Дисертації з теми "Magnetic carbon"

Magnetism of carbon-based materials is a challenging area for both fundamental research and possible applications. We present studies of low-dimensional carbon-based magnetic systems (fullerene-diluted molecular magnets, carbon nanotubes, graphite fluoride, and nanoporous carbon) by means of SQUID magnetometer, X-ray diffraction and vibrational spectroscopy, the latter techniques used as complementary instruments to find a correlation between the magnetic behaviour and the structure of the samples.In the first part of the thesis, characteristic features of the magnetization process in aligned films of carbon nanotubes with low concentration of iron are discussed. It is shown that the magnetism of such structures is influenced by quantum effects, and the anisotropy behaviour is opposite to what is observed in heavily doped nanotubes.In the second part, Mn12-based single molecular magnets with various carboxylic ligands and their 1:1 fullerene-diluted complexes are studied. We prove that magnetic properties of such systems strongly depend on the environment, and, in principle, it is possible to design a magnet with desirable properties. One of the studied compounds demonstrated a record blocking temperature for a single molecular magnet. Both fullerene-diluted complexes demonstrated “magnetization training” effect in alternating magnetic fields and the ability to preserve magnetic moment.The third and the fourth parts of the thesis are dedicated to the analysis of various contributions to the magnetic susceptibility of metal-free carbon-based systems – intercalated compounds of graphite fluorides and nanoporous oxygen-eroded graphite. The magnetic properties of these systems are strongly dependent on structure, and can be delicately tuned by altering the π-electron system of graphite, i. e. by degree of fluorination of intercalated compounds and by introduction of boron impurity to the host matrix of nanoporous graphite.
Magnetism av kolbaserade material är ett utmanande område för både grundforskning och möjliga tillämpningar. Vi presenterar studier med låg-dimensionella kolbaserade magnetiska system (fulleren-utspädda molekylära magneter, kolnanorör, grafit fluorid och nanoporösa kol) med hjälp av SQUID magnetometer, röntgendiffraktion och vibrerande spektroskopi, de senare tekniker som används som komplement instrument för att finna sambandet mellan den magnetiska uppträdande och strukturen hos proven. I den första delen av avhandlingen är egenheter från magnetisering processen i linje filmer av kolnanorör med låg koncentration av järn diskuteras. Det visas att magnetism av sådana strukturer påverkas av kvantmekaniska effekter och anisotropin beteende är motsatsen till vad som observerats i kraftigt dopade nanorör. I den tvåa delen är Mn12-baserade enda-molekyl magneter med olika karboxylsyror ligander och deras 1:1 fulleren-utspädda komplex studeras. Vi visar att magnetiska egenskaperna hos sådana system beror i hög grad på miljön, och i princip är det möjligt att utforma en magnet med önskvärda egenskaper. En av de studerade föreningarna visade en post blockeringstemperaturen för en enda molekylär magnet. Både fulleren-utspädda komplex visade "magnetisering utbildning" effekt i alternerande magnetfält och möjligheten att bevara magnetiskt moment. Den tredje och fjärde delarna av avhandlingen är avsedda för inneboende magnetism av analys av olika bidrag till magnetisk susceptibilitet av metall-fritt kol-baserade system -inskjutna föreningar grafit fluorider och nanoporösa O2-eroderade grafit. Magnetiska egenskaperna hos dessa system är starkt beroende av strukturen, och kan fint avstämmas genom att man ändrar π-elektronsystem av grafit, i. e. med graden av fluorering av inskjutna föreningar och genom införandet av bor föroreningar till värd matris av nanoporösa grafit.

Les nanotubes de carbone (NTCs), en raison de leurs propriétés exceptionnelles et d’une utilisation potentielle dans un grand nombre d'applications, constituent surement la classe la plus étudiée des nanomatériaux. Les NTCs fonctionnalisés, qui peuvent être facilement manipulés et modifiés par liaison covalente ou fonctionnalisation non covalente, apparaissent comme de nouveaux outils dans le domaine des biotechnologies et en biomédecine. En effet, les NTC ont des propriétés optiques, électroniques et mécaniques qui peuvent être exploitées dans des applications biologiques ou biomédicales. Les nanoparticules magnétiques métalliques (NPMMs) de la série 3d ainsi que leurs alliages présentent d'excellentes propriétés magnétiques contrairement à leurs homologues oxydes, qui peuvent être exploitées en biomédecine et pour l'enregistrement magnétique ultra-haute densité. Les nano-matériaux confinés dans les NTCs peuvent présenter des propriétés et des comportements différents par rapport aux matériaux massifs. Divers effets de confinement provenant de l'interaction entre les matériaux confinés et les cavités internes des nanotubes de carbone offrent des possibilités de réglage ou la conception de nouveaux nanocomposites. Cette thèse est consacrée à l’étude d’une nouvelle approche pour le développement de matériaux nanocomposites NPMMs@NTC et de leurs propriétés. Des NPMMs de taille et forme contrôlée de Co et de Fe ont été synthétisées avec de nouveaux ligands aromatiques comme stabilisants. Ces MMNPs ont ensuite été introduites de manière sélective dans la cavité de NTCs du fait d’interactions attractives/répulsives entre les nanotubes de carbone multi-parois fonctionnalisés et les NPMMs. Nous nous sommes ensuite intéressés à la protection de ces nanoparticules de l’oxydation par l’air. Les nanoparticules de fer confinées ont ainsi été revêtues par du polyisoprène. Pour ce faire, la surface des nanoparticules de Fe a été modifiée avec un catalyseur de polymérisation par échange de ligand, puis la polymérisation de l'isoprène a été réalisée à l'intérieur du canal des NTCs. La protection de l'oxydation par le polyisoprène a été évaluée par des mesures magnétiques après exposition à l'air. De façon tout à fait surprenante, cette étude a montré que les nanoparticules de fer les plus résistantes à l’oxydation étaient celles obtenues après échange de ligand et sans polymérisation. Dans ce cas seulement les propriétés des nanoparticules originales sont maintenues après mise à l’air. Enfin, des nanostructures (particules ou fils) magnétiques bimétalliques associant le Pt au cobalt ou au fer ont été obtenues et confinées dans les NTCs. Leurs structures chimiques ordonnées ont également été étudiées par des études de recuit thermique. Le travail développé dans cette thèse ouvre de nouvelles perspectives pour la production de nouveaux nanocomposites MMNPs@NTC résistants à l’oxydation
Carbon nanotubes (CNTs), because of their unique properties and potential use in a variety of applications, are probably the most studied class of nanomaterials. Functionalized CNTs, which can be easily manipulated and modified by covalent or non-covalent functionalization, appear as new tools in biotechnology and biomedicine. Indeed, CNTs have optical, electronic and mechanical properties that can be exploited in biological or biomedical applications. Metallic magnetic nanoparticles (MMNPs) of the 3d series and their alloys exhibit excellent magnetic properties unlike their oxide counterparts, which can be exploited in biomedicine and ultra-high density magnetic recording. When confined in CNTs nano-materials can have different properties and behaviors compared to bulk materials. Various confinement effects resulting from the interaction between the confined materials and the internal cavities of CNTs provide opportunities for regulating or designing new nanocomposites. This thesis is devoted to the study of a new approach for the development of nanocomposite materials MMNPs@CNTs and their properties. MMNPs of controlled size and shape of Co and Fe were synthesized with novel aromatic ligands as stabilizers. These MMNPs were then selectively introduced into the cavity of CNTs due to repulsive/attractive interactions between the functionalized multi-walled CNTs and the MMNPs. We were then interested in the protection of these nanoparticles from oxidation by air. Thus, confined iron nanoparticles have been coated with polyisoprene. To do this, the surface of the Fe nanoparticles has been modified with a polymerization catalyst by ligand exchange; then, polymerization of isoprene was conducted inside the channel of CNTs. The protection from oxidation by the polyisoprene was evaluated by magnetic measurements after exposure to air. Quite surprisingly, this study showed that the iron nanoparticles the more resistant to oxidation were those obtained after ligand exchange and without polymerization. In this case only, the original properties of the nanoparticles are maintained after venting. Finally, magnetic bimetallic nanostructures (particles or rods) combining Pt and cobalt or iron were obtained and confined in CNTs. Their chemical structure orderings were also studied by thermal annealing studies. The work developed in this thesis opens up new perspectives for the production of new MMNPs@NTC nanocomposites resistant to oxidation

