous nous sommes intéressés à des peptides modèles de la triple hélice du collagène en phase gazeuse, ce qui permet l’étude de leurs propriétés intrinsèques, dont les processus fondamentaux induits par des rayonnements ionisants. Une étude structurale de ces systèmes par spectrométrie de mobilité ionique a permis de s’assurer qu’ils conservent bien leurs propriétés structurales et de stabilité en l’absence de solvant. De plus, cette stabilité se manifeste aussi lors de l’irradiation par photons ionisants dans un piège à ions. Par ailleurs, nous avons observé, grâce à la spectrométrie de masse, une transition entre photo-excitation et photo-ionisation lorsque l’énergie du photon absorbé augmente dans la gamme VUV-X. Une partie de cette énergie est également redistribuée dans les modes de vibration du système, croît avec l’énergie du photon, et induit la fragmentation inter puis intramoléculaire de la triple hélice. Nous avons également irradié pour la première fois des peptides en phase gazeuse par un faisceau d’ions carbones à l’énergie cinétique pertinente dans le contexte de l’hadronthérapie. Un processus non-observé avec les photons a été mis en évidence : le détachement de proton. Enfin, la validation d’un nouveau dispositif expérimental dédié à l’irradiation de protéines et brins d’ADN par des ions en faisceaux croisés, ainsi que les premiers résultats obtenus, seront abordésCollagen is the most abundant protein in mammals, and the main constituent of the extracellular matrix of cartilage. The mechanical properties of this tissue are due to the particular triple helical structure of collagen. In this thesis, we focused on peptidic models of the collagen triple helix in thegas phase, which allows reaching their intrinsic properties, including fundamental processes induced by ionizing radiations. An ion mobility spectrometry study of these systems proved that they retain their structural and stability properties in the absence of solvent. In addition, these stability properties also play a role after irradiation with ionizing photons in an ion trap. Furthermore, we have observed, thanks to mass spectrometry, a transition between photo-excitation and photoionization as the energy of the absorbed photon increases in the VUV-X range. Part of this energy is also redistributed in the vibration modes of the system, increases with photon energy, and induces intramolecular as well as intramolecular fragmentation of the triple helix. For the first time, we irradiated peptides in the gas phase by a carbon ion beam having a kinetic energy relevant in the context of hadrontherapy. A process that was absent from studies with photons has been observed : proton detachment. In the last chapter, the validation of a new experimental device dedicated to the irradiation of proteins and DNA strands in a cross-beam configuration, as well as the first results obtained, will be reported
30
FONTENAY, CHAMPEAUX SANDRINE. "Etude d'un spectrometre gamma a effet compton pour hauts flux de photons dans la gamme d'energie 0,5-12 mev". Paris 11, 1995. http://www.theses.fr/1995PA112054.
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Cette these porte sur l'etude d'un spectrometre gamma visant l'observation de hauts flux de photons dans une gamme d'energie s'etendant de 0,5 a 12 mev avec une resolution de l'ordre de 0,3 mev. Le choix de l'instrument s'est porte sur un spectrometre a effet compton et a gradient de champ magnetique alliant compacite et grande gamme d'analyse spectrale. Le flux de photons frappe une cible mince et produit par effet compton des electrons dont l'energie est proche de celle des photons incidents dans un cone d'ouverture faible. Ces electrons sont analyses par le secteur magnetique et recueillis dans un plan focal. L'analyse du spectre electronique ainsi obtenu permet de remonter au spectre du flux de photons incidents. L'aspect theorique et numerique de cette etude fait l'objet de la premiere partie. Le premier chapitre debute par quelques rappels concernant l'interaction des photons gamma et la diffusion des electrons dans la matiere puis presente la simulation, de type monte carlo, permettant de prevoir l'angle et l'energie des electrons issus de la cible. L'ensemble des proprietes du secteur magnetique a gradient de champ ainsi que le calcul numerique de la trajectoire des electrons sont presentes dans le second chapitre. Les caracteristiques du spectrometre gamma sont etudiees dans le troisieme chapitre a l'aide de l'ensemble des calculs numeriques permettant de prevoir la reponse du spectrometre. La deuxieme partie est consacree a la validation experimentale des resultats obtenus par simulation. Le spectrometre prototype est decrit dans le premier chapitre. Les trois chapitres suivants presentent la mesure du champ magnetique puis l'etalonnage en electrons et en photons du spectrometre. Le dernier chapitre expose la mesure du spectre emis par un generateur de radiographie eclair, effectuee a l'aide du spectrometre prototype
31
Mayer, Paul Michael. "Photon emissions from ion beam-target gas collisions in a mass spectrometer and the thermochemistry of organic free radicals and cations". Thesis, University of Ottawa (Canada), 1994. http://hdl.handle.net/10393/10414.
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This thesis represents the culmination of four years of research into two aspects of gas phase ion chemistry. The first was an attempt to obtain information on internal excitation in polyatomic projectile - target gas collisions in a mass spectrometer. Knowledge of internal excitation is critical to the interpretation of collision induced dissociation (CID) mass spectra. A novel collision cell was designed for a VG ZAB-2F sector mass spectrometer which permitted the detection and analysis of photon emissions from keV projectile - target gas collisions. Early experiments performed in the second field-free region of the mass spectrometer (sec. 4.2) involved the analysis of emitted light with a series of wavelength cutoff filters. Histographic emission spectra were obtained for three $\rm C\sb2,H\sb4,O\sp{+\cdot}$ ions and two $\rm C\sb2,H\sb5,Cl\sp{+\cdot}$ ions. The spectral characteristics were found to be indicative of ion structure. This led to the development of a more elaborate apparatus in the third field-free region of the ZAB which enabled the aquisition of monochromated emission spectra (sec. 4.3). The emission spectra obtained for 8 keV $\rm N\sb2\sp{+\cdot},O\sb2\sp{+\cdot}\ and\ CO\sb2\sp{+\cdot}$ projectile ions with the target gases He, N$\sb2$, O$\sb2$ and CO$\sb2$ showed that (a) collisional excitation of the ions was a vertical process, (b) considerable translational kinetic energy was converted into internal energy in the collisions (up to 22 eV) and (c) the observed emissions relate to the relative geometries of the ground and excited states of the ions. Histographic spectra for these three projectiles obtained with 18 target gasses exhibited definite trends. The abundance of fragment ions in the collision induced dissociation mass spectra of N$\sb2\sp{+\cdot}$ and CO$\sb2\sp{+\cdot}$ was found to increase linearly with emission intensity, indicating that fragmentation was the result of electronic excitation in the ions. A review was made of the degree of charge delocalization in $-$CN substituted radical cations. Semi-empirical calculations showed that the $-$CN group acted primarily as an inductive electrol withdrawing group in radical cations, carrying very little positive charge. The $-$CN group was found to raise the ionic energy of molecules compared to $-$H independent of the nature of the rest of the molecule (containing saturated, double and triple bonds or aromatic ring). The heats of formation of the $-$CN containing radical cations were 43 $\pm$ 3 kcal mol$\sp{-1}$ higher than their $-$H substituted analogues in all cases. These results were consistent with an inductive electron withdrawing cyano group which does not participate in the charge distribution of the ions. (Abstract shortened by UMI.)
