Well-defined heterobifunctional homopolyethers and amphiphilic block copolyethers containing a variety of functionalities were designed, synthesized, and characterized via GPC and 1H NMR. These have included controlled molecular weight cholesterol-PEO-OH, mono- and trivinylsilyl-PEO-OH, monovinylsilyl-PEO-PPO-OH, monovinylsilyl-PEO-PPO-PEO-OH, maleimide-PEO-OH, stearyl alcohol-PEO-OH, propargyl alcohol-PEO-OH, trivinylsilyl-PPO-OH, trivinylsilyl-PPO-PEO-OH, and benzyl alcohol-initiated poly(allyl glycidyl ether)-OH. The focus of polymers utilized in this study involved the mono- and trivinylsilyl polyethers. The vinylsilyl endgroups on these materials were functionalized with various bifunctional thiols through free radical addition of SH groups across the vinylsilyl double bonds. The resultant end-functional polyethers were adsorbed onto magnetite nanoparticles and the stabilities of the polymer-magnetite complexes were compared as a function of the type of anchoring moiety and the number of anchoring moieties per chain. Anchoring chemistries investigated in this work included carboxylates, alkylammonium ions, and zwitterionic phosphonates. The anchor group-magnetite bond stability was investigated in water and phosphate buffered saline (PBS). Through these studies, the zwitterionic phosphonate group was shown to be a better anchoring group for magnetite than either carboxylate or ammonium ions. Tri-zwitterionic phosphonate anchor groups provided stability of the complexes in PBS for a broad range of polymer loadings. Thus, investigations into the stability of polyether-magnetite complexes in PBS focused on hydrophilic zwitterionic phosphonate-PEO-OH and amphiphilic zwitterionic phosphonate-PPO-b-PEO-OH oligomer coatings on the surface of magnetite. Superparamagnetic magnetite nanoparticles are of interest as potential contrast-enhancement agents for MRI imaging. Thus, transverse NMR relaxivities of these complexes were studied as a function of chemical composition and nanostructure size and compared to commercial contrast agents. The amphiphilic polyether-magnetite nanoparticles were shown to be stable in both aqueous media as well as physiological media and have much higher transverse relaxation values, r2, than those of commercial contrast agents and other materials in the literature. / Ph. D.

Magnetic nanoparticles are of considerable interest owing to their potential applications in biotechnology and the magnetic recording industry. Iron oxides have received much attention owing to their oxidative stability and biocompatibility; however, other transition metals and their alloys are also under investigation. Cobalt has one of the largest magnetic susceptibilities of these materials, but it readily oxidizes upon exposure to air resulting in antiferromagnetic oxide. Hence, coating cobalt nanoparticles with an oxygen-impermeable sheath would confer numerous benefits. Cobalt nanoparticles were prepared by the thermolysis of dicobalt octacarbonyl in two block copolymer micellar systems, wherein the copolymers were precursors to graphite or silica. Subsequent heat treatment of the samples at 600-700oC was conducted to condense the polymer coating around the cobalt nanoparticles and form oxygen impervious graphite or silica sheaths. Magnetic and structural characterization of these novel materials afforded pertinent information about their physical properties. Magnetic susceptometry indicated that the graphite coated cobalt nanoparticles resisted oxidation for over one year. The silica coated cobalt nanoparticles had high saturated specific magnetic moments, but the coatings were brittle and grinding the particles resulted in oxidation over time. Transmission electron microscopy (TEM), high-resolution TEM (HRTEM) and energy-filtered TEM (EFTEM) were employed to study particle size and structural differences of the cobalt nanoparticles before and after heat treatment. The mean particle size and size distribution increased for the graphite coated cobalt particles, due to particle sintering at 700oC. In the silica coated cobalt nanoparticle system, the mean particle size increased when the sample was heat-treated at 600oC leading to a bimodal distribution. This bimodal distribution was explained by a fraction of the particles sintering, while