Carbon nanotubes (CNTs) functionalized/embedded with ferromagnetic particles have several important advantages as materials for magnetic applications. The presence of ferromagnetic particles in a carbon matrix can substantially change the magnetic properties of CNT-based composites. For example, iron filled CNTs have been used as probes in magnetic force microscopy (MFM), and have potential in magnetic data storage applications. In addition, encapsulation in nanotubes provides iron nanoparticles with resistance to oxidation and mechanical damage. Chemical vapor deposition (CVD) is one of the most common single-step processes for the fabrication of high quality carbon nanotubes containing varying amounts of embedded ferromagnetic particles. This process results in the effective magnetic functionalization of CNTs and opens the door to numerous new applications. However, in order to optimize these materials for any application, their properties need to be understood. This study explores the ferromagnetic properties of carbon nanotubes containing nano-scaled iron particles which were derived from thermal decomposition of ferrocene. Both room temperature as well as low-temperature magnetic measurements will be presented and the results analyzed in the light of available theory.

This thesis describes studies of graphene, single walled carbon nanotubes (SWNTs) and InSb. Optical and electronic measurements probe the effects of high magnetic fields on these low-dimensional systems. Chapter 1 introduces a theoretical description and background behind the materials and physical phenomena studied in this work. The structure and unique properties of carbon nano-materials are described. The experimental methods used in this thesis are described in Chapter 2. Chapter 3 describes magnetotransport measurements on InSb/AlInSb heterostructures revealing that the large energy gaps, and extremely high mobility, associated with this system leads to exceptionally well defined quantum Hall plateaux for both even (Landau level) and odd (spin-split) filling factors. Even higher cyclotron energy gaps are expected in graphene. Chapter 4 reveals that due to a combination of large cyclotron energy gaps and fast electron-phonon energy loss rates, the quantum Hall effect (QHE) in graphene can be observed to unprecedented current densities (43 A/m) and temperatures (> 45 K). The behaviour of epitaxial graphene grown on silicon carbide in the quantum Hall regime is shown to be characterised by a strongly magnetic field dependent carrier density due to charge transfer from surface donor states in the substrate. Chapter 5 shows that polymer wrapping of SWNTs can achieve high quality purified samples. Individual SWNTs were probed using micro-photoluminescence measurements in magnetic fields up to 30 T. The combination of high magnetic fields and high spectral and spatial resolution allowed a detailed study of exciton fine structure. High intensity laser irradiation is shown to induce bound excitons in pristine tubes. The optical properties of a number of tubes are dominated by defect sites which may be imaged along the tube using the magnetic brightening of dark excitons associated with such defects.

Electrically detected magnetic resonance (EDMR) is a sensitive spectroscopic technique, which can be used to readout few to single electron spins in semiconductor and carbon nanodevices for applications in solid state quantum information processing (QIP). Since only electrically active defects contribute to the EDMR signal, this technique can be used further to investigate defects and impurities in photovoltaic devices, in which they limit the sunlight-to-energy conversion efficiency significantly. Here, I employ X-band EDMR for semiconductor defect analysis and identify the most important recombination centres in Czochralski silicon with oxide precipitates, which can be intentionally grown to confine detrimental metallic impurities to inactive regions of the wafer in order to serve as a defect-free substrate for modern silicon photovoltaic devices. Those experiments show that oxide precipitation is accompanied by the formation of silicon dangling bonds. Furthermore, I describe a very promising route towards the fabrication and readout of few to single electron spins in carbon nanotube devices, which can be characterised structurally via transmission electron microscopy in order to relate their electrical and spin properties with their structure. Finally, I employ EDMR to read out electron spin states in donor-doped silicon field-effect transistors as a prerequisite for their application in QIP. I report on a novel cryogenic probe head for EDMR experiments in resonant microwave cavities operating at 0.35 T (9.7 GHz, X-band) and 3.34 T (94 GHz, W-band). This approach overcomes the inherent limitations of conventional X-band EDMR and permits the investigation of paramagnetic states with a higher spectroscopic resolution and signal intensity. Both advantages are demonstrated and discussed. I further report on a novel mechanism giving rise to the EDMR effect in donor-doped silicon field-effect transistors, which is capable of explaining why the EDMR signal intensities of the conduction electrons are enhanced by a factor of ∼100, while the donor resonance signals increase by a factor of ∼20 from X- to W-band only. The spin-relaxation and dephasing times are extracted from a series of pulsed-EDMR measurements and confirm this model. The author gratefully acknowledges funding from Trinity College Oxford, Department of Materials, EPSRC DTA, and Konrad-Adenauer-Stiftung e.V. (Begabtenförderung).

Multifunctional nanocomposites are promising for a variety of applications ranging from microwave devices to biomedicine. High demand exists for magnetically tunable nanocomposite materials. My thesis focuses on synthesis and characterization of novel nanomaterials such as polymer nanocomposites (PNCs) and multi-walled carbon nanotubes (MWCNTs) with magnetic nanoparticle (NP) fillers. Magnetite (Fe3O4) and cobalt ferrite (CoFe2O4) NPs with controlled shape, size, and crystallinity were successfully synthesized and used as PNC fillers in a commercial polymer provided by the Rogers Corporation and poly(vinylidene fluoride). Magnetic and microwave experiments were conducted under frequencies of 1-6 GHz in the presence of transverse external magnetic fields of up to 4.5 kOe. Experiments confirm strong magnetic field dependence across all samples. When incorporated in to a cavity resonator device, tangent losses were reduced, quality factor increased by 5.6 times, and tunability of the resonance frequency was demonstrated, regardless of NP-loading. Work on PNC materials revealed the importance of NP interactions in confined spaces and motivated the study of confinement effects of magnetic NPs in more controlled environments, such as MWCNTs with varying diameters. MWCNTs were synthesized with diameters of 60 nm, 100 nm, 250 nm, and 450 nm to contain magnetic NP fillers (~10 nm) consisting of ferrites of the form MFe2O4, where M = Co2+, Ni2+, or Fe2+. All confined samples exhibit superparamagnetic-like behavior with stronger magnetic response with respect to increasing MWCNT diameter up to 250 nm due to the enhancement of interparticle interactions. This thesis provides the first systematic study of this class of nanocomposites, which paves the way to inclusion of novel nanostructured materials in real-world applications.

Los nanomateriales, especialmente las nanopartículas, se convierten en una de las áreas más atractivas no sólo en la investigación científica, sino también en las aplicaciones industriales. En esta tesis se ha estudiado la preparación de nanopartículas de magnetita, sus nanocompuestos relacionados y la aplicación de los nanomateriales obtenidos. Las nanopartículas core-shell de Fe3O4@SiO2 se sintetizaron mediante métodos de microemulsión inversa estándar y de microondas. Las nanopartículas obtenidas se caracterizaron con diferentes técnicas de laboratorio y se estudiaron los diferentes efectos al cambiar algunos parámetros (temperatura, concentración, tiempo) de la reacción. Las nanopartículas se utilizaron como soporte de catalizadores de Ag y los nanocompuestos sintetizados mostraron una buena propiedad catalítica y una alta capacidad de reciclaje. También se prepararon nuevas nanocápsulas de Fe3O4@GNF@SiO2 mediante la formación in situ de nanopartículas de magnetita y el proceso de cobertura de sílica. Los nanocapsulados obtenidos tienen una buena estabilidad incluso en ambientes ácidos. También se estudió la posible aplicación de estas nanocápsulas por resonancia magnética. Por otra parte, se estudió la citotoxidad e interacción del core-shell Fe3O4 @ SiO2 de las nanopartículas unidas a células, para asegurarse una posible aplicación en investigación biomédica obteniendo un resultado favorable y de baja toxicidad. A continuación, las nanopartículas Fe3O4 @ SiO2 se decoraron añadiendo biomoléculas tales como MC540 y L-tiroxina las cuales muestran una posible aplicación en el estudio de biosensores.
Nanomaterials especially nanoparticles become one of the most attractive area not only in scientific research but also in industrial applications. In this thesis, the preparation of magnetite nanoparticles, their related nanocomposites and the application of those obtained nanomaterials have been studied. The Fe3O4@SiO2 core-shell nanoparticles were synthesized via normal and microwave assistance reverse microemulsion methods. The obtained nanoparticles were fully characterized with different laboratory techniques and the effect of reaction parameters on final products was also studied. These nanoparticles were used as a support of Ag catalysts nanoparticles and the as synthesized nanocomposites shown nice catalytic property and high recyclability. A novel Fe3O4@GNF@SiO2 nanocapsulates were also prepared via in situ formation of magnetite nanoparticles and silica coverage process. The obtained nanocapsulates have nice stabilities even in the acid environments. The potential application of these nanocapsulates in magnetic resonance imaging research was also studied. On the other hand, the cytotoxity and interaction with cell of Fe3O4@SiO2 core-shell nanoparticles were studied which indicate the possibility of using them in biomedical research. Then, the Fe3O4@SiO2 core-shell nanoparticles were further decorated with biomolecules such as MC540 and L-thyroxine. The Fe3O4@SiO2 core-shell nanoparticles with the surface functionalized with molecule imprinted polymers also suggested the potential application in biosensor research.