32
Jelínek, Martin. "Analýza neutronového pole laboratorního AmBe zdroje s využitím měřícího stendu". Master's thesis, Vysoké učení technické v Brně. Fakulta elektrotechniky a komunikačních technologií, 2017. http://www.nusl.cz/ntk/nusl-316943.
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This master’s thesis provides a comprehensive overview of the conventional neutron sources from the perspective of reactions which lead to the production of neutrons, advantages, disadvantages, properties and their possible utilization. In the relation to the assembly of the laboratory neutron source and the unique experimental stand “Candle” basic methods of the neutron field analysis are outlined and two of them, the neutron activation analysis and the calculation using the MCNP software code are discussed in depth to apply and compare these methods. The experimental part deals with the realization of neutron activation analysis from its design itself, through gamma spectrometry to the cadmium ratio calculation. In compliance with the measurements, a calculation with MCNP code was run and both methods were evaluated and compared. The computation is complemented with the analysis of radiation situation on the borders of the supervised area, which is compared to the legal limit.
33
Nouvel, Guy. "Etude par spectrometrie raman des phonons et des excitations electroniques dans les trichalcogenures d'uranium". Toulouse 3, 1987. http://www.theses.fr/1987TOU30056.
Texto completo da fonteResumo:
Etude des phonons a k = 0 de ux::(3) (x = s, se, te) quasi-unidimensionnels par diffusion raman a 300 k. L'analyse des spectres a ete completee par un calcul de dynamique de reseau fonde sur un modele d'interaction a deux corps et a courte portee. L'etude des composes suggere l'existence d'une transition magnetique, vers 50 k dans le seleniure, vers 10 k pour le tellurure. Des structures dues a des transitions electroniques au sein de la configuration 5f**(2) de l'ion u**(4+) ont ete mises en evidence dans le sulfure et le seleniure
34
Kosev, Krasimir. "A High-Resolution Time-of-Flight Spectrometer for Fission Fragments and Ion Beams". Doctoral thesis, Technische Universität Dresden, 2007. https://tud.qucosa.de/id/qucosa%3A23920.
Texto completo da fonteResumo:
1. A quantitive understanding of the nucleosynthesis process requires the knowledge of the production rates, the masses and the ?-decay characteristics of exotic neutron-rich nu- clei. Nuclear fission is a suitable method of producing such nuclei with masses from 60 - 150. Neutron-rich nuclei close to the r-process path can be produced via photo-fission at the Rossendorf superconducting linear accelerator of high brilliance and low emittance (ELBE) or by means of nuclear reactions at relativistic energies (for example at GSI). If the fission prod- ucts are identified and also their charge numbers are obtained, it will be principally possible to investigate their structure by means of beta-gamma spectroscopy. 2. For the purpose of fission-fragment detection a double time-of-flight (TOF) spectrometer has been developed. The key component of the TOF spectrometer is a TOF detector consisting of multichannel-plate (MCP) detectors with a position-sensitive readout, a foil for secondary electron (SE) production and an electrostatic mirror. The fission fragments are detected by measuring the SEs impinging on the position-sensitive anode after emission from the foil, ac- celeration and deflection by the electrostatic mirror. 3. In the first part of the work, special attention is paid to the relevant methods of building a spectrometer of such type. The functionality of the different detector components is proven in detail. A unique method for the determination of the SE foil thickness with ?-particles is pre- sented. Values for the mirror transmission and scattering are deduced. A dedicated SIMION 3D simulation showed that introducing serpentine like wires with pitch distance of 1 mm is capable of providing transparency of more than 90% without significant impact on the time resolution. 4. Since the performance of the MCP detectors is crucial, optimised schemes for their high- voltage supplies have been implemented successfully. Further enhancement of the setup was achieved by introducing surface-mount device (SMD) elements for signal decoupling, positioned close to the detector surface. Thus, we succeeded in avoiding signal deterioration coming from the additional capacitances and inductivities caused by extra cable lengths. Because the MCP signal decoupling takes place by means of rings with not well-defined impedance, impedance- matching problems arise, causing signal ringing and distortion. An approach towards solving this problem was to build a special fast, wide-band transimpedance amplifier. Using its circuit mounted close to the detectors, a significant reduction of the signal ringing was observed while maintaining the rise time of the detector signal. In order to process the multichannel-plate de- tector signals optimally, a new state-of-the-art constant-fraction discriminator (CFD) based on the amplitude and rise time compensated (ARC) technique with very low threshold capabilities and optimised walk properties has been developed and incorporated into the setup. 5. In our first laboratory test measurements conducted with an ?-particle source, we demonstrated ability of the setup to resolve pattern images placed directly in front of the MCP detector or reflected by the electrostatic mirror. The obtained position resolution for the second case is in the order of 2 mm. We showed that the detection efficiency of the system for ions like He is less than 30 %. This is mainly due to the low number of the electrons liberated from the SE foil. In a setup consisting of two mirror MCP detectors, we could successfully observe the TOF spectrum of a mixed (226Ra, 222Rn, 210Po, 218Po, 214Po) ?-source and found a good agreement with a SRIM simulation. 6. Measurements performed at the FZ Dresden-Rossendorf 5 MV tandem accelerator en- abled us to learn more about the response of the TOF detectors to various beams of heavy ions. The first in-beam experiments clearly showed that the applied setup consisting of two mirror detectors is capable of resolving different 35Cl beam charge states. In a combination with the specially designed wide-band amplifier and dedicated CFDs based on the ARC technique, we managed to achieve an in-beam time resolution of 170 ps per TOF detector. Measurements with ions of Z > 30 resulted in detection efficiencies of greater than 90%. At foil accelerating potentials approximately two times larger than the mirror deflection voltage, most of the SEs gain enough energy to pass through the electrostatic mirror without being deflected towards the MCP surface. Thus, an abrupt drop of the efficiency curve was observed - the “transparent” mode of the mirror. 7. Properties of electrons ejected from thin foils from heavy ions have been also investigated. From the MCP pulse-height-distribution spectra, a number for the forward-emitted SEs ejected by 35Cl beam was deduced. A method for obtaining widths of the SE energy distributions from the drop of the efficiency curve for various ions has been proposed. Assuming that the efficiency curve as a function of the accelerating voltage follows an error function, its standard deviation gives the standard deviation of the SE energy distribution. Another method based on the TOF technique for reconstructing the secondary electron velocity and energy distribution was also invented. It was found that the resulting mean SE velocity closely approaches the one of the beam ions. This phenomenon was attributed to the so-called “convoy” electrons. 8. The obtained position resolution for beams like 35Cl, 79Br and 107Ag at stable detection efficiency was better than 1.8 mm. It was demonstrated that with increasing the foil accelerat- ing voltage, the position resolution improves due to the minimised SE angular spread. Such a mode of operation was favoured until the mirror “semi-transparency” regime was reached, after which increasing further the accelerating potential could lead to a position resolution worsen- ing. An explanation of the fact could be the deterioration of the anode timing signals or some defocusing effects arising from the mirror wires field at high accelerating voltages. 9. Testing photo-fission experiments were performed at the bremsstrahlung facility at the ELBE accelerator. For the first time a spectrometer of this kind was successfully employed for bremsstrahlung-induced photo-fission measurements. The setup consisted of two mirror detectors (first arm) and a 80 mm diameter MCP detector (second arm) with a 238U target positioned in between. TOF measurements with two bremsstrahlung end-point energies of 12.9 and 16.0 MeV were carried out. A clear cut separation of the TOF peaks for the medium- mass and heavy fission fragments was observed. At these experimental test runs, we did not aim at one-by-one fission fragment mass resolution, since this may be the purpose of a more specific experiment utilising a much thinner fissile source than the one applied here (minimum straggling of the fragments inside the target is required) and considerably better statistics. It was possible to estimate the photo-fission production rate for the two measuring cases and to compare the obtained results with data from other measurements.