others remained discrete. When the silica system was heat treated at 700oC, the particle size and size distribution remained similar to those of the pre-heat-treated sample, indicating that no sintering had taken place. The rapid pyrolysis of the polymer at 700oC may serve to lock the cobalt nanoparticles into a silica matrix, thus preventing them from coming into contact with one another and sintering. Several diffraction techniques (selected area electron diffraction (SAD), nano-beam electron diffraction (NBD) and x-ray diffraction (XRD)) were used to probe the crystal structure of graphite and silica coated cobalt nanoparticles, which was determined to be predominantly face-centered cubic. Anisotropic magnetic nanoparticles (nanorods) have an increased magnetophoretic mobility over spherical magnetic nanoparticles with the same equatorial radius. This property makes them attractive candidates for in vivo biological applications. Anisotropic mixed ferrite nanoparticles were coated with a biocompatible hydrophilic block copolymer to render them dispersible in aqueous media. Polymer coated mixed ferrite particles exhibited magnetic properties similar to that of pure magnetite, as the total level of other transition metals in the nanoparticulate system was less than 5%. Electron energy loss spectroscopy (EELS) and (EFTEM) confirmed that the dominant elements in the mixed ferrite nanoparticles were iron and oxygen. Furthermore, HRTEM, SAD and XRD analyses indicated that the crystal structure for the mixed ferrite nanoparticles was inverse spinel. X-ray diffraction peaks at low angles for the coated mixed ferrite rods corresponded to poly(ethylene oxide) peaks, suggesting that the block copolymer employed as a dispersant was associated with the particles. / Ph. D.

The composition and stability of polymer-magnetite complexes is essential for their use as a treatment for retinal detachment, for drug targeting and delivery, and for use as a MRI contrast agent. This work outlines a general methodology to design well-defined, stable polymer-magnetite complexes. Colloidal modeling was developed and validated to describe polymer brush extension from the magnetite core. This allowed for the observation of deviations from expected behavior as well as the precise control of polymer-particle complex size. Application of the modified Derjaguin-Verwey-Landau-Overbeek (DLVO) theory allowed the determination of the polymer loading and molecular weight necessary to sterically stabilize primary magnetite particles. Anchoring of polyethers to the magnetite nanoparticle surface was examined using three different types of anchor groups: carboxylic acid, ammonium, and zwitterionic phosphonate. As assessed by dynamic light scattering (DLS), the zwitterionic phosphonate group provided far more robust anchoring than either the carboxylic acid or ammonium anchor groups, which was attributed to an extremely strong interaction between the phosphonate anchor and the magnetite surface. Coverage of the magnetite surface by the anchor group was found to be a critical design variable for the stability of the zwitterionic phosphonate groups, and the use of a tri-zwitterionic phosphonate anchor provided stability in phosphate buffered saline (PBS) for a large range of polymer loadings. Incorporation of an amphiphlic poly(propylene oxide)-b-poly(ethyelene oxide) (PPO-b-PEO) diblock copolymer attached to the magnetite surface was examined through colloidal modeling and DLS. The relaxivity of the complexes was related to aggregation behavior observed through DLS. This indicated the presence of a hydrophobic interaction between the PPO layers of neighboring complexes. When this interaction was large enough, the complexes exhibited an increased relaxivity and cellular uptake. Thus, we have developed a methodology that allows for design of polymer-magnetite complexes with controlled sizes (within 8% of predicted values). Application of this methodology incorporated with modified DLVO theory aids in the design of colloidally stable complexes with minimum polymer loading. Finally, determination of an anchor group stable in the presence of phosphate salts at all magnetite loadings allows for the design of materials with minimum polymer loadings in biological systems. / Ph. D.