La découverte des nanotubes de carbone, il y a maintenant une vingtaine d'années, a été un des moteurs de la recherche des nanotechnologies. Ces particules illustrent l'amalgame entre le monde macroscopique et le monde appelé nano. Cette discipline a également relancée la recherche sur le graphite et le carbone en général, qui atteint un nouveau sommet avec la découverte du graphène, une monocouche de graphite. Rapidement la physique des nanotubes et du graphène ont suscité l'intérêt d'être étudié sous champ magnétique avec la découverte de l'effet Aharonov-Bohm dans les nanotubes ou l'effet hall quantique dans le graphène. Cette thèse a pour but d'approfondir la connaissance des propriétés optiques des nanotubes, du graphène et du graphite sous champ magnétique intense. Pour cela nous nous interesserons dans un premier temps à la problématique des excitons sombres. Nous étudierons ensuite les propriétés magnétiques et dynamiques des tubes. La famille métallique est paramagnétique le long de son axe et diamagnétique perpendiculaire à celui-ci. La famille semiconductrice est diamagnétique par rapport à ces deux orientations mais la valeur perpendiculaire est plus élevée. De ce fait tous les nanotubes vont s'aligner parallèlement à un champ magnétique appliqué. Nous utiliserons des méthodes de spectroscopie optique pour étudier ce phénomène. La deuxième partie de la thèse consistera à examiner les propriétés optiques du graphène et du graphite et plus précisément les transitions entre niveaux de Landau sous champs intenses. La particularité du graphène est que ses porteurs de charge se comportent comme des particules relativistes avec une masse nulle. Les niveaux de Landau se trouvent modifiés avec une dépendance en racine du champ magnétique, par rapport aux systèmes deux dimensionels classiques, où l'on retrouve une dépendance linéaire comme pour l'électron libre par exemple. Ceci nous entrainera également à reéxaminer les propriétés du graphite et d'approfondir les connaissances, notamment à champ très élevé, sur ce matériau à priori bien connu et étudié dans le passé.

La découverte des nanotubes de carbone, il y a maintenant une vingtaine d'années, a été un des moteurs de la recherche des nanotechnologies. Ces particules illustrent l'amalgame entre le monde macroscopique et le monde appelé nano. Cette discipline a également relancée la recherche sur le graphite et le carbone en général, qui atteint un nouveau sommet avec la découverte du graphène, une monocouche de graphite. Rapidement la physique des nanotubes et du graphène ont suscité l'intérêt d'être étudié sous champ magnétique avec la découverte de l'effet Aharonov-Bohm dans les nanotubes ou l'effet hall quantique dans le graphène. Cette thèse a pour but d'approfondir la connaissance des propriétés optiques des nanotubes, du graphène et du graphite sous champ magnétique intense. Pour cela nous nous interesserons dans un premier temps à la problématique des excitons sombres. Nous étudierons ensuite les propriétés magnétiques et dynamiques des tubes. La famille métallique est paramagnétique le long de son axe et diamagnétique perpendiculaire à celui-ci. La famille semiconductrice est diamagnétique par rapport à ces deux orientations mais la valeur perpendiculaire est plus élevée. De ce fait tous les nanotubes vont s'aligner parallèlement à un champ magnétique appliqué. Nous utiliserons des méthodes de spectroscopie optique pour étudier ce phénomène. La deuxième partie de la thèse consistera à examiner les propriétés optiques du graphène et du graphite et plus précisément les transitions entre niveaux de Landau sous champs intenses. La particularité du graphène est que ses porteurs de charge se comportent comme des particules relativistes avec une masse nulle. Les niveaux de Landau se trouvent modifiés avec une dépendance en racine du champ magnétique, par rapport aux systèmes deux dimensionels classiques, où l'on retrouve une dépendance linéaire comme pour l'électron libre par exemple. Ceci nous entrainera également à reéxaminer les propriétés du graphite et d'approfondir les connaissances, notamment à champ très élevé, sur ce matériau à priori bien connu et étudié dans le passé
Carbon nanotubes are unique nano-objects with highly anisotropic electrical, magnetic and optical properties. In the past years the physics of carbon nanotubes made important steps toward the comprehension of its various complex physical properties. The optical response of nanotubes is driven by excitons. Of the sixteen possible exciton states only one decays radiatively. However a magnetic field can brighten one of the dark states. The aim of the first part of this thesis investigates the issue of the brightening of dark excitons. In the second part we use the magnetic properties of single walled carbon nanotubes to investigate their dynamic alignment in a pulsed magnetic field. Semiconducting tubes are diamagnetic both along and perpendicular to their long axis but the magnitude of the perpendicular susceptibility is higher. Metallic tubes are paramagnetic along their long axis and diamagnetic perpendicular to it. This constrains SWNT to align parallel to a magnetic field. Our data will be analysed with the aid of a theoretical model based on rotational diffusion of rigid rods. In the third part we study the magneto-optical properties of epitaxially grown multi-layer graphene. The Landau levels of graphene are different from standard two dimensional electron gases. They show a sqrt{B}dependence due to the relativistic nature of their charge carriers. We measure the system at high fields and high energies to probe the limit of massless Dirac fermions. The discovery of massless relativistic particles in graphene, a mono-layer of graphite, has completely renewed the interest in graphite. As a matter of fact graphite the optical properties of graphite are best described by bi-layer graphene. We show that the magneto-transmission experiments on thin graphite are in very good agreement with an effective bi-layer model. In addition we observe a non-predicted double structure in the graphene-like transitions which is not reported before

Iron filled carbon nanotubes (FeCNT) can be described as carbon nanotubes which contain an iron nanowire of several micrometers length and a diameter of approximately 10-100 nm. The carbon shells protect the iron core from oxidation and mechanical damage thus enabling a wide range of applications that require a long-term stability. The magnetic properties of the enclosed nanowire are in part determined by its small size and elongated shape. Magnetic force microscopy (MFM) measurements show that the iron wire exhibits a single domain behavior. Due to the large shape anisotropy it is magnetized along the long wire axis in the remanent state. Two magnetic monopoles of opposing polarity are located at the wire extremities. Depending on the structure and geometry of the individual nanowire, switching fields in the range of 100-400 mT can be found when the external field is applied along the FeCNT’s easy axis. Cantilever magnetometry shows that the switching can be attributed to a thermally assisted magnetization reversal mechanism with the nucleation and propagation of a domain wall. The defined magnetic properties of individual FeCNT combined with their mechanical strength make them ideal candidates for an application as high resolution high stability MFM probes. The fabrication of such probes can be achieved with the help of a micromanipulation setup in a scanning electron microscope. FeCNT MFM probes achieve a sub 25 nm lateral magnetic resolution. MFM measurements with FeCNT MFM probes in external fields show that the magnetization of these probes is exceptionally stable compared to conventional coated MFM probes. This greatly simplifies the data evaluation of such applied field MFM measurements. The emphasis of this work was put on the calibration of FeCNT probes to enable straightforward quantitative MFM measurements. The defined shape of the magnetically active iron nanowire allows an application of a point monopole description. Microscale parallel current carrying lines that produce a defined magnetic field are used as calibration structures to determine the effective magnetic moment of different MFM probes. The line geometry is varied in order to produce multiple magnetic field decay lengths and investigate the influence on the effective probe moment. The results show that while the effective magnetic monopole moment of a conventional MFM probe increases with an increasing sample stray field decay length, the effective moment of a FeCNT MFM probe remains constant. This enables a MFM probe calibration that stays valid for a large variety of magnetic samples. Furthermore, the fitted monopole moment of a FeCNT probe (in the order of 10E-9 Am) is consistent with the moment calculated from the nanowire geometry and the saturation magnetization of iron.

