La recombinaison dissociative (RD) est le processus dans lequel un ion moléculaire positif se recombine avec un électron et se dissocie après en fragments neutres. Parmi les différents types de réactions entre ions moléculaires et électrons, la RD mérite une attention particulière à cause du rôle important qu'elle joue dans les plasmas à basse température et de faible densité, telles que celles rencontrées dans les ionosphères planétaires et les nuages interstellaires. En dépit de l'apparente simplicité de la RD, son étude s'est avéré difficile aussi bien du point de vue expérimental que théorique. Afin d'apporter plus de lumière sur ce processus, la technique de la post-décharge en écoulement a été introduite et a été largement utilisée ces dernières décennies. La présente thèse est dédiée aux études expérimentales de la réaction RD, à l'aide du spectromètre de masse à sonde Langmuir (FALP-MS) en post-décharge en écoulement, à l'Université de Rennes 1, à Rennes, en France. Nous avons étudié la réaction RD à température ambiante a été étudiée pour les ions moléculaires d'acétone ( ) et les cations de diméthylamine cations ( ainsi que les vitesses de réaction des cations de triméthylamine ( cations, et nous avons obtenu des valeurs avec des incertitudes de of ± 30 %. De plus, nous avons étudié l'attachement électronique à la diméthylamine neutre et nous avons trouvé une constante de vitesse de = 4.81 x 10-10 cm3 s-1. Un nouveau système d'injection pour l'anneau de stockage électrostatique de KACST a été conçu et construit dans le laboratoire de l'IPR à Rennes. Le couplage de la source d'ions avec un analyseur de masse quadripolaire et l'utilisation d'un système de vannes pulsées assurant un pompage différentiel entre différentes régions de la ligne d'injection constitue une méthode nouvelle dans le contexte d'un anneau de stockage. Le but final de ce projet est l'étude des réactions à ions lourds tels que les ions moléculaires biologiques. / Dissociative recombination (DR) is a process in which a positive molecular ion recombines with an electron and subsequently dissociates into neutral fragments. Among the different types of molecular ion-electron reactions DR deserves particular attention due to the important role it plays in low-temperature and low-density plasmas such as those encountered in planetary ionospheres and interstellar clouds. Despite the apparent simplicity of the DR reaction, its investigation has proven to be a difficult task from both experimental and theoretical perspectives. In order to shed more light upon this process the flowing afterglow technique has been introduced and utilised extensively for the last few decades. This thesis is devoted to experimental studies into the DR reaction using the flowing afterglow Langmuir probe mass spectrometer FALP-MS at the University of Rennes 1, in Rennes, France. The DR reaction at room temperature has been investigated for the acetone molecular ions ( ) and dimethylamine cations ( as well as the reaction rates of trimethylamine ( cations, and the obtained values were with uncertainties of ± 30 %. In addition, the electronic attachment to neutral dimethylamine was also studied and the rate constant was determined to be = 4.81 x 10-10 cm3 s-1. A new ion injection system system for the KACST electrostatic storage ring has been designed and built in the IPR laboratory in Rennes. The coupling of an ion source with a quadrupole mass analyzer and the use of a gas pulsing system to maintain the differential pumping between different regions of the injection line, is a novel technique for use with a storage ring. The final goal of this system is to study the reactivity of heavy ions such as biological molecular ions.