Polymers, among metals and ceramics, are major solid materials which are widely used in all kinds of applications. Polymers are of particular interest because they can be tailored with desirable properties. Polymer-based complexes and composites, which contain both the polymers and other components such as metal oxide/salts, are playing a more and more important role in the material fields. Such complexes and composites may display the benefits of both the polymer and other materials, endowing them with excellent functionalities for targeted applications. In this dissertation, a great deal of research was conducted to synthesize novel polymers and build polymeric complexes and composites for biomedical and aerospace applications. In chapter 3, two methods were developed and optimized to fabricate sub-micron high-performance polymer particles which were subsequently used to coat onto functional carbon fibers via electrostatic interactions, for the purpose of fabricating carbon fiber reinforced polymer composites. In chapter 4, a novel Pluronic® P85-bearing penta-block copolymer was synthesized and formed complexes with magnetite. The complexes displayed non-toxicity to cells normally but were able to selectively kill cancer cells without killing normal cells when subjected to a low-frequency alternating current magnetic field. Such results demonstrated the potential of such polymeric complexes in cancer treatment. Chapter 5 described the synthesis of several ionic graft copolymers primarily bisphosphonate-containing polymers, and the fabrication of polymer-magnetite complexes. The in-depth investigation results indicated the capability of the complexes for potential drug delivery, imaging, and other biomedical applications. Chapter 6 described additional polymer synthesis and particle or complex fabrication for potential drug delivery and imaging, as well as radiation shielding. / PHD / Polymers, metals, and ceramics are three major classes of solid materials that are used every day and everywhere. Polymers are of particular significance because they can be tailored to possess certain desirable properties, and, hence, they are playing a more and more important role as substitutes for metals and ceramics in a wide array of applications. Engineering and high-performance polymers were synthesized with excellent properties for biomedical and aerospace applications. Polymers can be fabricated into composites and complexes which contain not only polymers but also other materials, such as metal oxides/salts, carbon fibers, glass fibers, etc. When composites and complexes are made with sufficient stability, the materials may display the advantages of each component, making them more promising for specific applications. In this dissertation, effort was focused on developing versatile polymer-based complexes and composites for aerospace and biomedical applications. Chapter 3 describes the fabrication of sub-micron high-performance polymer particles by two methods and they were subsequently coated onto functional carbon fibers for making composites. Chapter 4 describes the synthesis of a novel copolymer that formed complexes with magnetite nanoparticles. The complexes were able to selectively kill cancerous cells without killing normal cells when exposed to an external magnetic field, and thus these materials have potential for cancer treatment. Chapter 5 describes the fabrication of phosphonate-bearing ionic copolymer-magnetite complexes and their potential applications in drug delivery, imaging, and other biomedical applications. Chapter 6 describes the synthesis of polymers and their corresponding complexes for potential drug delivery and imaging, as well as potential radiation shielding applications.

The research presented in this thesis focuses on the synthesis of three amphiphilic block copolymer systems containing poly(ethylene oxide) (PEO) blocks. The polymer systems were developed for use in biomedical applications. The first of these is a series of poly(ethylene oxide-b-oxazoline) (PEO-b-POX) diblock copolymers for use in the progress towards novel non-viral gene transfer vectors. Poly(ethylene oxide-b-2-ethyl-2-oxazoline) (PEO-b-PEOX) and poly(ethylene oxide-b-2-methyl-2-oxazoline) (PEO-b-PMOX) were investigated. The PEOX block was hydrolyzed with acid to form linear polyethylenimine (L-PEI). The polycation L-PEI is well known for its DNA binding efficiency but the water solubility of the resulting DNA/polymer complex is limited. Addition of a PEO block is directed towards the formation of a water dispersible DNA/copolymer complex. Dynamic light scattering of the PEO-b-PEOX and PEO-b-PEI block copolymers indicated that both systems existed as single chains in aqueous solution at pH 7. PEO copolymers also play a significant role in the formation of magnetic magnetite nanoparticles, which are dispersible in water at biological pH (pH =7). There is significant interest in the design of magnetic nanoparticle fluids for biomedical applications including magnetic field-directed drug delivery, magnetic cell separations, and blood