35
Xia, Zhixuan. "Highly sensitive, multiplexed integrated photonic structures for lab-on-a-chip sensing". Diss., Georgia Institute of Technology, 2015. http://hdl.handle.net/1853/54848.
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The objective of this work is to develop essential building blocks for the lab-on-a-chip optical sensing systems with high performance. In this study, the silicon-on-insulator (SOI) platform is chosen because of its compatibility with the mature microelectronics industry for the great potential in terms of powerful data processing and massive production. Despite the impressing progress in optical sensors based on the silicon photonic technologies, two constant challenges are larger sensitivity and better selectivity. To address the first issue, we incorporate porous materials to the silicon photonics platform. Two porous materials are investigated: porous silicon and porous titania. The demonstrated travelling-wave resonators with the magnesiothermically reacted porous silicon cladding have shown significant enhancement in the sensitivity. The process is then further optimized by replacing the thermal oxide with a flowable oxide for the magnesiothermic reduction. A different approach of making porous silicon using porous anodized alumina membrane leads to better flexibility in controlling the pore size and porosity. Porous titania is successfully integrated with silicon nitride resonators. To improve the selectivity, an array of integrated optical sensors are coated with different polymers, such that each incoming gas analyte has its own signature in the collective response matrix. A multiplexed gas sensor with four polymers has been demonstrated. It also includes on chip references compensating for the adverse environmental effects. On chip spectral analysis is also very critical for lab-on-a-chip sensing systems. For that matter, based on an array of microdonut resonators, we demonstrate an 81 channel microspectrometer. The demonstrated spectrometer leads to a high spectral resolution of 0.6 nm, and a large operating bandwidth of ~ 50 nm.
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Sioud, Salim. "Improvement of the detection of organic environmental pollutants and comprehension of the gas-phase chemical ionization mechanism using dopant-aided vacuum ultraviolet photoionization high- resolution mass spectrometry". Electronic Thesis or Diss., Sorbonne université, 2023. http://www.theses.fr/2023SORUS527.
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Des méthodes analytiques innovantes sont nécessaires pour surveiller ces polluants organiques en réponse au changement climatique. La spectrométrie de masse haute résolution couplée à la photoionisation à pression atmosphérique (APPI-HRMS) associée à la chromatographie liquide ultra-performante (UHPLC) est un outil de pointe pour l'analyse des molécules aromatiques apolaires. En effet, des mélanges multicomposants et un nouveau système de délivrance de dopants (tête d'impression piézoélectrique) ont été développés pour les applications APPI afin d'améliorer les performances d'ionisation et de détection des HAP en spectrométrie de masse à photoionisation à pression atmosphérique.Cela nous a permis de séparer et de détecter 14 des 18 HAP etudiés à de faibles concentrations en pg/µl avec des précisions de masse élevées de ≤4 ppm en 5 minutes. De plus, ces innovations ont amélioré de 2 à 10 fois les limites de détection et de quantification (LOD et LOQ) des HAP testés. Dans un second temps, afin de comprendre les mécanismes d'ionisation détaillés conduisant à la formation de cations radicaux ([M]+•), et a la formation d'ions [M–H]+ pour une classe de dérivés de TPD-N-substitués, de multiples études expérimentales ont été investiguées. Ainsi, un seul type de cation radicalaire, [M]+•, a été observé pour les HAP en utilisant des dopants multicomposants à base d'éthanol. D'autre part, les ions [M–H]+ pour les dérivés N-alkyl-TPD ont été observés en plus grande abondance dans les conditions APPI. De plus, le dopant de type benzène halogéné et la longueur de la chaîne alkyle (CnH2n+1), avec n ≥4, ont influencé la formation des ions [M–H]+Innovative analytical methods are needed to monitor these organic pollutants in response to climate change. High-resolution mass spectrometry coupled with atmospheric pressure photoionization (APPI-HRMS) associated with ultra-performance liquid chromatography (UHPLC) is a state-of-the-art tool for the analysis of non-polar aromatic molecules. Indeed, multicomponent mixtures and new dopant delivery system (piezoelectric printhead) have been developed for APPI applications to improve the ionization and detection performance of PAHs during atmospheric pressure photoionization mass spectrometry. This allowed us to separate and detect 14 of the 18 studied PAHs at low pg/µl concentrations with high mass accuracies of ≤4 ppm in 5 minutes. In addition, these innovations improved the limits of detection and quantification (LOD and LOQ) of the PAHs tested by 2 to 10 times. Secondly, in order to understand the detailed ionization mechanisms leading to the formation of radical cations ([M]+•), and to the formation of [M–H]+ ions for a class of derivatives of TPD- N-substituted, multiple experimental studies have been investigated. Thus, only one radical cation type, [M]+•, was observed for PAHs using ethanol-based multicomponent dopants. On the other hand, [M–H]+ ions for N-alkyl-TPD derivatives were observed in greater abundance under APPI conditions. In addition, the halogenated benzene-type dopant and the length of the alkyl chain (CnH2n+1), with n ≥4, influenced the formation of [M–H]+ ions
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Liu, Min. "Radiation-induced processes within DNA in the gas phase". Electronic Thesis or Diss., Normandie, 2023. http://www.theses.fr/2023NORMC292.
