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<p dir="ltr">The field of nanoclusters includes a broad range of sizes and structures that influence both their physical and chemical properties. Scientists use several techniques, such as atom-by-atom substitution, to synthesize atomically precise nanoclusters, and ligand shell mixing to protect nanoclusters from unwanted side reactions, while controlling their reactivity and solubility. These combined techniques can provide stable products, but isomers and structural analogs often remain in the product mixture, complicating the structural characterization of individual nanoclusters. Leading structural characterization techniques in nanocluster research are often limited in their ability to examine both the structure of the metal core and ligand shell in sufficient detail. The primary aim of this research is to systematically characterize the structures and chemical properties of several types of transition metal oxide nanoclusters of interest to applications in energy production, catalysis, and magnetic resonance imaging, without requiring purification. Specifically, this work focuses on 1) Polyoxovanadates (POV) with a mixture of methoxy, ethoxy, and ether ligands, 2) Fe- and W-substituted POV alkoxides, and 3) Octanuclear iron oxide clusters substituted with In atoms. Mass spectrometry techniques enable the structural characterization of individual clusters from multicomponent mixtures without interference. Specifically, we use ion mobility spectrometry to explore how surface ligands affect the metal core in mixed-ligand POV alkoxide species. We examine structure-specific fragments to identify the positions of ligands and heteroatoms within the metal core of mixed-ligand species and W and Fe-substituted POV methoxides. Additionally, we use ion soft-landing to purify W-substituted POV methoxide anions on surfaces for characterization using cyclic voltammetry and infrared spectroscopy. We discovered unique characteristics of each nanocluster including the position of heteroatoms, ligands shell mobilities, structures and collisional cross sections, and provided first insights into the redox properties of W-substituted POV alkoxide. These results highlight the growing influence of mass spectrometry in the field of nanocluster characterization and design.</p>

In this dissertation, different approaches have been employed to address the quest of understanding the formation and growth mechanisms of carbon-containing molecular ions with relevance to astrochemistry. Ion mobility mass spectrometry and DFT computations were used to investigate how a second nitrogen in the pyrimidine ring will affect the formation of a covalent bond between the benzene radical cation and the neutral pyrimidine molecule, after it was shown that a stable covalent adduct can be formed between benzene radical cation and the neutral pyridine. Evidence for the formation of a more stable covalent adduct between the benzene radical cation and the pyrimidine is reported here. The effect of substituents on substituted-benzene cations on their solvation by an HCN solvent was also investigated using ion mobility mass spectrometry and DFT computations were also investigated. We looked at the effect of the presence of electron-withdrawing substituents in fluorobenzene, 1,4 di- fluorobenzene, and benzonitrile on their solvation by up to four HCN ligands, and compared it to previous work done to determine the solvation chemistry of benzene and phenylacetylene by HCN. We report here the observed increase in the binding of the HCN molecule to the aromatic ring as the electronegativity of the substituent increased. We also show in this dissertation, DFT calculations that reveal the formation of both hydrogen-bonded and electrostatic isomers, of similar energies for each addition to the ions respectively. The catalytic activity of the 1st and 2nd row TM ions towards the polymerization of acetylene done using the reflectron time of flight mass spectrometry and DFT calculations is also reported in this dissertation. We explain the variation in the observed trend in C-H/C-C activity of these ions. We also report the formation of carbide complexes by Zr+, Nb+, and Mo+, with the acetylene ligands, and show the thermodynamic considerations that influence the formation of these dehydrogenated ion-ligand complexes. Finally, we show in this dissertation, a novel ionization technique that we employed to generate ions that could be relevant to the interstellar and circumstellar media using the reflectron time of flight mass spectrometry.