purification. For use in vivo, the magnetite nanoparticles must be coated with biocompatible materials. Such polymers render the nanoparticles dispersible in water. Harris1 et al. synthesized PEO based, polyurethane triblocks with pendant carboxylic acid groups for use in formation of stable aqueous magnetic fluids. Building from this work, two polyurethane and polyurethaneurea systems were synthesized with 1300 g/mol PEOX and 2500 g/mol and PEOX2070 g/mol poly(ethylene oxide-co-propylene oxide) tailblocks, respectively. The PEO/PPO random copolymer contained about 25 weight percent PPO, and this disrupted the capacity of the PEO to crystallize. The PEOX based urethane triblocks were synthesized through reacting the tailblocks with the monomers for the center block whereas the PEO/PPO based polyurethaneurea was synthesized through forming the central urethane block with pendant acid groups first and then terminating the copolymer with the monofunctional copolymer. Terminal amine groups on the PEO/PPO tailblock afforded a triblock linked with two urea groups. The new polyurethanes with the PEOX tailblocks and the new polyurethaneurea with the PEO/PPO tailblocks could be utilized to efficiently stabilize magnetite nanoparticles in water. / Master of Science

In the 50+ years since the discovery of magnetic compass orientation by migratory songbirds, evidence for the use of magnetic cues has been obtained for a range of taxonomic groups, including several classes of vertebrate and invertebrate taxa. Surprisingly, however, the biophysical mechanisms and biological substrate that underlie magnetic sensing are still not fully understood. Moreover, while use of magnetic cues for compass orientation is intuitive, the functional significance of other forms of behavioral responses mediated by magnetic cues, such as spontaneous magnetic alignment, is less clear. The following research was carried out to investigate the mechanisms underlying magnetic orientation in vertebrates and invertebrates. This involved the modification of existing experimental systems to characterize responses to magnetic cues in laboratory animals (flies, mice) and the development of novel techniques for studying the role of magnetic cues in the spatial behavior of free-living animals (red foxes). Chapter II examines magnetic orientation in wild-type Drosophila melanogaster larvae. We show that three strains of larvae reared under non-directional ultraviolet (UV) light exhibit quadramodal spontaneous orientation along the anti-cardinal compass directions (i.e. northeast, southeast, southwest, northwest) when tested in a radially symmetrical environment under UV light. Double-blind experiments cancelling the horizontal component of the magnetic field confirmed that the response is dependent on magnetic cues rather non-magnetic features of the test environment. Furthermore, we argue that the larval quadramodal pattern of response is consistent with properties of magnetic compass orientation observed in previous studies of adult Drosophila and laboratory mice, both of which have been proposed to be mediated by a light-dependent magnetic compass mechanism. Chapter III explores the use of novel biologging techniques to collect behavioral and spatial data from free-roaming mammals. Specifically, a previous observational study of free- roaming red foxes found a 4-fold increase in the success of predatory 'mousing' attacks when foxes were facing ~north-northeast, consistent with magnetic alignment responses reported for a range of terrestrial animals. The authors propose that the magnetic field may be used to increase accuracy of mousing attacks. Using tri-axial accelerometer and magnetometer bio-loggers fitted to semi-domesticated red foxes, we created ']magnetic ethograms' from behavioral and magnetic machine learning algorithms 'trained'] to identify three discrete behaviors (i.e. foraging, trotting, and mousing-like jumps) from raw accelerometer signatures and to classify the magnetic headings of mousing-like jumps into 45° sectors from raw magnetometer data. The classifier's ability to accurately identify behaviors from a separate fox not used to train the algorithm suggests that these techniques can be used in future experiments to obtain reliable magnetic ethograms for free-roaming foxes. We also developed the first radio-frequency emitting collar that broadcasts in the low MHz frequency range shown to disrupt magnetic compass responses in a host of animals. The radio-frequency collars coupled with biologgers will provide a powerful tool to characterize magnetic alignment responses in predatory red foxes and can be adapted for use in studies of magnetic alignment and magnetic compass orientation in other free-roaming mammals. Chapter 3 discusses findings from a magnetic nest building assay involving male labratory mice. Mice trained to position nests in one of four directions relative to the magnetic field exhibited both learned magnetic compass responses and fixed magnetic nest positioning orientation consistent with northeast-southwest spontaneous magnetic