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Les dommages à l’ADN sont généralement considérés comme les lésions cellulaires les plus courantes et le plus importantes parmi celles causées par les rayonnements ionisants. Ces dommages présentent de graves risques pour la santé humaine, mais ils font également de la radiothérapie un outil puissant pour tuer les cellules cancéreuses et sauver des vies. Pour ces raisons, de nombreuses recherches se sont concentrées sur les processus induits par les radiations au sein de l’ADN. Cependant, la plupart de ces travaux ont été réalisés en phase condensée, ce qui ne permet pas d'éliminer l'influence du milieu environnant. Afin d'étudier les conséquences de l'interaction directe de l'ADN avec les rayonnements ionisants à l'échelle moléculaire, nous avons irradié une séquence d'ADN auto-complémentaire en phase gazeuse avec un rayonnement synchrotron ou des faisceaux d'ions, et analysé par spectrométrie de masse les ions moléculaires produits. Grâce à la spectrométrie de mobilité ionique, nous avons établi que les doubles brins déprotonés de cette séquence forment bien une double hélice stable dans un piège à ions, si l'état de charge est supérieur à 5-. Ensuite, nous avons étudié les conséquences de la photoabsorption spécifique se produisant au niveau du squelette oligonucléotidique de l'ADN en phase gazeuse. En surveillant le détachement non dissociatif d'un seul électron des précurseurs déprotonés en fonction de l'énergie des photons autour du bord K du phosphore, nous avons identifié la signature spectrale des rayons X de la photoabsorption sélective au niveau des atomes de phosphore situés uniquement dans le squelette. Nous avons également détecté d’abondants cations de fragments de bases nucléiques résultant du détachement de plusieurs électrons et avons ainsi démontré le transfert de charge, d’énergie et d’hydrogène du squelette vers les bases nucléiques. Dans la dernière partie de la thèse, nous présentons les résultats de l'irradiation des oligonucléotides d'ADN par des ions carbone en phase gazeuse. Nous avons observé un détachement non dissociatif d'un seul électron et des ions fragments positifs tout aussi abondants après l'impact d'ions carbone, comme dans le cas de l'irradiation par des photons de rayons X. Plus important encore, nous avons réussi pour la première fois à irradier un double brin d’ADN hélicoïdal en phase gazeuse. 70% des produits ioniques résultants proviennent d’un détachement non dissociatif d’un seul électron, ce qui est beaucoup plus élevé que dans le cas des simples brins. Par conséquent, l’ionisation directe d’une double hélice d’ADN après interaction avec un seul ion carbone n’entraîne pas de séparation des brins, ce qui a des implications importantes concernant les dommages à l’ADN, notamment dans le contexte de l’hadronthérapieDNA damage is generally considered to be the most common and most important type of lesions in cells caused by ionizing radiation. While DNA damage caused by ionizing radiation poses serious risks to human health, it also makes radiation therapy a powerful tool for killing cancer cells and saving lives. For these reasons, a great deal of research has focused on radiation-induced processes within DNA. However, most of this work has been carried out in the condensed phase, which cannot remove the influence of the surrounding environment. In order to investigate the consequences of direct interaction of DNA with ionizing radiation at the molecular scale, we have irradiated a self-complementary DNA sequence in the gas phase with synchrotron radiation or ion beams, and analyzed the resulting product ions by mass spectrometry. Thanks to ion mobility spectrometry, we have established that deprotonated double strands of this sequence indeed form a double helix that is stable in an ion trap, if the charge state is higher than 5-. Then, we have investigated the consequences of specific photoabsorption occurring at the DNA oligonucleotide backbone in the gas phase. By monitoring non-dissociative single electron detachment from deprotonated precursors as a function of photon energy around the phosphorus K-edge, we have identified the X-ray spectral signature of selective photoabsorption at the phosphorus atoms located only in the backbone. We also detected abundant nucleobase fragment cations resulting from multiple electron detachment and thus demonstrated the charge, energy and hydrogen transfer from the backbone to the nucleobases. In the final part of the thesis, we present the results of irradiation of the DNA oligonucleotides by carbon ions in the gas phase. We have observed similar non-dissociative single electron detachment and similarly abundant positive fragment ions after carbon ion impact as in the case of irradiation by X-ray photons. More importantly, we have successfully irradiated a helical DNA double strand in the gas phase for the first time. 70% of the resulting ionic products come from non-dissociative single electron detachment, which is much higher than the case of single strands. Therefore, direct ionization of a DNA double helix after interaction with a single carbon ion does not lead to separation of the strands, which has important implications regarding DNA damage, notably in the context of hadrontherapy
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Manrique, John Peter Oyardo. "Reconstrução do espectro de fótons de aceleradores lineares clínicos com base na curva de transmissão e no algoritmo de recozimento simulado generalizado". Universidade de São Paulo, 2015. http://www.teses.usp.br/teses/disponiveis/59/59135/tde-31012016-151001/.
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A distribuição espectral de raios X de megavoltagem utilizados em departamentos de radioterapia é uma grandeza fundamental a partir da qual, em princípio, todas as informações requeridas relevantes para tratamentos de radioterapia podem ser determinadas. A medição direta é difícil de realizar clinicamente, e a análise da transmissão é um método indireto clinicamente viável para determinar espectros de fótons de aceleradores lineares clínicos. Neste método, os sinais de transmissão são adquiridos após o feixe passar através de diferentes espessuras de atenuadores. O objetivo deste trabalho foi o estabelecimento e a aplicação de um método indireto que utilizou um modelo espectral baseado no algoritmo de recozimento simulado generalizado para determinar o espectro de fótons de aceleradores lineares clínicos com base na curva de transmissão. A análise dos espectros obtidos foi feita por determinação analítica de grandezas dosimétricas e parâmetros relacionados.The spectral distribution of megavoltage X-rays used in radiotherapy departments is a fundamental quantity from which, in principle, all relevant information required for radiotherapy treatments can be determined. The direct measurement is difficult to achieve clinically and analyzing the transmission is a clinically viable indirect method for determining clinical linear accelerators photon spectra. In this method, transmission signals are acquired after the beam passes through different thicknesses of attenuators. The objective of this work was the establishment and application of an indirect method that used a spectral model based on generalized simulated annealing algorithm to determine the spectrum of clinical linear accelerators photons based on the transmission curve. Analysis of the spectra was made by analytical determination of dosimetric quantities and related parameters.