La thèse porte sur des études expérimentales de réactions d’ions positifs et négatifs pour lesquelles on cherche à caractériser l’effet des différentes formes d’énergie : excitation des ions parents et/ou énergie de collision sur la réactivité. Deux buts sont poursuivis. Le premier, fondamental, est de comprendre la dynamique réactionnelle des systèmes étudiés. Le deuxième est plus appliqué. Il s’agit de fournir des données pour la modélisation de la chimie des milieux complexes (ionosphères, plasmas…). Les systèmes étudiés concernent la réactivité de cations excités CH₃⁺ avec des hydrocarbures saturés et insaturés (alc-ane, -ènes et -ynes en C1 à C4) pour sonder la réactivité sur des molécules de fonctionnalité et de tailles variées ainsi que la réactivité de l’anion C₃N⁻ avec l’acétylène C₂H₂. Ces systèmes sont d’intérêt pour l’étude de l’ionosphère de Titan. Nous avons étudié la réactivité de ces systèmes sur le dispositif CERISES en fonction de l’énergie de collision et de l’énergie interne des ions parents. Les anions C₃N⁻ sont produits par attachement dissociatif d’électrons sur le précurseur BrC₃N. Les cations CH₃⁺ peuvent être formés par deux méthodes. Au laboratoire, l’impact électronique conduit, sur le méthane CH₄, à la formation de CH₃⁺ peu excité, et sur le chlorométhane CH₃Cl, à la formation de CH₃⁺ plus excité. Cette observation a permis de préparer les expériences au synchrotron SOLEIL où on utilise la photoionisation des radicaux CH₃ produits par la pyrolyse du nitrométhane CH₃NO₂ pour former les ions CH₃⁺ et contrôler leur excitation. La variation de l’énergie de photon entre 9.8 et 15 eV a permis de faire varier la distribution d’énergie vibrationnelle ou électronique des ions CH₃⁺. Le développement d’un détecteur de photoélectrons adapté à la source de radicaux a permis la réalisation d’expériences TPEPICO (Threshold PhotoElectron PhotoIon Coincidence) où les ions sont extraits de la source en coïncidence avec des électrons de seuil permettant ainsi un contrôle complet de leur énergie. Nous avons observé que l’énergie interne de CH₃⁺ peut jouer un rôle important sur sa réactivité en ouvrant certaines voies de réaction comme la dissociation séquentielle de certains produits (réactions avec le méthane, le propène…) ou bien la voie de transfert de charge endothermique (réactions avec le méthane, l’éthène) que l’énergie de collision ne favorise pas efficacement. L’observation de l’évolution de la section efficace de formation des produits en fonction des deux types d’énergie nous a également permis de discuter les mécanismes de formation de certains produits, comme ceux passant par la décomposition d’un complexe ou par des transferts plus directs. On a pu montrer que la réaction de C₃N⁻ + C₂H₂ produisait des ions C₂H⁻, CN⁻ et C₅N⁻ en faibles quantités et seulement au-dessus de seuils en énergie de collision qui excluent leur formation dans des atmosphères très froides comme celle de Titan, sauf s’il existe des processus formant les anions C₃N⁻ avec de l’énergie. / This PhD project is focused on the experimental study of reactions of positive and negative ions for which we want to characterize the effect of different energies: internal energy of parents ions and/or collisional energy on the reactivity. There are two main goals. The first is to understand the reaction dynamics of the studied systems. The second one is to obtain data for modelisation of the chemistry in complex areas (ionosphere, plasmas...). Studied systems will concern the reactivity of excited cations CH₃⁺ with saturated and unsaturated hydrocarbons (alcane, alcene and alcyne from C1 to C4) as well as the reactivity of the C₃N⁻ anion with acetylene C₂H₂. Targets are chosen for theirs different chemical functions and interesting size for theoretical studies of Titan. We have studied the reactivity of these systems on the CERISES setup as a function of internal and collisional energies of the parent ions. C₃N⁻ anions are produced by dissociative electron attachment on BrC₃N. CH₃⁺ cations can be produced by two different methods. At the LCP, electronic impact on methane CH₄ produce CH₃⁺ cations with low internal energy whereas electronic impact on chloromethane CH₃Cl produce CH₃⁺ cations with more internal energy. This observation allowed us to prepare for the experiments at the SOLEIL synchrotron where CH₃⁺ cations are produced with controlled internal energy by photoionisation of CH₃ radicals produced in-situ by pyrolysis of nitromethane CH₃NO₂. Tuning of the photon energy between 9.8 and 15 eV allowed us to change the vibrational or electronic energy distribution of the CH₃⁺ cations. The development of a photoelectron detector fitted to the radical source enabled TPEPICO experiments (Threshold PhotoElectron PhotoIon Coincidence) where ions are extracted from the source in coincidence with threshold electrons which allow a total control of their energy.We saw that the internal energy of CH₃⁺ can have an important role on its reactivity by opening paths of reaction like sequential dissociation of products (seen in reactions with methane, propene…) or endothermic charge transfer (with methane and ethene) which is not efficiently enhanced by collisional energy. From the evolution of the absolute reaction cross section with the two different energies we discussed the mechanisms of formation of the observed products (decomposition of a complex or direct transfer). The reaction C₃N⁻ + C₂H₂ produce C₂H⁻, CN⁻ and C₅N⁻ anions in small quantities and only above collisional energy threshold which exclude their formation in cold atmosphere like Titan’s one unless there is processes leading to the production of C₃N⁻ with energy.