alignment behavior previously reported for wild mice and bank voles. This is the first mammalian assay in which both learned magnetic compass orientation and spontaneous magnetic alignment were exhibited in the same species, and suggests that the use of magnetic cues in rodents may be more flexible that previously realized. / Ph. D. / A variety of animals have been shown to use the Earth’s magnetic field to help guide diverse spatial behaviors, however, the underlying sensory mechanisms mediating this sense remain elusive. Evidence for two distinct sensory mechanisms has come from behavioral studies involving a wide range of organisms, including migratory birds, newts, mole rats, mice, and several classes of invertebrates. The following research was carried out to determine the underlying sensory mechanisms mediating magnetic sensing in larval fruit flies. Properties consistent with a light-dependent, photoreceptor-based mechanism were found to underlie innate magnetic alignment behavior in larval flies, similar to the proposed compass mechanism thought to mediate compass responses in migratory birds and newts. A reanalysis of two previous studies of learned magnetic compass responses in adult fruit flies and laboratory mice show similar behaviors when compared to that of larval flies, suggesting a common underlying light-dependent magnetic mechanism across these groups. Furthermore, we provide evidence for learned magnetic compass responses in laboratory mice, where the orientation of individuals appears to be dependent on properties of the local environment (e.g. electromagnetic, temperature, humidity) in training and testing. These data suggest that the use of magnetic cues in mammals is context-dependent and more flexible than previously recognized. We have also developed new technologies for studies of magnetic orientation in free-roaming animals. Specifically, bio-logging devices containing triaxial accelerometer and magnetometer sensors where used to create ‘magnetic ethograms’, where the behavior and magnetic alignment of an animal can be reliably and accurately extracted from raw sensor data. We also discuss possible field experiments that can be performed to provide a specific test of the underlying sensory mechanism mediating magnetic behavior in free-roaming animals. This work will likely be of interest to a broad range of disciplines including sensory ecology, ethology, quantum chemistry, biophysics, wildlife management, and conservation.

The iron apatite mineralizations of northern Sweden are mainly situated in supracrustal rocks and are thought to have formed during approximately the same time as the major plutonic suites in northern Sweden. In this thesis the Malmberget iron apatite ore deposit have been compared to the Kiruna iron apatite ore deposit to see whether the role of hydrothermal processes are different between the two ore districts. Also, since it has proven problematic to distinguish between the different mafic and ultramafic members of the major plutonic suites in northern Sweden (i.e. the Haparanda suite (1.94-1.85 Ga), the Perthite-monzonite suite (PMS) (1.87 Ga) and the Edefors suite (1.80-1.79 Ga)), a second goal is to trace the distribution and distinguish between these suites. Major elements, REE and trace elements have been studied along with polished sections from the ores and oxygen isotopes of magnetites from the ore districts to trace the ore formation process and separate between suites. All ore districts display a close similarity in geochemistry between host rocks and magnetites, especially regarding the REE pattern. Oxygen isotopes show that samples from the Kiruna district plot exclusively at positive δ18O-values with the majority of them at values < 1‰. Samples from the Malmberget district display δ18O-values either close to the igenous range or at slightly negative values. However, samples that display very low or negative δ18O-values show signs of either high temperature hydrothermal alteration, oxidation or crustal contamination. The δ18O composition along with textural observations from the polished sections and geochemistry, points towards a magmatic origin for these deposits. No apparent evidence has been found to support a primary ore formation by hydrothermal process in any of the districts studied. Regarding the suites, normalized spider plot patterns of REEs and trace elements served as a basis for subdivision into groups by similarities in key identification parameters. Several patterns are characterized by a pronounced Eu-trough while the middle- to HREEs display a rather flat trend, criteria that are related to rocks from the Haparanda suite, while samples with positive Eu-anomaly (Eu/Eu* > 1) and a nearly flat trend from La to Pr with a marked positive peak at Sr and generally less enriched in LILE, are consistent with the Edefors suite. Also, the Edefors suite generally display low concentrations of both Th and U but are somewhat enriched in Sr with relation to Pr. No distinct geochemical features could help to separate between the Haparanda and the PMS suites.