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Momeni, Babak. "Design and Implementation of Dispersive Photonic Nanostructures". Diss., Georgia Institute of Technology, 2007. http://hdl.handle.net/1853/16186.
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Photonic crystals (PCs), consisting of a periodic pattern of variations in the material properties, are one of the platforms proposed as synthetic optical materials to meet the need for optical materials with desired properties. Recently, applications based on dispersive properties of the PCs have been proposed in which PCs are envisioned as optical materials with controllable dispersive properties. Unlike the conventional use of PCs to achieve localization, in these new applications propagation inside the photonic crystal is studied, and their dispersive properties are utilized. Among these applications, the possibility of demultiplexing light using the superprism effect is of particular interest.
Possibility of integration and compactness are two main advantages of PC-based wavelength demultiplexers compared to other demultiplexing techniques, for applications including compact spectrometers (for sensing applications), demultiplexers (for communications), and spectral analysis (for information processing systems). I develop the necessary simulation tools to study the dispersive properties of photonic crystals. In particular, I will focus on superprism-based demultiplexing in PCs, and define a phenomenological model to describe different effects in these structures and to study important parameters and trends. A systematic method for the optimization and design of these structures is presented. Implementation of these structures is experimentally demonstrated using the devices fabricated in a planar SOI platform based on designed parameters. In the next step, different approaches to improve the performance of these devices (for better resolution and lower insertion loss) are studied, and extension of the concepts to other material platforms is discussed.
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Macleod, Kenneth Alexander. "Validation and application of a photo-acoustic gas analyser for multiple breath inert gas washout in children". Thesis, University of Edinburgh, 2014. http://hdl.handle.net/1842/33295.
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Multiple breath washout (MBW) of inert gas for assessment of airway disease in children is an emerging technique. In many studies Lung Clearance Index (LCI), derived from multiple breath washout of SF6, is more able to detect early or mild lung disease than standard lung function measurements. It is also able to detect very early lung disease in progressive conditions such as Cystic Fibrosis (CF). Where infants born with this condition were thought to have minimal lung disease activity, LCI is higher in these children than healthy controls. Lack of available commercial devices has hampered expansion of this technique to centres other than specialist research teams. Innocor (Innovision, Dk), a photoacoustic mass spectrometer capable of performing multiple breath washout, was adapted within this research group for use in adults. This thesis describes the setup, adaptation and validation of Innocor for use in children. In 4 studies, healthy controls, children with asthma and children with CF were recruited to perform MBW. In one study, 29 healthy controls and 31 children with asthma were recruited. Healthy controls performed 1 set of washouts, establishing a normative range. Children with asthma performed measurements before and after bronchodilator. Results showed increased LCI in children with asthma even though they were clinically stable as defined by symptoms. LCI stayed high even following bronchodilator suggesting evidence of residual airway disease in well controlled asthmatics despite adequate symptom control. To investigate short term variability of MBW measurements, two other studies recruited 18 children with CF in each. They performed measurements before and after standard physiotherapy manoeuvres and during sitting and lying posture. LCI did not change significantly after airway clearance physiotherapy, compared with children who did no intervention. Variability was high in both groups however suggesting CF lung disease is a complex interaction of changing ventilation in adjacent lung units. Lying posture induced greater changes in lung function in children with CF than controls. LCI appears to be more sensitive to this change than standard lung function measurements (spirometry). In another study 32 children with CF were recruited to perform serial lung function measurements over 18 months. These were data collected as part of the UK Cystic Fibrosis Gene Therapy Consortium (CFGTC) clinical studies in preparation for planned gene therapy trials. LCI appears comparable to FEV1 and may be able to detect another aspect of airway disease. All initial studies were performed in older children (>5yrs). The basic Innocor device is unsuitable for testing of younger patients with low breath volume and high respiratory rate. In-house adaptations following detailed lung model experimentation led to a faster analyser response, potentially capable of MBW in younger children. The second part of this thesis concerns lab experiments and an in-vivo comparison with the current gold-standard MBW device, a respiratory mass spectrometer. 16 healthy volunteers and 9 children with CF were recruited. Ages ranged from 0.4 yrs to 49 yrs. Innocor values for lung volume estimation compared favourably with the mass spectrometer. No evidence of bias caused by Innocor error was seen, however intra-test variability was rather high, reducing the precision of the results. These studies indicate Innocor is a robust, simple to use device with potential as a commercial lung function system. Modifications were made to make it suitable for use in all ages. Further development will need to focus on the patient interface and software, which is the domain of the manufacturers. The experiments contained in this thesis are therefore of interest to the wider respiratory research community as well as manufacturers of MBW devices.
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Forysinski, Piotr Wojciech. "A new photoelectron/photoion spectrometer for the characterisation of molecules and clusters using XUV and UV radiation". Thesis, University of British Columbia, 2011. http://hdl.handle.net/2429/38189.
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A new photoelectron/photoion spectrometer with a light source tuneable from 17.9 eV to 1.5 eV (bandwidth ≲ 0.7 cm⁻¹) for the characterisation of molecules, clusters and ultrafine aerosol particles is described. The first vibrationally resolved PFI-ZEKE (pulsed field ionisation-zero kinetic energy) photoelectron spectra of acetic acid and difluoromethane are presented, which in the case of acetic acid leads to a revision of earlier values for the adiabatic ionisation energy. For the difluoromethane cation a long-standing mystery regarding its vibrational progression previously observed in low resolution photoelectron spectra is unravelled, and the vibrationally resolved PFI-ZEKE photoelectron spectrum is assigned based on full dimensional anharmonic calculations.
A sodium oven was incorporated into the spectrometer to dope clusters and ultrafine aerosol particles with a single atom of sodium. Doped species are subsequently ionised with a single UV (ultraviolet) photon. The composition of the molecular beam can be assessed independently using XUV (extreme ultraviolet) radiation. The results of comparing these two techniques for the first time on the case study of small acetic acid clusters are presented. Fragmentation processes which occur following sodium capture and subsequent photoionisation are strongly dependent on the particular cluster. For the small acetic acid clusters studied (n ≤ 8) the total number of monomer units which evaporate from the sodium doped cluster is determined to be ≲ 4.
This amount of evaporation is insignificant for larger clusters and ultrafine aerosol particles. An almost “fragmentation free” particle sizer for volatile ultrafine aerosol particles is thus proposed based on the sodium doping technique. As a first step towards this goal it is shown that the sodium doping technique can indeed be applied to ultrafine aerosol particles. On the examples of large clusters of acetic acid and dimethyl ether, the technique is demonstrated to preserve the size and chemical composition of the clusters. This is in contrast to other ionisation techniques such as XUV ionisation, for which substantial cluster fragmentation is observed.