Magnetic fluid hyperthermia is a potential therapy for achieving interstitial hyperthermia and is currently under clinical trials. This approach is based on the instillation of magnetic nanoparticles at the tumour site, which dissipate heat when exposed to an alternating magnetic field. This procedure leads to a local increase of temperature and induction of tumour death or regression. Nanoparticles of metallic iron are potential heating agents for this therapy, but rely on the presence of a protecting coat that avoids reactions with their environment. In this work, iron nanospheres and iron nanowires with a graphite coat are explored for this purpose. From these two nanostructures, the nanospheres are shown to have a greater potential in terms of heat dissipation. The graphite shell is further investigated as an interface for conjugation with other molecules of relevance such as drugs and fluorescent probes. The effect of acidic treatments on the magnetic and surface properties of the nanospheres is systematically studied and a suitable method to generate carboxylic functionalities on the nanoparticle surface alongside with a good preservation of the magnetic properties is developed. These carboxylic groups are shown to work as a bridge for conjugation with a model molecule, methylamine, as well as with a fluorescent dye, allowing the detection of the nanoparticles in cells by means of optical methods. The carboxylic functionalities are further explored for the conjugation with the anti-cancer drug cisplatin, where the amount of drug loaded per particle is found to be dependent on the density of free carboxylic groups. The release of the drug in physiological salt solutions is time and temperature dependent, making them particularly interesting for multi-modal anti-cancer therapies, where concomitant hyperthermia and chemotherapy could be achieved. Their potential for such therapies is shown in vitro by inducing hyperthermia in cell suspensions containing these nanoparticles. These results are finally translated to a three dimensional cell culture model where the in vitro growth of tumour spheroids is inhibited. The developed nanostructures have a great potential for therapeutic approaches based on the synergistic effects of hyperthermia and chemotherapy.

This thesis presents a detailed study of magnetic reconnection in a quasi-two-dimensional pulsed-power driven laboratory experiment. These experiments were performed at the 1.4 MA, 240 ns rise time Magpie facility at Imperial College London. Initial experiments are presented which demonstrate the viability of carbon as a wire material, and the use of exploding wire arrays as a platform for laboratory astrophysics. In the reconnection experiments, two exploding carbon wire arrays are placed side-by-side and driven in parallel by the Magpie current pulse. The carbon wires become plasma, creating super-sonic, sub-Alfvénic flows which advect anti-parallel magnetic fields towards the mid-plane between the two arrays, where the fields mutually annihilate inside a thin current sheet. A suite of temporally and spatially resolved diagnostics are used to study the reconnection process, including optical fast-framing, laser interferometry, Faraday Rotation imaging and Thomson Scattering. These detailed measurements allow the structure and dynamics of the reconnection layer to be determined, along with the nature of the inflows and outflows and the detailed energy partition during the reconnection process. The layer is unstable, exhibiting the repeated formation and ejection of plasmoids which have an associated magnetic structure measured by magnetic probes. The number and growth rate of these plasmoids agrees well with the predictions of semi-collisional tearing instability theory, and represent the first experimental observation of plasmoids in this regime. High electron and ion temperatures are observed, far in excess of what can be attributed to classical (Spitzer--Braginskii) resistivity or viscosity. Some possible anomalous heating mechanisms are discussed, including kinetic turbulence, and the plasmoid instability. Preliminary measurements of the out-of-plane velocity and magnetic field are presented along with the outlook for future experiments.

Le but poursuivi dans ce travail est l'analyse des propriétés physiques des nanotubes de carbone et certains de ses dérivées, à l'aide des techniques RMN. Premièrement, nous avons étudié les propriétés structurales des nanotubes. D'une part une relation entre les diamètres des tubes et les déplacements chimiques est proposée et les largeurs des raies et les nombres des feuilles des tubes d'autre part. Deuxièmement, nous avons étudié la fonctionalisation des nanotubes de carbone. Nous avons observé des réponses précises sur la nature des liaisons chimiques formées, leur réversibilité et la présence des défauts structuraux. Nous avons apporté la confirmation de l'interaction diamagnétique entre les nanotubes et des chaînes polymères (SPEEK). Troisièment, nous avons mis en évidence les propriétes magnétiques et dynamiques des "peapods". Nous avons proposé un mécanisme à l'origine de l'écrantage diamagnétique à l'intérieur des nanotubes, lié aux courants de cycle à la surface de nanotubes qui entraine des déplacements diamagnetiques. Les défauts à la surface des tubes éliminent cet effet pour créer un déplacement paramagnétique. Nous avons également déterminé les dynamiques de réorientations des molécules C60 à l'intérieur des nanotubes. Nous avons montré que la plupart des molécules C60 subissent une transition de phase d'une rotation isotropique à une rotation entravée vers 100 K et un blocage complet vers 30K. Quatrièment, nous avons révélé les détails des propriétes physiques et chimiques associés à des molécules C60 hydrogénées à l' intérieur des nanotubes. Nous avons observé des déplacements diamagnétiques et paramagnétiques des signatures RMN et des carbones de type sp3. Enfin, nous avons étudié les propriétés électromagnétiques des nanotubes bifeuillets. Nous avons trouvé deux types des nanotubes, métalique de type 1-D et semiconducteur
This work deals with physical properties of carbon nanotubes and some derivatives, using NMR spectroscopy. Firstly, we studied the structural properties of nanotubes. According to the size and shape, we established the dependence of their NMR signatures and find two empiric expressions for the line shifts and line widths. Secondly, we reported a detailed analysis based on high resolution 13 C NMR of functionalized nanotubes. We identified the chemical groups or defects present in functionalized carbon nanotubes. We confirmed the magnetic interaction between carbon nanotubes functionalized with polymer chains (SPEEK). Thirdly, we investigated the local magnetic properties and the 1-D dynamics of C60 molecules inside carbon nanotubes (peapods). We modelized the origine of the diamagnetic shielding inside carbon nanotubes. We reported this diamagnetic shift to the ring-currents at the nanotube surface. Moreover, defects like C-vacancies, pentagons and chemical functionalization of the outer nanotube quench this diamagnetic effect and restore NMR signatures to slightly paramagnetic shifts. Equally, we determined the rotational dynamics of the 1-D C60 molecules inside carbon nanotubes. We have shown that the majority of C60 molecules undergo dynamical phase transitions, from free rotations to hindered rotations at 100 K and to frozen states at 30 K. Forthly, we studied the chemical and physical modifications of hydrogenated C60 molecules inside nanotubes. We observed the characterestic diamagnetic and paramagnetic shifts of the NMR lines and the appearance of sp3 carbon resonances. Finally, se studied the electomagnetic properties of inner nanotubes in double-walled carbon nanotubes. We found two kinds of nanotubes, 1-D metal and semiconducting