This dissertation thesis summarizes results of experiments that have been carried out during my PhD studies related to the new mass spectrometric methods for trace gas analysis of human breath. The thesis is divided into the theoretical and experimental part. The chapter at the beginning of this dissertation summarizes the current research in the area of breath analysis. It is describing the common breath metabolites, benefits and challenges of the method for therapeutic monitoring and clinical diagnosis and current applications. The next chapter of the theoretical introduction describes the techniques suitable for this area of research, with a special emphasis on mass-spectrometric techniques (in particular the selected ion flow tube mass spectrometry, SIFT-MS, method that allows accurate quantification of trace gases and vapours in humid air/human breath). All these parts are elaborated via the scientific literature review. The following chapters are then directly related to my own research and describes the conducted experiment, including the results obtained. This experimental part "Results and Discussion" is divided to the individual subsections, which are conceived as the commentaries to the enclosed research papers published in peer reviewed journals. The first is the detailed step by step...

<p>This dissertation presents several examples of diverse applications of mass spectrometry. For example, high-resolution mass spectrometry was utilized for qualitative and quantitative chemical characterization of ionized compounds in petrochemical samples, specifically, in condensate-like oil samples. Further, the ability to use tandem mass spectrometry to rapidly detect trace amounts of short-lived reaction intermediates in solution reactions is demonstrated. Finally, selective tandem mass spectrometry methods based on diagnostic gas-phase ion-molecule reactions were developed for the identification of carboxylic acid functionalities in protonated analytes.</p>

A multiplexed method for performing MS/MS on multiple ions simultaneously in a miniature rectilinear ion trap (RIT) mass spectrometer has been developed. This method uses an ion encoding procedure that relies on the mass bias that exists when ions are externally injected into an RIT operated with only a single phase RF applied to one pair of electrodes. The ion injection profile under such conditions ions is Gaussian-like over a wide range of RF amplitudes, or low mass cutoff (LMCO) values, during ion accumulation. We show that this distribution is related to ion m/z and is likely caused by ions having an optimal range of pseudo-potential well depths for efficient trapping. Based on this observation, precursor ion intensity changes between two different injection LMCO values can be predicted, and these ion intensity changes are found to be carried through to their corresponding product ions, enabling multiplexed MS/MS spectra to be deconvoluted. The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n]y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWA. Results show that the metal complex ions can react with low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n]2+ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below the median lethal doses for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations. Mass spectrometry has become a tool for studying noncovalently bound complexes. Specifically, electrospray ionization mass spectrometry (ESI-MS) has found increasing use for the determination of affinity (Ka) or dissociation (Kd) constants. Direct measurement of the equilibrium components by ESI-MS is the most straightforward approach for determining binding equilibrium constants, but this approach is prone to error and has some inherent limitations. Transferring complexes from solution to the gas phase may perturb the equilibrium concentrations and/or different ionization efficiencies may cause the resulting ion signals not to reflect actual solution concentrations. Furthermore, ESI only works under a limited range of solvent conditions (i.e. low ionic strengths), which limits the broad applicability of this approach. We propose an approach based on covalent labeling in the context of metal-catalyzed oxidation (MCO) reactions that, when combined with MS, overcomes such limitations when determining metal-ligand binding constants. The MCO-MS approach will provide concurrent information regarding metal binding site and metal-protein binding affinity. Optimization of the MCO reaction through isotopic mass tags will permit enhanced identification of modified residues. Application of this method to study the affinity and binding interactions of other divalent metals with β2m are likely to provide insight into the specificity of copper for causing β2m amyloid formation.