Ce travail concerne le développement, la mise au point et la modélisation d’un procédé de précipitation de nanoparticules. Le précipité « modèle » étudié est la magnétite (Fe3O4). La méthode chimique de Massart est choisie pour fabriquer les nanoparticules de magnétite, car elle est déjà bien étudiée. Un procédé de précipitation est conçu en réacteur semi-fermé et à recirculation du fluide de la cuve, permettant ainsi de réaliser un mélange intensif des fluides réactifs par des mélangeurs rapides (un tube en T et deux mélangeurs Hartridge-Roughton de tailles différentes). Différents paramètres opératoires sont testés pour déterminer leur influence sur la qualité du précipité. De nombreuses techniques analytiques sont mises en œuvre pour déterminer les propriétés des nanoparticules obtenues. Les résultats montrent que, malgré une chimie inchangée, le type de microréacteur choisi influence sensiblement la qualité des nanoparticules élémentaires et des agglomérats de magnétite. Le potentiel de nano-adsorption de la magnétite est aussi étudié et se révèle prometteur. Enfin, la modélisation hydrodynamique des mélangeurs rapides est réalisée par CFD / The present work is focused on developing and modeling a precipitation process for the production of magnetite (Fe3O4) nanoparticles. The Massart chemical method is chosen to obtain the magnetite nanoparticles owing to its detailed study on the reaction parameters. A semi-batch reactor with a recirculation system is chosen to realize this precipitation process and rapid mixers (T mixer and Hartridge-Roughton mixers of different dimensions) are used to provide an intensive mixing of reagent fluids. Different operating parameters are tested to determine their influences on the precipitate quality. Many analytic techniques are employed to determine the properties of obtained nanoparticles. The results indicate that, without changing of chemical parameters, the quality of magnetite elementary nanoparticles and agglomerates depend sensibly on the type of microreactors utilized. In addition, the magnetite nanoparticles are considered to be a hopeful nanoadsorbent and the related tests are studied. Finally, the CFD technique is used to model the hydrodynamic behaviors of the rapid mixers

Die Wechselwirkung von Wasser und CO2 mit Oxidoberflächen ist vor allem ein bedeutsames Thema für Umweltnaturwissenschaftler. Der Gebrauch von Wasser als Wasserstoff-Ressource für die Reduktion/Hydrierung von CO2 würde zu einer Reduktion der CO2-Emmissionen in der Atmosphäre führen. Trotz einiger Fortschritte in diesem Bereich sind weitere grundlegende Studien notwendig, um die Wechselwirkung von Wasser und CO2 mit Metalloxidoberflächen zu verstehen und darauf aufbauend eine rationale Gestaltung Katalyse-Prozesse zu ermöglichen. Die vorliegende Arbeit präsentiert grundlegende Studien der Adsorption von Wasser und CO2 auf wohldefinierten Fe3O4(111) Filmen, welche auf einem Pt(111) Einkristall aufgewachsen wurden. Die Oberfläche wurde zuerst durch Adsorption von CO als Sondenmolekül gestützt. Es zeigt sich, dass die Magnetitoberfläche aus einer 1/4-Monoschicht tetraedrisch angeordneter Fe3+-Ionen auf einer dicht gepackten Sauerstoffschicht besteht. Auf dieser gut charakterisierten Oberfläche wurde die Wechselwirkung mit Wasser und CO2 sodann detailliert untersucht. Kombinierte IRAS- und TPD-Daten deckten auf, dass Wasser leicht an der Oberfläche dissoziiert und unter Einbeziehung von Sauerstoffatomen aus dem Wasser selbst bzw. von der Oxidoberfläche zwei Hydroxylspezies bildet. Diese Spezies fungieren als Anker für die molekulare Wasseradsorption, die schließlich zu einer geordneten Struktur führt. DFT-Rechnungen rationalisieren diese Ergebnisse im Rahmen einer kooperativen Bildung des Wasserstoffbrückenbindungsnetzwerkes. Die Magnetitoberfläche scheint hingegen eher träge gegenüber der CO2-Chemisorption zu sein. Bei niedrigen Temperaturen kann die Bildung schwacher chemisorbierter Spezies als durch Oberflächendefekte bedingt interpretiert werden. In jedem Fall spielt bei höheren Temperaturen das Vorhandensein von Wasser auf der regulären Oberfläche eine entscheidende Rolle in der CO2-Aktivierung und fördert die Bildung von Bikarbonat-Spezies. / The interaction of water and CO2 with oxide surfaces is nowadays a hot topic especially for environmental scientists. The use of water as hydrogen for CO2 reduction/hydrogenation would be the most ideal process, which would contribute to reduce