The structural and electronic properties of covalently and non-covalently functionalized graphene are investigated by means of first-principles density-functional-theory. The electronic characteristics of non-covalently functionalized graphene by a planar covalent organic framework (COF) are investigated. The aromatic central molecule of the COF acts as an electron donor while the linker of the COF acts as an electron acceptor. The concerted interaction of donor acceptor promotes the formation of planar COF networks on graphene. The distinctive electronic properties of covalently functionalized fluorinated epitaxial graphene are attributed to the polar covalent C–F bond. The partial ionic character of the C–F bond results in the hyperconjugation of C–F σ-bonds with an sp2 network of graphene. The implications of resonant-orbital-induced doping for the electronic and magnetic properties of fluorinated epitaxial graphene are discussed. Isolation of single-walled carbon nanotubes (SWNTs) with specific chirality and diameters is critical. Water-soluble poly [(m- phenyleneethynylene)- alt- (p- phenyleneethynylene)], 3, is found to exhibit high selectivity in dispersing SWNT (6,5). The polymer’s ability to sort out SWNT (6,5) appears to be related to the carbon–carbon triple bond, whose free rotation allows a unique assembly. We have also demonstrated the important role of dispersion forces on the structural and electronic stability of parallel displaced and Y-shaped benzene dimer conformations. Long-range dispersive forces play a significant role in determining the relative stability of benzene dimer. The effective dispersion of SWNT depends on the helical pitch length associated with the conformations of linkages as well as π-π stacking configurations. We have revisited the constructing schemes for a large family of stable hollow boron fullerenes with 80 + 8n (n = 0,2,3,...) atoms. In contrast to the hollow pentagon boron fullerenes the stable structures constitute 12 filled pentagons and 12 additional hollow hexagons. Based on results from density-functional calculations, an empirical rule for filled pentagons is proposed along with a revised electron counting scheme. We have also studied the relative stability of various boron fullerene structures and structural and electronic properties of B80 bucky ball and boron nanotubes. Our results reveal that the energy order of fullerenes strongly depends on the exchange-correlation functional employed in the calculation. A systematic study elucidates the importance of incorporating dispersion forces to account for the intricate interplay of two and three centered bonding in boron nanostructures.

Carbon nanotubes (CNTs) exhibit unique and fascinating intrinsic electrical, optical, thermal or mechanical properties that lead to a plethora of potential applications in composite materials, electronics, energy storage, medicine, among others. However, the manipulation of nanotubes is not trivial and there are significant difficulties to overcome before achieving their full potential in applications. Because of their high aspect ratio and strong tube-to-tube van der Waals interactions, nanotubes form bundles and ropes that are difficult to disperse in liquids. In this thesis, the topic of dispersing carbon nanotubes in water was addressed by several experimental methods such as nuclear magnetic resonance (NMR) diffusometry and light/electron microcopy. The main goal was to obtain molecular information on how the dispersants interact with carbon nanotubes. In dispersions of single-walled carbon nanotubes (SWNTs) in water, only a small fraction of the polymeric dispersant (Pluronic F127) was shown to be adsorbed at the CNT surface. Regarding dynamic features, the residence time of F127 on the SWNT surface was measured to be in the order of hundred milliseconds, and the lateral diffusion coefficient of the polymer along the nanotube surface proved to be an order of magnitude slower than that in the solution. The surface coverage of SWNTs by F127 was also investigated and the competitive adsorption of F127 and the protein bovine serum albumin, BSA, was assessed. F127 was found to bind stronger to the CNT surface than BSA does. Low molecular weight dispersants, viz. surfactants, were also investigated. Using carefully controlled conditions for the sonication and centrifugation steps, reproducible sigmoidal dispersibility curves were obtained, that exhibited an interesting variation with molecular properties of the surfactants. Various metrics that quantify the ability of different surfactants to disperse CNTs were obtained. In particular, the concentration of surfactant required to attain maximal dispersibility depends linearly on alkyl chain length, which indicates that the CNT-surfactant association, although hydrophobic in nature, is different from a micellization process. No correlation between dispersibility and the critical micellization concentration, cmc, of the surfactants was found. For gemini surfactants of the n-s-n type with spacer length s and hydrophobic tail length n, the dispersibility of multiwalled carbon nanotubes (MWNTs) also followed sigmoidal curves that were compared to those obtained with single-tailed homologues. The increase in spacer length caused an increase in the dispersion efficiency. The observations indicate a loose type of monolayer adsorption rather than the formation of micelle-like aggregates on the nanotube surface. With the future goal of embedding nanotubes in liquid crystal (LC) phases and thereby creating nanocomposites, the effect of the spacer length on the thermotropic behavior of the gemini 12-s-12 surfactant was investigated. Different mesophases were observed and a non-monotonic effect of the spacer length was found and rationalized within a model of the surfactant packing in the solid state. The relative binding strength of simple surfactants to CNTs was assessed by the amount of F127 they displace from the CNT surface upon addition. Anionic surfactants were found to replace more F127, which was interpreted as a sign of stronger binding to CNT. The data collected for all surfactants showed a good correlation with their critical dispersibility concentration that suggests the existence of a surface coverage threshold for dispersing nanotubes. On the macroscopic scale, the formation of weakly bound CNT aggregates in homogeneous dispersions was found to be induced by vortex-shaking. These aggregates could quickly and easily be re-dispersed by mild sonication. This counterintuitive behavior was related to the type of dispersant used and of the duration of mechanical agitation and was explained as a result of loose coverage by the dispersant.

This Ph.D thesis was completed under the Thesis Co-supervision Agreement between KTH Royal Institute of Technology and the University of Port. QC 20151105

Multiwall carbon nanotubes filled with continuous single-crystals of the ferromagnetic phase -Fe were produced with two new synthesis methods: the boundary layer chemical vapour synthesis and the perturbed vapour chemical vapour deposition. In the first method, the nanotubes nucleate and grow radially from a central agglomeration of homogeneously nucleated spherical particles in a randomly fluctuating vapour created in the viscous boundary layer between a rough surface and a laminar pyrolyzed-ferrocene/Ar vapour flow. In the second method, the nanotubes nucleate and form in a flower-like arrangement departing from homogeneously nucleated particles. These particles are produced by the creation of a local perturbation in a vapour with a high density of Fe and C species obtained from the pyrolysis of ferrocene in a laminar Ar flow. Electron microscopy investigations revealed that the continuous single crystals obtained with both methods exhibit diameters much lower than the critical diameter for a single magnetic domain of -Fe (~ 66 nm). In the radial structures, the single-crystal diameter is in the range of ~ 17-37 nm, while in the flower-like structures the single crystals show mainly a diameter of ~ 30 nm and ~ 55 nm. The average single crystals length is 7-8 m in the case of the radial structures and 19-21 m in the case of the flower-like structures. DC magnetization measurements at 5 K show different magnetic behaviours. The flower-like structures present a very high saturation magnetization of 189.5 emu/g and a high coercivity of 580 Oe. The radial structures exhibit an exchange-coupled ferromagnetic/antiferromagnetic system despite only 2% of -Fe is present inside the nanotubes. The radial structures obtained at flow-rates of 3.5 ccm and 20 ccm, show saturation-magnetizations of 31emu/g and 13 emu/g, and coercivities of 790 Oe and 843 Oe respectively.