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Michail, Evripidis [Verfasser], e Christoph [Gutachter] Lambert. "Design and Development of a Two-Photon Absorption Induced Fluorescence Spectrometer and the Investigation of Nonlinear Optical Properties of Organic Chromophores / Evripidis Michail ; Gutachter: Christoph Lambert". Würzburg : Universität Würzburg, 2021. http://d-nb.info/1238018491/34.
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Badieirostami, Majid. "Design and implementation of ultra-high resolution, large bandwidth, and compact diffuse light spectrometers". Diss., Atlanta, Ga. : Georgia Institute of Technology, 2008. http://hdl.handle.net/1853/26644.
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Thesis (Ph.D)--Electrical and Computer Engineering, Georgia Institute of Technology, 2009.Committee Chair: Adibi, Ali; Committee Member: Bhatti, Pamela; Committee Member: Callen, William; Committee Member: Gaylord, Thomas; Committee Member: Zhou, Hao-Min. Part of the SMARTech Electronic Thesis and Dissertation Collection.
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Ignasiak, Marta. "Study of the mechanism of radiation- and photo-induced oxidation of methionine containing peptides". Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112098/document.
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Plusieurs facteurs conduisent à la génération de radicaux libres oxydants dans les organismes qui endommagent les biomolécules et en particulier les protéines du vivant. L’une des cibles de l’oxydation dans les protéines est la méthionine (Met). Son oxydation provoque des effets très dommageables, comme la maladie d’Alzheimer ou les maladies à prion. Nous avons étudié la réaction des radicaux hydroxyle (•OH) et de l’état triplet de la 3-carboxybenzophénone (3CB*) avec ces peptides. Le but de ce travail était de caractériser les espèces transitoires et les produits stables formés après oxydation radiolytique et photolytique de peptides contenant la Met (les dipeptides contenant de la Met et les pepetides plus longs tels que la bradykinine, une hormone humaine importante impliquée dans la diminution de la pression artérielle). Nous avons utilisé la photolyse éclair laser (LFP) et la radiolyse pulsée (PR) (pour les espèces transitoires de courte durée de vie), tandis que la radiolyse gamma et la photolyse continue (pour obtenir une caractérisation des produits stables). Les modifications structurelles ont été caractérisées par des techniques de HPLC et par couplage de la spectrométrie de masse (MS) et la détection par spectrométrie infrarouge couplée à la MS (IRMPD, CLIO laser à électrons libres). En outre, il nous a paru intéressant d’étudier deux autres dérivés de la benzophénone (BP), l’oxybenzone (OXB) et le sulisobenzone (SB), qui sont largement utilisés dans les produits de protection solaire commerciaux. En effet, l’application d’écrans solaires est controversée car certaines études épidémiologiques ont indiqué un risque accru de mélanome malin pour leurs utilisateurs. L’oxydation de dipeptides contenant Met par les radicaux •OH ou photosensibilisée par la ³(CB)* a conduit à la formation de radicaux cations centrés sur le soufre de la Met (>S•⁺) qui ont été en outre stabilisés par la formation de liaison deux centres à trois électrons (S∴Y)⁺, Y étant un atome possédant un doublet libre, ou qui ont subi une déprotonation donnant les radicaux contrés sur le carbone en α (α-S). L’oxydation des dipeptides par •OH a abouti à la formation de sulfoxyde de Met (MetSO) en tant que produit principal. Sans aucun doute, l’identification et la caractérisation des MetSO en solutions désoxygénées contenant la catalase est une étape importante dans la quête de produits stables. Toutefois, dans certains cas, d’autres produits ont été identifiés. En ce qui concerne, les produits stables de photolyse, ce sont des adduits avec le groupement 3CB, probablement résultant de la réaction de recombinaison radical-radical. Un autre produit formé au cours de la photolyse était 3CB-3CB résultant d’une photo-addition, qui a une structure similaire à celle du produit d’irradiations de la BP. Tous les produits identifiés (MetSO et la photo-adduits) ont été formés à partir des radicaux α-S par l’intermédiaire d’une dismutation ou une réaction avec 3CBH•/3CB•⁻. L’oxydation de la Met-Lys-bradykinine (MKBR) a abouti à la formation de photo-adduits similaires par réaction sensibilisée avec 3CB. L’oxydation induite de MKBR par •OH a abouti à plusieurs produits, en accord avec la non sélectivité des radicaux •OH. L’un des principaux produits est le MetSO et la phénylalanine hydroxylée. Notons que l’arginine n’est pas oxydée. Enfin, la photolyse de SB et OXB a été étudiée à l’aide de photolyse éclair au laser femto-et nanoseconde, ainsi que l’oxydation à un électron de ces molécules par radicaux •OH ont été réalisées en PR. Les résultats obtenus ont été comparés à ceux d’autres dérivés de la BP. L’état singulet excité subit un quenching à 100 % par transfert de proton intraomléculaire à l’état excité (ESIPT) en milieu aprotique et en milieu non polaire. Dans le cas d’un solvant polaire, la formation de radicaux phénoxyles a été identifiée. La réactivité des filtres solaires UV-excité vers dérivés simples de méthionine est également en cours d’étudeSeveral factors (radiation, metabolism, pollutants) lead to the generation of oxidizing free radicals in living organisms that damage all biomolecules and especially proteins. One of the protein targets is Methionine (Met). Its oxidation causes highly damaging effects, such as Alzheimer’s or prion disease. The aim of this work was to investigate the transient species and the stable products formed after radiolytic and photolytic oxidation of Met-containing peptides. The reaction of hydroxyl radicals (•OH) and 3-carboxybenzophenone triplet state with Met-residue in peptides was investigated for model compounds (Met-dipeptides) and for longer peptides (e.g. Bradykinin). Laser flash photolysis and pulse radiolysis were used to characterize short-lived transient species, while gamma radiolysis and steady-state photolysis were used for quantitative and qualitative characterization of stable products. The structural modifications induced by oxidation have been characterized by the HPLC coupled with mass spectrometry and Infrared Multi Photon Dissociation Spectroscopy (IRMPD, CLIO Free electron laser). The oxidation of investigated Met-containing compounds by •OH or 3CB* led to the formation of S-centered radical cation >S•+ on Met-residue, that were further stabilized by formation of two-centered three-electron bond (S∴Y)+ or underwent the deprotonation reaction yielding the α-(alkylthio)alkyl radicals (α-S). The oxidation of Met-containing dipeptides by •OH radicals yielded the formation of Met sulfoxide (MetSO) as a main product. Undoubtedly, the identification and characterization of MetSO