CO2 emission into the atmosphere and minimize the dependence of society on fossil fuels. Despite certain advances in this field, further fundamental studies need to be addressed to understand the interaction of water and CO2 with metal-oxide surfaces for a rational design of heterogeneous catalytic processes. This work presents a fundamental study of the adsorption of water and CO2 on well-defined Fe3O4(111) films grown on Pt(111) single crystal. To understand the adsorption properties of the iron oxide film, the surface has been characterized using CO as probe molecule. The characterization showed that the magnetite surface is terminated by a 1/4 monolayer of tetrahedrally coordinated Fe3+ ions on top of a close-packed oxygen layer. On this well characterized surface, the interaction with water and CO2 has been investigated in detail. Combined IRAS and TPD data revealed that water readily dissociates on the surface, forming two hydroxyl species, OwH and OsH, involving oxygen atoms from the water (w) itself and from the oxide surface (s), respectively. At increasing coverage, these species act as anchors for molecular water adsorption ultimately giving rise to a long-range ordered architecture. DFT calculations rationalized these data in the framework of cooperative formation of the hydrogen bonding network. Moreover, Fe3O4(111) seems to be rather inert towards CO2 chemisorption at low temperatures, and the formation of weak chemisorbed species may be interpreted as driven by surface imperfections. At higher temperatures, the presence of water on the regular surface (induced and/or just as residual gas adsorption) plays a critical role in the CO2 activation, promoting the formation of bicarbonate-like species.

Le fer et ses composés, notamment les (oxyhydr)oxydes, sont présents dans la nature et produits par les activités anthropiques. Ce caractère ubiquiste du fer et sa sensibilité aux conditions environnementales en fait un excellent traceur de sources et de processus.Cette thèse a pour objectif de tracer l’impact de l’Homme sur les matières en suspension (MES) de la Seine à partir des propriétés magnétiques de sa fraction ferrugineuse en utilisant les outils et méthodes du magnétisme environnemental.Un échantillonnage des MES a permis de couvrir le cours de la Seine et ses affluents durant différents contextes hydrologiques. Des analyses ont été conduites sur ces MES afin de caractériser les particules ferrugineuses magnétiques et d'examiner leurs relations avec les conditions environnementales dans lesquelles elles se sont formées et/ou ont évolué.La magnétite apparait comme l’oxyde dominant et montre une forte affinité avec la fraction fine des MES et ses propriétés magnétiques peuvent être utilisées pour décrire la charge sédimentaire de la Seine et les phénomènes de remise en suspension.Des augmentations de tailles et de concentration de magnétites sont associées à l’urbanisation et aux activités industrielles. Les variations spatiales entre amont et aval des confluences et les variations temporelles montrent que le cours d’eau joue un rôle dans les mécanismes d’accumulation, transport et dilution de ces particules. / Iron and its compounds, in particular iron (hoxyhydr)oxides are ubiquitous in both nature and human activity, and are sensitive to environmental conditions. They can hence be used as environmental source and process tracers.This thesis focuses on tracing the human activities impact in the ferruginous compound of the suspended particulate matter (SPM) in the Seine River (France) using environmental magnetism tools.SPM sampling was conducted along the Seine path and its tributaries during different hydrological contexts. Magnetic properties were measured to characterize the ferruginous magnetic particles and to examine their relationship with the environment in which they have been formed.The main magnetic carrier is magnetite. It is concentrated in the fine sediment fraction and its magnetic properties can be used to trace the sediment load and hydrodynamic processes of the Seine.Increases in concentration and grain size of magnetite particles are associated to urbanization and industrial activities which are sources of anthropogenic particles. Significant variations can be observed between upstream and downstream of confluences and in the temporal scale and can be associated to hydrodynamic processes such as dilution, accretion, transport and re-suspension of the ferruginous particles.