Thesis advisor: Michael J. Naughton
Magnetic resonance force microscope (MRFM) is a relatively new form of microscopy, which provides very high-resolution images in three dimensions (3D). Further development of this microscope would provide a great instrument that would further many areas of research, including physics, material science, and biology. This research project aims to explore the possibilities of making a MRFM more sensitive by using carbon nanotubes or zinc oxide nanowires as cantilevers, making the resolution much higher and the scans accurate to a much smaller scale. The Magnetic resonance force microscopy is a cross between a magnetic resonance microscope (MFM) and atomic force microscopy (AFM). It combines Magnetic Resonance Imaging (MRI) technology with scanning probe microscopy to create an apparatus that can scan a surface and obtain images somewhat like those obtained by current MRI technology but on a much smaller scale. These images can be put back together to create a 3D image of the material
Thesis (BS) — Boston College, 2004
Submitted to: Boston College. College of Arts and Sciences
Discipline: Physics
Discipline: College Honors Program

FREIRE, Rafael Melo. Magnetic nanoparticles and carbon quantum dots: interdisciplinary nanoparticles for sensing and/or education. 182 f. 2016. Tese (Doutorado em Química)-Universidade Federal do Ceará, Fortaleza, 2016.
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In this work, a sensing strategy for detection and identification of proteins with magnetic nanoparticles (MNPs) and carbon quantum dots (CQDs) was developed. In this sense, mixed ferrites of general formula M0.5Zn0.5Fe2O4 (M=Mn or Ni) were first investigated. Therefore, the hydro/solvothermal synthesis of these magnetic nanoparticles was performed under different conditions (solvent, reaction time and base concentration). Based on the magnetic properties of the two MNPs investigated, the mixed ferrite of formula Mn0.5Zn0.5Fe2O4 (MnZn) synthesized using water showed the greatest potential for sensing. Since among all synthesized MNPs, this sample displayed the highest saturation magnetization value ( M S  50 emu/g), lower crystallite size around 12 nm and superparamagnetic behavior. Once the first part of the doctoral thesis was concluded, the next step was to find a fluorescence probe. In this regard, it was performed the synthesis, as well as the application of branched poliethylenimine-functionalized carbon quantum dots (CQDs.BPEI). These new carbon-based nanoparticles were found to be protein-responsive. Since CQDs.BPEI were able to detect eight different proteins (four metallic and four non-metallic) even using concentrations in the range of 5 – 40 nM. Fluorescence titrations performed at 298 and 310 K displayed the fluorescence quenching through collisional mechanism. Therefore, it was also possible to conclude that the fluorescence quench comes from the amino acid residues on the surface of the proteins. To further check the potential of the CQDs.BPEI, it was developed a “nose” based methodology to identify proteins. Using materials as cheap as Cu2+ and ethylenediaminetetraacetic acid, the chemical “nose” approach was able to discriminate six different proteins at 40 nM concentration in phosphate buffered saline (PBS, pH 7.4). The identification accuracy of the random unknown set was 90% with all misclassification occurring for albumin proteins (e.g., Bovine Serum Albumin and Human Serum Albumin). The displayed results evidence the great potential of CQDs.BPEI as a protein-responsive probe to detect and identify proteins. Taken together, MnZn and CQDs.BPEI were capable to build up a powerful protein sensing approach. In addition, realizing the great potential of CQDs in the educational field, it was also developed and successfully applied (for more than 70 students from biotechnology, pharmacy, engineers and geology courses) a lab experiment to demonstrate lightrelated quantum phenomena.
Neste trabalho, uma estratégia para detecção e identificação de proteínas incluindo nanopartículas magnéticas (MNPs) e pontos quânticos de carbono (CQDs) foi desenvolvida. Assim, ferritas mistas de fórmula M0.5Zn0.5Fe2O4 (M=Mn or Ni) foram inicialmente investigadas. Neste sentido, suas sínteses foram feitas utilizando diferentes condições (solvente, tempo reacional e concentração de base). Logo, baseado nas propriedades magnéticas das MNPs sintetizadas, escolheu-se a Mn0.5Zn0.5Fe2O4 (MnZn) sintetizada em água por mostrar grande potencial, uma vez que essa amostra apresentou alto valor de magnetização de saturação ( M S  50 emu/g) em comparação com outras ferritas de composição semelhante, baixo tamanho de cristalito por volta de 12 nm e comportamento superparamagnético. Com a primeira parte do trabalho concluída, a próxima etapa foi encontrar uma sonda fluorescente. Assim, realizou-se a síntese dos CQDs funcionalizados com grupamentos amina (CQDs.BPEI). Quando testada contra 8 diferentes proteínas (4 metálicas e 4 não-metálicas), apresentou variação da emissão para concentrações na faixa de 5 – 40 nM. Titulações fluorescentes também foram realizadas e observou-se que a supressão da fluorescência ocorre via mecanismo colisional a partir de resíduos aminoácidos na superfície da proteína. Para adicionalmente checar o potencial dos CQDs.BPEI, foi desenvolvida abordagem para identificar proteínas utilizando materiais Cu2+ e o ácido etilenodiamino tetraacético. No total, a estratégia desenvolvida foi capaz de identificar corretamente 6 diferentes proteínas a 40 nM. A precisão da identificação encontrada foi 90% para as amostras desconhecidas. Contudo, vale ressaltar que os 10% de engano foram apenas entre BSA e HSA, duas proteínas albumínicas muito similares. Os resultados obtidos nessa parte do trabalho evidenciam o alto potencial de CQDs.BPEI para detecção e identificação de proteínas. Observando os resultados do trabalho como um todo, pode-se afirmar que MnZn e CQDs.BPEI são capazes de compor excelente abordagem para detecção e identificação de proteínas. Adicionalmente, foi explorada a utilidade dos CQDs para o campo educacional. Dessa forma, foi também desenvolvido e aplicado (mais de 70 estudantes de graduação oriundos dos cursos de biotecnologia, farmácia, engenharias e geologia) um experimento de laboratório para demonstrar fenômenos quânticos relacionados com a luz.

The main goal of this project was the development of carbon nanotubes as a candidate for dual-functioning magnetic hyperthermia structure and magnetic resonance imaging contrast agent. This was achieved by filling carbon nanotubes with continuous ferromagnetic α-Fe nanowires and surface functionalized with paramagnetic Gd(III). Also, length control of both nanotube and nanowire was investigated. Firstly, a low vapour flow-rate and constant evaporation temperature chemical vapour deposition method based on the thermal decomposition of ferrocene was employed which achieved continuous α-Fe nanowires on the same scale as the nanotube for lengths >10 m without the necessity of post-synthesis heat-treatment or introduction of other precursor elements. The low vapour flow-rate regime has the advantage of sustaining the intrinsic temperature gradient at the tip of the forming structure which drives the vapour feedstock to the growth front to guarantee continuous nanowire formation. For initially mixed-phase nanowires of length less than 10 μm, the continuous α-Fe nanowires were achieved by postsynthesis heat treatment. Secondly, a simple wet chemical method involving only sonication in aqueous GdCl3 solution was used for surface functionalization of iron-filled multiwalled carbon nanotubes with gadolinium. Functional groups on the sidewalls produced by the sonication provide active nucleation sites for the loading of Gd3+ ions. Characterization by electron paramagnetic resonance, electron energy loss spectroscopy, and high-resolution transmission electron microscopy confirmed the presence of Gd3+ ions on the sidewall surface. The ferromagnetic properties of the encapsulated iron nanowire maintained after surface functionalization. At room temperature a saturation magnetization of 40 emu/g and a coercivity of 600 Oe were observed. Heating functionality in an alternating applied magnetic field was quantified through the measurement of specific absorption rate: 50 W/gFe and the intrinsic loss power: 1.12 nHm²kg⁻¹ at magnetic field strength 8 kA/m and frequency of 696 kHz. These structures exhibited an extremely high relaxivity r₁ ~ 200 mM⁻¹ s⁻¹ at high magnetic field (9.4 T).

The aeolian sediment loess, which consists of mineral dust, is one of the most detailed terrestrial record of both global and regional climate changes. As climate changes in the past cover a much wider range of climate variability than humans have directly recorded, the soil memory of loess is vital for understanding the Earth’s climate system. By examining past climate records and analyzing past climate changes and factors that have instigated changes, inferences regarding future climate can be made. Therefore, the aim of this research was to define the specific depositional and post-depositional conditions of a loess sequence in Primel-Tr gastel, Brittany, north-western France. This was done by examining the magnetic susceptibility (MS), and loss on ignition (LOI) of 63 samples from the Primel-Tr gastel sequence. The result suggests that the lower part was formed during a relatively long, cold and dry period, with significant temperature oscillations, resulting in several periglacial phases. The data also shows an increase in the MS signal for the middle units, which then gradually decreases simultaneously as there is a sharp rise in the proportion of organic matter (OM). This is followed by a steep drop and finally an overall increase in OM, which suggests that this period has been characterized by both stadial and interstadial phases. The upper part displays a general increase in MS values, as well as increased organic matter, which implies a milder climate with increased temperatures. The study provides the first comprehensive estimate of the regional climate variability and provides a base towards a more comprehensive and overarching understanding of our climate system.