in deoxygenated solutions containing catalase was a milestone in investigation of stable products. However, in some cases, other products were identified. The stable products of photolysis were adducts with 3-carboxybenzophenone moiety, resulting from radical recombination reaction. Another identified product formed during photolysis was 3CB-3CB benzpinacol photoadduct, which has similar structure to the product of BP irradiations. Identified products (MetSO and the photo-adduct) were formed from the α-S via disproportionation or reaction with 3CBH•/3CBH•⁻. The oxidation of Met-Lys-Bradykinin (MKBR) yielded formation of similar photo-adducts via sensitized reaction with the 3CB*. The •OH induced oxidation of MKBR yielded several products, e.g. the sulfoxide and hydroxylated phenylalanine. In addition, other derivatives of benzophenone (oxybenzone (OXB) and sulisobenzone (SB)) were investigated due. They are widely used in commercial sun-protecting products dp to their unique photophysical properties. However the application of sunscreens awakes controversies because some epidemiological studies indicated an increased risk of malignant melanoma for their users. Photo-instability of sunscreen filters would result in reduced protection and may produce reactive free radicals or mutagens. In addition, the reactions of the sunscreens with oxygen free radicals e.g. hydroxyl radicals are likely to arise and they were not yet sufficiently documented. Finally, the radiolytic and photolytic properties of SB and OXB were investigated using femto-and nanosecond laser flash photolysis. Pulse radiolysis studies of the oxidation of those molecules by •OH radicals were performed. The results obtained for SB and OXB were compared to several other benzophenone derivatives. The results shown the formation of excited singlet state that was deactivated efficiently via the Excited State Intramolecular Proton Transfer (ESIPT). In case of polar solvent, the formation of trace amounts phenoxyl radicals was identified, while for nonpolar media those radicals were not observed. The reactivity of UV-excited sun filters towards simple derivatives of Met was also investigated, however, this topic requires further and more detailed investigations
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Cavalier, Paul. "Echantillonnage direct de franges lumineuses avec des nanodétecteurs supraconducteurs dans un interféromètre en optique intégrée : application à la conception et la réalisation d'un micro-spectromètre SWIFTS". Phd thesis, Université de Grenoble, 2011. http://tel.archives-ouvertes.fr/tel-00622518.
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Ce travail porte sur la réalisation d'un microspectromètre SWIFTS (Stationary Wave Integrated Fourier Transform Spectrometer) incluant des compteurs de photons SNSPD (Superconducting Nanowire Single Photon Detector). Il met en œuvre un interféromètre intégré à guide d'onde en arête bouclé, en SiN, sous lequel sont disposés 24 nanofils supraconducteurs SNSPD en NbN échantillonnant les interférences au pas de 160nm, à une longueur d'onde centrée sur 1.55µm. La conception, l'étude des composantes optique et électronique, la fabrication et la caractérisation à 4.2K sont décrites, jusqu'à la mise en évidence d'une modulation de puissance lumineuse dans le guide conformément à la formation attendue d'interférences. Le SWIFTS-SNSPD constitue le premier dispositif optoélectronique supraconducteur à part entière, doublement intégré. Sa capacité unique d'échantillonnage direct de franges d'interférences ouvre de nombreuses perspectives, pour des applications allant de l'astrophysique aux télécoms.
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Brook, Nicholas H. "The flavour dependence of charged hadron production at large transverse momenta using high energy photon and hadron beams at the OMEGA spectrometer : equipped with a ring imaging Cherenkov detector". Thesis, University of Manchester, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.328282.
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Enjalbert, Quentin. "Nouvel outil de quantification de biomarqueurs couplant la spectroscopie optique et de la spectrométrie de masse, la Photo-SRM". Phd thesis, Université Claude Bernard - Lyon I, 2013. http://tel.archives-ouvertes.fr/tel-01072242.
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La spectrométrie de masse apparaît au travers de la technologie SRM (Selected Reaction Monitoring) comme une alternative crédible aux tests immunologiques pour la quantification de biomarqueurs. Cependant, les limites de quantifications et de détections atteintes ne sont pas suffisantes pour réaliser des dosages cliniques. Afin d'améliorer les limites de détections, nous nous sommes intéressés au couplage de la spectroscopie optique avec la spectrométrie de masse pour le dosage de biomarqueurs. Ce couplage s'appelle la Photo-SRM. Je me suis donc appliqué, dans un premier temps, à étudier les propriétés optiques de biomolécules dans des domaines de longueurs d'ondes différents allant du VUV au visible. Par la suite, la preuve de concept de l'outil Photo-SRM a été réalisée. Suite à une modification instrumentale réalisée sur un spectromètre de masse de type triple quadripôle, un laser continu émettant des photons dans le domaine du visible, 532 nm, a été implémenté dans cet instrument. Cet outil a ensuite été appliqué pour un dosage multiplexé des protéines endogènes majoritaires du sérum humain. Ces protéines ont été dosées via des peptides protéotypiques contenant des cystéines. L'ensemble du sérum a donc été dérivé en amont de l'analyse. Nous avons souhaité appliquer la Photo-SRM au dosage des métabolites. En effet, dans de nombreuses pathologies, les métabolites et les protéines jouent un rôle important. Par exemple, les œstrogènes utilisés comme contraceptif ont un impact sur les concentrations des protéines de coagulation. Il semble donc intéressant de pouvoir étudier ces deux familles de biomolécules lors d'une même analyse. Enfin, avec l'avènement des instruments hybrides, tels que les Q-TOF et le Q-exactive, la quantification n'est plus réservée qu'à l'usage des instruments de type triple quadripôle. Ces instruments permettent de doser des biomolécules aux mêmes ordres de grandeur que les triples quadripôles en mode SRM. Ces instruments permettent également de réaliser des expériences de découvertes en protéomique. La modification instrumentale d'un Q-exactive, hybride quadripôle-Orbitrap, est présentée suivie d'expériences préliminaires. Ce couplage ouvre donc de nouvelles perspectives d'étude en quantification mais également en découverte protéomique
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Nguema, Agnandji Edwin. "Génération et détection Terahertz : application à la caractérisation de matériaux en couches minces". Thesis, Bordeaux 1, 2009. http://www.theses.fr/2009BOR13796/document.