L’étude de la structure de complexes non-covalents présente un intérêt fondamental dans la recherche en chimie des protéines. Le premier objectif est de caractériser les interactions physico-chimiques sur lesquelles repose l’adoption d’une structure tridimensionnelle fonctionnelle par un édifice multimoléculaire. Le second objectif est de mettre en évidence les changements structuraux induits par le phénomène de complexation, et leur influence sur la fonction du système. Le couplage entre la spectrométrie de masse et la mobilité ionique (IM/MS) est une technique d’étude structurale en phase gazeuse, dont le principe repose sur la séparation d’ions selon leur forme et leur rapport masse sur charge, et qui permet en outre de mesurer leurs sections efficaces de diffusion. Grâce à cette technique, nous avons réalisé l’étude structurale de trois complexes non-covalents : l’agrégation de molécules de tanin sur la protéine salivaire humaine IB5, la fixation du ligand Ac2KAA sur la vancomycine, et la complexation de cations métalliques sur des polymères poly-lactide. L’évolution des sections efficaces en fonction de la taille du système ou de l’état de complexation met en évidence la présence de transitions structurales. De plus, utilisé avec de la modélisation moléculaire ou de la spectroscopie laser, le couplage IM/MS s’avère pertinent pour caractériser les interactions responsables de la stabilisation de tels complexes. Ces travaux de thèse montrent que cette technique , au-delà du simple aspect analytique (séparation d’isomères), peut également être utilisée au sein d’études plus globales, mettant en jeu plusieurs techniques afin de résoudre la structure de systèmes complexes / Knowing the structure of non-covalent complexes is essential to understand many biological processes. The first step is the characterization of the interactions leading to the adoption of a functional tridimensional structure by a multimeric assembly. The second step consists of underlining the structural modifications induced by the complexation, and their influence on the system’s function. The Ion Mobility/Mass Spectrometry (IM/MS) is a gas-phase method that is used to separate ions according to their geometry and their masse-to-charge ratio. IM/MS also provides insights on their intrinsic properties, by measuring their collision cross sections. Using this method, we have studied the structure of three different non-covalent complexes: the aggregation of tannins on the human salivary protein IB-5, the fixation of a small ligand (Ac2KAA) on vancomycin, and the complexation between metallic cations and poly-lactid polymers. The evolution of the collision cross-sections as a function of the size of the system or the complexation state clearly shows structural transitions. Moreover, combined with molecular modeling or laser spectroscopy, the IM/MS technique reveals to be a powerful tool to characterize the relevant interactions in such systems. This work proves that IM/MS, besides a powerful analytical aspect, can also be used in global studies that involve several structural methods to resolve the structure of large multimeric assemblies

Ce travail de thèse repose sur le développement de méthodes en spectrométrie de masse native et mobilité ionique pour la caractérisation structurale de protéines d’intérêt thérapeutique et de complexes multiprotéiques. L’optimisation fine et conséquente de la préparation d’échantillon et des conditions analytiques ont permis la caractérisation de protéines membranaires solubilisées en milieu détergent, protéines hydrophobes habituellement réfractaires à l’analyse par MS. D’autre part, une nouvelle approche de mobilité ionique appelée Collision Induced Unfolding a été évaluée et mise en place au laboratoire. Elle a permis une caractérisation conformationnelle approfondie et originale de plusieurs formats d’anticorps monoclonaux thérapeutiques. Enfin, les techniques de MS native et de mobilité ionique ont été utilisées pour caractériser des complexes multiprotéiques d’hétérogénéité variable mettant ainsi en lumière leurs avantages et les progrès réalisés dans le domaine de la MS structurale. / This PhD work focuses on developments in native mass spectrometry and ion mobility methods for the structural characterization of therapeutic proteins and multiprotein complexes. First, careful optimizations of sample preparation and analytical conditions allowed the characterization of membrane proteins, which are hydrophobic proteins difficult to analyze by MS approaches in detergent environment. Then, a new ion mobility-based activation approach called Collision Induced Unfolding has been set up and evaluated. CIU allowed extensive and original conformational characterization of several therapeutic monoclonal antibody formats. Finally, native MS and ion mobility techniques were used for the characterization of heterogeneous multiprotein complexes depicting their benefit when combined to other biophysical techniques for the structural characterization of multiprotein complexes.