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
O presente trabalho teve como principal objetivo estudar a atividade catalítica de soroalbumina bovina (BSA) em reações formadoras de uma nova ligação C-C: Reações aldólica, de Henry e Morita-Baylis-Hillman (MBH). Em todos os casos a BSA atuou como catalisador, visto que quando as reações foram realizadas sem sua presença, não houve formação dos produtos desejados. Os rendimentos obtidos para as reações aldólica (37%), Henry (80%) e MBH (73%), variaram de bons a moderados e não foi observada enantiosseletividade para nenhuma das reações estudadas. As soroalbuminas são proteínas que formam muita emulsão dificultando os processos downstream na separação dos produtos e materiais de partida. Visando minimizar este inconveniente, a BSA foi submetida à imobilização em MCLEA (magnetic cross-linking enzyme aggregates) utilizando nanopartículas magnéticas de óxido de ferro. Nestes casos, o biocatalisador pôde ser facilmente retirado do meio reacional com aplicação de um campo magnético externo. Esta metodologia afetou diretamente no rendimento da reação de Henry, passando de 80% para 89%. Porém, para as outras reações a melhoria no rendimento não foi tão expressiva. A imobilização também não foi eficaz para o aumento dos excessos enantioméricos. Até o momento para a reação de MBH com os substratos utilizados, não há relatos na literatura para a síntese do aduto desejado catalisado pela BSA. Sendo assim, optamos por realizar um planejamento fatorial completo dessa reação visando otimizar as condições reacionais bem como os rendimentos. As variáveis estudadas foram: temperatura, concentração do biocatalisador e condição do biocatalisador (livre ou imobilizado). Os resultados obtidos mostraram que a variável com maior influência na reação, é a concentração do biocatalisador. A conversão obtida passou de 30% para 40% utilizando 2,2 μmol de BSA. Em seguida, realizamos um estudo de ascendência da concentração do catalisador visando otimizar este parâmetro. A conversão obtida passou para 73% quando foram utilizadas 3,7 μmol de biocatalisador imobilizado. Realizamos um estudo de reciclagem do biocatalisador imobilizado. Foi possível reutiliza-lo porém com diminuição da conversão a partir do segundo ciclo. Os resultados obtidos nesta dissertação evidenciam o potencial biocatalítico da BSA em reações para a formação de ligação C-C.
This work aimed to study the catalytic activity of bovine serum albumin (BSA) in reactions that form a new C-C bond: aldol reactions, Henry and Morita-Baylis-Hillman (MBH). In all cases BSA served as the catalyst, whereas when the reactions were carried out without their presence there was no formation of the desired products. The yields obtained for aldol reactions (37%), Henry (80%) and MBH (73%), ranged from good to moderate enantioselectivity and was not observed for any of the studied reactions. The serum albumins are proteins that form the much emulsion difficulting downstream processes in separation of the products and starting materials. To minimize this inconvenience, the BSA was subjected to immobilization in M-CLEA (magnetic cross-linking enzyme aggregates) using magnetic nanoparticles of iron oxide. In these cases the biocatalyst could be easily removed from the reaction medium by applying an external magnetic field. This methodology directly affect the yield of the Henry reaction, from 80% to 89%. However, for other reactions the improvement of yields was less pronounced. The immobilization was also not effective for improving the enantiomeric excess. So far for the MBH reaction with the worked substrates, there are no reports in the literature for the synthesis of the desired adduct catalyzed by BSA. So we decided to study a full factorial design of this reaction to optimize the reaction conditions and yields. The variables studied were: temperature, the biocatalyst concentration and biocatalyst conditions (free and immobilized). The concentration of biocatalyst was the major factor with interference in all reactions. The conversion increased from 30% to 40% using 2.2 μmol of BSA. Then we perform a study of catalyst concentration to optimize this parameter. The conversion increased to 73% when they were used 3.7 μmol immobilized biocatalyst. To evaluate the retention of catalytic activity of BSA immobilized, it was performed a study of the immobilized biocatalyst recycling. It was possible the reuse but with reduced conversion from the second cycle. The results obtained in this work demonstrated the potential of BSA in C-C bond formation reactions.

The role of nanohybrid materials in the fields of polymer composites and electrochemical energy systems is significant since they affect the enhanced physical properties and improved electrochemical performance, respectively. As basic nanomaterials, carbon nanotubes and graphene were utilized due to their outstanding physical properties. With these materials, hybrid nanostructures were generated through a novel synthesis method, modified sol-gel process; namely, carbon nanotubes (CNTs)-maghemite and reduced graphene oxide (rGO)-maghemite nanohybrid materials were developed. In the study on polymer composities, developed CNTs-maghemite (magnetic carbon nanotbues (m-CNTs)) were readily aligned under an externally applied magnetic field, and due to the aligned features of m-CNTs in polymer matrices, it showed much enhanced anisotropic electrical and mechanical properties. In the study on electrochemical energy system (Li-ion batteries), rGO-maghemite were used as anode materials; as a result, they showed improved electrochemical performance for Li-ion batteries due to their specific morphology and characteristics.

Les travaux de cette thèse ont été consacrés à la synthèse de nanoparticules magnétiques d'oxyde de fer et d'oxyde de cobalt et de nanoparticules coeur-coquille constituées d'un coeur d'oxyde de fer recouvert d'oxyde de cobalt et à l'élaboration de nanomatériaux - composites nanostructures carbonées/nanoparticules d'oxyde métallique - pour des applications dans le domaine biomédical et celui de l'énergie. Pour la synthèse des NPs, la forme et la taille des NPs sont fortement dépendantes des conditions de réaction (nature des ligands, des solvants, température de réaction ... ) , ce qui affecte leurs propriétés magnétiques. De plus, des simulations ont montré que les chaînes de stéarate peuvent désorber plus facilement les atomes de fer que les atomes de cobalt et se libérer pour former des germes, ce qui pourrait expliquer le comportement distinctif entre les deux complexes. Ces nanoparticules magnétiques ont été synthétisées à l'intérieur de nanotubes de carbone en deux étapes aboutissant à des taux de remplissage très importants. Après fonctionnalisation, ces nanocomposites ont été introduits dans de cellules tumorales et ont été magnétiquement manipulées. Ils se sont révélés être très efficaces en tant qu'agents de contraste en IRM mais également dans le domaine de l'hyperthermie (activation sous éclairage dans le domaine de !'Infrarouge proche). Enfin, de nouveaux composites à partir de nanoparticules de Nb20 5 et de graphène (ou NTCs) ont été synthétisés et des résultat~prometteurs ont été obtenus dans des tests de batterie lithium-ion : leur utilisation en tant qu'anode a permis d'obtenir des capacités réversibles de 260 mAh/g
This thesis was focused on the synthesis of magnetic nanoparticles of iron oxide and cobalt oxide and core-shell nanoparticles, consisting of a cobalt oxide coated iron oxide and on the development of composite nanomaterials - nanostructures carbon /metal oxide nanoparticles - for applications in the biomedical field and the energy. For the synthesis of NPs, the shape and size of NPs are dependent of the reaction conditions, which further affect their magnetic properties. Meanwhile, simulation showed that stearate chains can desorb more easily from iron atoms and release to form seeds than from cobalt atoms, which might explain distinctive behavior between the bath complexes. Regarding nanostructures carbon/metal oxide nanoparticles hybrid materials, the properties of the filled magnetic CNTs as heat mediator for photothermal ablation and as contrast agent for MRI were then evaluated and promising results have been obtained. Last, new composite materials (Nb205 nanoparticles/graphene or NTCs) were synthesized and promising results were obtaines in lithium battery tests : their use as anode allowed obtaining reversible capacities of 260 mAh/g