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Ce travail porte sur la caractérisation de matériaux en couches minces par spectroscopie terahertz dépendant du temps. Dans ce but, nous avons élaboré un banc d’analyse spectroscopique dont l’émission et la détection terahertz reposent sur l’utilisation de laser femtoseconde, de semi-conducteurs, de photocommutateurs ultrarapides ou de cristaux électro-optiques. La réponse diélectrique quantitative de matériaux ferroélectriques (titanate de baryum/ - Ba1-xSrxTiO3) déposés sous forme de couches minces, a permis de mettre en évidence l’importance des modes mous de phonon par une étude en température. Enfin, le comportement électromagnétique de polymères conducteurs à base de polyaniline a été effectué notamment leur efficacité de blindage en bande millimétrique et submillimétriqueThis work concerns the characterization of thin film materials by terahertz time domain spectroscopy. For this purpose, we elaborated a terahertz setup in which the terahertz emission and terahertz detection are based on the use of femtosecond laser, semiconductors, ultrafast photoswitches or electro-optic crystals. The study of dielectric function of ferroelectrics thin film (barium titanate/-Ba1-xSrxTiO3) with temperature, give the importance of soft phonon mode. Finally, the electromagnetic behavior of conducting polymers based on polyaniline was made, in particular their shelding effectiveness in millimeter and sub-millimeter length
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Brunelle, Alain. "Spectrometrie de masse par temps de vol a multi-sonde de desorption-ionisation (photons u. V. Et particules kev et mev). Des atomes aux agregats comme projectiles". Paris 11, 1990. http://www.theses.fr/1990PA112195.
Texto completo da fonteResumo:
Un nouveau spectrometre de masse par temps de vol, super-depil, est utilise pour etudier l'emission ionique secondaire a partir de surfaces solides bombardees par divers types de particules incidentes. Cet appareil a la particularite de reunir dans le meme instrument trois sondes de desorption-ionisation differentes: une source de californium 252, emettant par fission spontanee des ions lourds d'energie environ 1 mev/u, une source d'ions cesium pulsee, d'energie 5 a 30 kev, et un laser a azote pulse, de longueur d'onde 337 nm. Un reflecteur electrostatique a deux etages equipe le spectrometre. Des calculs et des experiences ont ete realises afin d'optimiser la compensation des vitesses initiales que les ions secondaires ont acquis lors de la desorption. La resolution en masse m/m ainsi obtenue est superieure a 5000. Ce miroir permet aussi de definir de tres bonnes conditions d'analyses d'echantillons isolants epais, pour lesquels la variation du potentiel en surface, a la suite de l'irradiation, est souvent penalisante. L'emission ionique secondaire, stimulee successivement par les trois sondes, mev, kev et laser, a ete comparee pour la premiere fois dans des conditions experimentales rigoureusement identiques. Divers composes organiques ont ete etudies, en particulier des films de polymeres, pour lesquels des fragments de masse superieure a 4000 ont ete desorbes. L'analyse de terpenes glycosidiques a montre la complementarite des trois sondes. L'etude des ions metastables realisee avec le reflecteur electrostatique a revele des effets de memoire de structures stereochimiques. Enfin, l'utilisation d'ions agregats comme nouvelle sonde de desorption a montre des effets non lineaires d'augmentation de l'emission ionique secondaire en fonction du nombre de constituants du projectile. Les ions polyatomiques de quelques kev d'energie se sont reveles presque aussi efficaces, sur de no
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Abdelmouleh, Marwa. "Processus intrinsèques radio-induits dans des complexes non-covalents d'intérêt biologique et pharmaceutique". Thesis, Normandie, 2020. http://www.theses.fr/2020NORMC219.
Texto completo da fonteResumo:
Les liaisons non-covalentes jouent un rôle crucial dans de nombreux phénomènes impliquant les systèmes moléculaires d'intérêt biologique et pharmaceutique, notamment dans la reconnaissance moléculaire entre un ligand et son récepteur. Cependant, les effets des rayonnements ionisants sur ces complexes non-covalents ont été très peu étudiés. Dans la première partie de cette thèse, nous présentons les résultats d'expériences de photo-absorption de complexes contenant un antibiotique, la vancomycine, réalisées au moyen d’un spectromètre de masse couplé à des lignes de faisceau synchrotron produisant des photons dans la gamme d'énergie X et VUV. D'abord, nous montrons que la fragmentation des systèmes moléculaires après absorption d'un photon VUV est en partie corrélée à la structure géométrique du complexe. De plus, les processus induits dépendent fortement de l'état de charge des complexes vancomycine/récepteur (protonés ou déprotonés). Pour le complexe protoné, la rupture des liaisons non-covalentes est beaucoup plus probable que pour le complexe déprotoné, dans lequel les interactions natives sont conservées en phase gazeuse. Par ailleurs, l'absorption d'un photon X par la vancomycine mène à des fragments qui peuvent être considérés comme une signature spectrale de ses modifications post-traductionelles. Cette signature est robuste non seulement vis-à-vis de l'énergie des photons X mais aussi de l'environnement moléculaire de la vancomycine. La seconde partie traite de l'étude en phase gazeuse par spectrométrie de masse et de mobilité ionique d'un tri-peptide protoné, et plus particulièrement des effets de la nano-solvatation par la présence d'une ou plusieurs molécules d'éther couronne. Nous nous sommes intéressés à la fragmentation induite par collision avec un gaz rare, ainsi que par transfert ou capture électroniques, et nous avons montré que l'éther couronne n'est pas toujours spectatrice puisqu'elle peut baisser l’état de charge du peptide protoné en lui arrachant un proton ou une molécule protonée, et peut même changer de site de liaison suite à un transfert d’électronNon-covalent bonds play a crucial role in many processes involving molecular systems of biological and pharmaceutical interest, in particular in molecular recognition between a ligand and its receptor. However, their response upon ionizing radiation has scarcely been investigated for understanding radio induced processes. In the first part of this thesis, we present results of photo-absorption experiments of non-covalent complexes containing the vancomycin antibiotic, carried out by means of a mass spectrometer coupled to synchrotron beamlines producing photons in the X and VUV energy range. First, we show that the fragmentation of molecular systems after absorption of one VUV photon is partly correlated with the geometrical structure of the complex. In addition, the processes induced strongly depend on the charge state of the vancomycin/receptor complexes (protonated or deprotonated). For the protonated complex, the cleavage of non-covalent bonds is much more probable than for the deprotonated complex, in which the native interactions are conserved in the gas phase. Moreover, the absorption of one X-Ray photon by vancomycin leads to fragments that can be considered as a spectral signature of its post-translational modifications. This signature is robust not only in terms of photon energy but also of the molecular environment of vancomycin. The second part deals with the study of a protonated tri-peptid in the gas phase by mass and ion mobility spectrometry, and more particularly the effects of nano-solvation by the presence of one or more molecules of crown-ether. We are interested in the fragmentation induced by collision with a rare gas, or by electron transfer or capture, and we have shown that crown ether is not always spectator since it can lower the charge state of protonated peptides by abstracting a proton or a protonated molecule from it, and can even change binding site after electron transfer