No description available.

Popular catalytic cycles, such as the Heck, Suzuki, and Negishi, utilize metal centers that oscillate between two oxidation states (II/0) during the three main steps of catalysis: reductive elimination, oxidative addition, and transmetallation. There has been a push to use less toxic, cheaper metal centers in catalytic cycles, leading to interest in first-row transition metals, such as nickel and cobalt. With these metals, the cycles can potentially pass through the +1 oxidation state, which acts as reactive intermediates, undergoing oxidative additions to form products, potentially with radical characteristics. The oxidative addition steps of catalytic cycles are critical to determining overall rates and products, however in many cases, these steps have not been amenable to study, in either condensed phase or gas phase, in the past. Through the use of electron transfer dissociation (ETD) technology on a modified Thermo Electron LTQ XLTM mass spectrometer, it is possible to generate intermediates in these catalytic cycles, including those in unusual oxidation states. Using sequentially coupled ion/ion-ion/molecule reactions, the reduced, reactive intermediate can be readily generated, isolated, and studied.As a model set of reactions, the mono- and bis-phenanthroline complexes of Fe(I), Co(I), Ni(I), Cu(I), and Zn(I) were formed by reduction of the corresponding M(II) species in an ion/ion reaction with the fluoranthenyl radical anion. The chemistry of the M(I) species was probed in ion/molecule reactions with allyl iodide. In order to explore ligand effects and the scope of oxidative addition reagents further, bipyridine and terpyridine were studied with these five first-row transition metal complexes while using an acetate series and other substrates for oxidative additions. Through these studies, the roles of the metal and ligand in dictating the product distributions and reaction rates were assessed. Metal electron count, ligand flexibility, and coordination number are critical factors. The overall reactivity is in accord with density functional theory calculations and mirrors that of proposed intermediates in condensed-phase catalytic cycles. In addition, second- and third-row transition metals (Ru(I), Pd(I), and Pt(I)) were explored with bipyridine, mono- and bis-triphenylphosphine, and 1,2-bis(diphenylphosphino)benzene ligation schemes. A variety of oxidative addition reagents were surveyed to determine the scope of reactivity and preference toward metal-carbon bond formation or carbon radical formation.

Gas phase molecular clusters present an ideal medium for observing factors that drive chemical reactions without outside interferences from excessive solvent molecules. Introducing an ion into the cluster promotes ion-molecule interactions that may manifest in a variety of non-covalent or even covalent binding motifs and are of significant importance in many fields including atmospheric and astronomical sciences. For instance, in outer space, molecules are subject to ionizing radiation where ion-molecule reactions become increasingly competitive to molecule-molecule interactions. To elucidate individual ion-molecule interaction information, mass spectrometry was used in conjunction with appropriate theoretical calculations. Three main categories of experiment were conducted in this dissertation. The first of which were thermochemical equilibrium measurements where an ion was introduced to an ion mobility drift cell wherein thermalizing collisions occur with helium buffer gas facilitating a reversible reaction with a neutral molecule allowing the standard changes in enthalpy and entropy to be determined. The second type of experiment was an ion mobility experiment where an ionized homo- or hetero-cluster was injected into the drift cell at specific conditions allowing the reduced mobility and collisional cross-section to be evaluated. Thirdly, kinetics measurements were taken following injection of an ion into the drift cell were an irreversible reaction ensued with the neutral species hindering equilibrium, but prompting rate constant assessment. Previous research has laid the groundwork for this dissertation as the results and discussion contained herein will build upon existing data while maintaining originality. For example, past work has given support for ion-molecule reactions involving precursor species such as acetylene and hydrogen cyanide to form more complex organics, perhaps leading to biologically relevant species. The chemical systems studied for this research are either ionized substituted benzenes like phenylacetylene and benzonitrile or polycyclic aromatic nitrogen-containing hydrocarbons like quinoline and quinoxaline interacting with a variety of neutral species. Hydrogen bonding and its many sub-sections are of the utmost importance to the kinds of reactions studied here. Past work has shown the tendency of organic radical cations to form conventional and unconventional ionic hydrogen bonds with gas phase solvents. Other non-covalent modes of interaction have also been detected in addition to the formation of covalently bound species. Gas phase reactions studied here will explore, via mass-selected ion mobility, reversible and irreversible reactions leading to binding enthalpy and entropy and rate constant determination, respectively, in addition to collisional cross-section determination.

As part of this project and in preparation for future experimental studies of gas-phase ion-molecule reactions, extensive modification and characterization of the crossed molecular beam machine in the Department of Chemistry, University of Canterbury has been carried out. This instrument has been configured and some preliminary testing completed to enable the future study of gas-phase ion-molecule collisions of H⁺₃ and Y⁻ (Y = F, Cl, Br) with dipole-oriented CZ₃X (Z = H, F and X = F, Cl, Br). Theoretical calculations (ab initio and density functional theory) are reported on previously experimentally characterized Na + CH₃NO₂, Na + CH₃NC, and K + CH₃NC systems, and several other systems of relevance. All gas-phase experimental and theoretical studies have the common theme of studying collision orientation dependence of reaction under singlecollision conditions. Experimental measurements, theoretical simulations and calculations are also reported on some selected ferrous (Fe²⁺) high-spin (S=2) crystals, in an attempt to resolve microscopic contributions of two fundamental macroscopic tensor properties: the electric-field gradient (efg); and the mean square displacement (msd) in the case when more than one symmetry related site of low local point-group symmetry contributes to the same quadrupole doublet. These determinations have been made using the nuclear spectroscopic technique of Mössbauer spectroscopy, and complemented with X-ray crystallographic measurements.

<div>This dissertation details three studies which utilize nontraditional applications of electrospray ionization mass spectrometry. The first study explores and discusses the limitations of identifying unknown drug metabolites using ion-molecule reactions performed inside a mass spectrometer and coupled with high performance liquid chromatography. Ultimately, it was concluded that some highly-efficient, MS² ion-molecule reactions coupled with some drug metabolites would be sufficiently sensitive for <i>in vivo</i> drug metabolism studies. However, this study also concluded that the rate of false-positives and false-negatives may be higher than previous publications suggest.</div><div><br></div><div>The next study analyzed sulfur-containing compounds under atypical negative mode electrospray ionization mass spectrometry conditions. After noting that low analyte flow rates during electrospray ionization experiments on ethanethiol resulted in significant oxygen incorporation, the aim of this study was to understand the chemistry behind the oxygen incorporation and search for ways to experimentally limit the degree of oxygen inclusion. The atypical conditions were ultimately shown to induce significant ozonolysis and other oxidation reactions. Ultimately, only the use of high flow rates or switching to a different ionization technique were successful in mitigating the oxidation product formation. A new reaction mechanism for the oxidation of ethanethiol with ozone was proposed. Quantum chemical calculations were used to support the mechanism.</div><div><br></div><div>Finally, electrospray ionization mass spectrometry was used to analyze mixtures of selenium and/or tellurium in amine-thiol solvent systems. Selenium and tellurium are essential components in many thin film solar cells and other photovoltaics and amine-thiol solvent systems have been identified as a key solution processing strategy for synthesizing selenium and tellurium thin films. However, the reaction between selenium/tellurium and the amine-thiol solvent system is poorly understood and requires detailed study before large-scale industrial synthesis can be achieved. In this study, the dissolution mechanisms for selenium and tellurium in two different amine-thiol solvent systems were explored and discussed. The role of the basicity of the amine, the relative concentrations of the thiol, and the presence of co-dissolved chalcogens were all studied and used to propose dissolution mechanisms. The results of the experiments were used to control the synthesis of lead-selenium-tellurium alloy nanoparticles and could inform further studies on controlling metal chalcogenide synthesis through the appropriate choice of amine-thiol solvents.<br></div>