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Mechanical Engineering, 2010.
Cataloged from PDF version of thesis.
Includes bibliographical references (p. 123-133).
Carbon nanotubes (CNTs), in particular the vertically-aligned variety grown through a plasma enhanced chemical vapor deposition (PECVD)-based process, are highly versatile nanostructures that can be used in a variety of nanomanufacturing applications. However, process and material compatibility issues have prevented the nanotubes from becoming more fully integrated into various micro- and nanomanufacturing applications. In this thesis, the integration of in situ CNT growth with a 3-D nanomanufacturing platform, namely the Nanostructured Origami TM process, will be shown. Due to the high temperatures involved in CNT growth, a new origami membrane material, titanium nitride (TiN), is introduced. This new origami membrane serves as an excellent diffusion barrier layer throughout the CNT growth process while promoting consistent nanotube growth and maintaining electrical conductivity to the CNTs. Various further modifications are made to the origami process, for example in metallization techniques, to accommodate the addition of CNTs to origami devices. Based on the presented CNT-origami process, a functioning microscale supercapacitor is also fabricated and tested. The integration of high surface area CNT electrodes with a unique 3-D device geometry results in a fabfriendly, high-performance supercapacitor that can easily be integrated as an onboard power source in self-powered microsystem applications. Finally, the magnetic properties of our in situ grown CNTs, derived from their naturally occurring, tip-encapsulated catalyst particles, will be characterized. Furthermore, these properties will be used to magnetically actuate, align, and latch individual as well as large arrays of CNTs and the entire membranes on which they are grown. The magnetic behaviors of CNTs and their underlying membranes will be investigated through computer simulation and experimental verification.
by Hyun Jin In.
Ph.D.

碩士
國立交通大學
應用化學系所
96
The thesis are divided into four parts. In the first part, acetylene was decomposed inside the anodic aluminum oxide membranes (AAO) channels to form carbon nanotube (CNT) at 823 K. The CNT diameter varied with the diameter of the AAO channels. The graphite layers of carbon nanotubes were parallel to the tube axis, and the d–spacing of the graphite layers was estimated to be 0.343 nm and length was about several μm. In the second part, iron oxide filled CNTs arrays were synthesized via anodic aluminum oxide (AAO) template-assisted aqueous solution method, which involved an aqueous ammonia solution in the reduction of ferrous and ferric ions. From many characterizations such as TEM, XRD, and XPS, we confirm these magnetic carbon nanotubes to Fe3O4@CNT magnetite phase. In the third part, poly(acrylic acid) treated magnetic carbon nanotubes were employed as affinity probes to selectively concentrate traces of positively charged analytes from sample solutions through electrostatic interactions. Because proteins have their unique isoelectric points (pI), by varying the values of pH of the same solution, specific proteins can be concentrated selectively on the surface of the poly(acrylic acid) treated magnetic carbon nanotubes. The results were confirmed using UV-visible spectroscopy. In the four part, the feasibility of using MCNT as surface-assisted laser desorption/ionization (SALDI) matrix for the analysis of peptides and insulin was examined.

碩士
國立成功大學
物理學系碩博士班
92
We use the tight-binding model to calculate the magneto band structures of single-walled carbon nanotubes. They strongly depend on the geometric structures,the curvature effects, the mixture effects, and the spin-B interaction. Their features are directly reflected in the magnetization and the differential susceptibility. Within the presence of the metal-semiconductor transition, the magnetization exhibits the discontinuous cusp structures and the differential susceptibility occurs logarithmic divergencies. At the small flux, the curvature effect and the -electron would decrease the magnetization and the differential susceptibility, but would not change the magnetism. When the flux equals to zero, the curvature effect and the -electron would not affect the magnetization ( M=0 ), but have effect on the differential susceptibility.

碩士
國立中興大學
材料工程學系所
94
Polypyrrole (PPy), an intrinsic conducting polymer, contains relative ease of synthesis, excellent electrical conductivity and environmental stability and can be used as electrical sensor and device. The conductivity of PPy is dependent on its preparation and doping level and is in the range of 10‾³~10² S/cm. In this study, a new design of PPy composite possessing both electrical and magnetic properties can be synthesized by in situ chemical oxidative polymerization using uniformly Fe3O4 nanoparticle and carbon nanotube (CNT) to improve the properties of PPy. The morphology and physical properties of fabricated composites will be discussed. The morphology of PPy/Fe3O4 composites is spherical using various contents of 4 nm, 6 nm and 8 nm Fe3O4, except the content of 4 nm Fe3O4 is higher than 24 wt%. The diameter of PPy/Fe3O4 sphere is decreased as increasing the content of Fe3O4. The electrical conductivity of PPy/Fe3O4 composites increases as increasing the content of Fe3O4. The magnetic properties of PPy/Fe3O4 composites show superparamagnetism at high content of Fe3O4. For PPy/Fe3O4/CNT system, the morphology of fabricated composites shows core-shell structure with the thickness of PPy layer in the range of 70-130 nm. The conductivities of PPy/Fe3O4/CNT composite with 4 nm, 6 nm and 8 nm Fe3O4 are 67.114, 87.719, 64.516 S/cm, respectively, as the contents of CNT is 2.64 wt% and Fe3O4 0.8 wt%. The results of FTIR and Raman indicate the interaction between PPy, Fe3O4 and CNT occurs as the characteristic peaks shift. The magnetic properties of composites reveal ferromagnetic behavior, which is mainly influenced by CNT.

碩士
國立成功大學
物理學系碩博士班
90
Abstract We use the tight-binding model to calculate the magneto band structures of finite carbon nanotubes. They strongly depend on the edge structures(armchair and zigzag structures), the radius, the length, and the spin-B interaction. Their features are directly reflected in the persistent currents. Such currents exhibit the discontinuous cusp structures in the presence of the metal-semiconductor transition. Temperature changes cusp structures into peak structures and reduces the magnitude of currents

碩士
國立屏東教育大學
應用物理系
102
The study of heterogeneous materials is a very attractive field of research. In properly designed, the combination of semiconductor materials and ferromagnetic, inducing a variety of strong spin-dependent phenomena, for example, the magnetoresistive effect, abnormal Hall effect, magneto-optical effects. In this work, we study the magnetic and magneto-optical properties of Co doped amorphous carbon(a-C) composites constructed by Co/C discontinuous multilayer before and after annealing. Energy-dependent magnetic circular dichroism (MCD) spectroscopy can be useful for studying this magnetic coupling between Co and C. Remnant circular dichroism (CD) was observed from the Co/C discontinuous multilayer and could be enhanced after annealing. In addition, the remnant CD peaks at 5.5 eV, which is similar to the Cσ-σ* gap transition. We suggest that the distance between Co grains and Co/C interface structures play important roles for Co-C coupling.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Master of Science Johannesburg September 2012
Electron spin resonance (ESR) was used to characterize a suite of carbon nanospheres (CNS) samples with varying nitrogen concentrations at room temperature. The CNS were produced using two different reactors (vertical and horizontal) under different preparatory conditions. Resonance spectra of samples produced from the vertical reactor showed resonance lines- a narrow paramagnetic component, and broader component. They were attributed to nitrogen paramagnetic impurities and carrier spins, respectively. Samples produced in the horizontal reactor revealed stronger line spectra that were narrower and Dysonian in shape. The nitrogen content of the samples produced by the horizontal reactor was determined through ESR analysis which involves integration of the resonance peak, and normalizing to the mass of the sample. The relative g-shift was also measured by using a DPPH reference sample. Room temperature power saturation experiments were performed on samples produced from the horizontal reactor with the aim of estimating the spin relaxation times. Two samples from the horizontal reactor were further investigated at low temperatures (4 K- 320 K) at a constant microwave power. The resonance parameters investigated were linewidth, asymmetry ratio and amplitude, and possible spin-lattice relaxation mechanisms were investigated. The variation of the amplitude with temperature was investigated using two models: (1) a model based on lattice vibrations, and (2) a model based on nanographites assembly (considered interaction between carrier and localized spins). At low temperatures both models have amplitude that changes inversely with temperature in accordance with Curie law. At high temperatures (T > 200 K) a model based on nanographites assembly provide an alternative; it describes the rise in the signal amplitude in terms of thermally activated paramagnetic electrons from non-magnetic ground state to excited state at energy . Analysis of linewidth and asymmetry ratio data confirmed that the spin-lattice relaxation governed by thermal activated electrons is a dominant relaxation mechanism at high temperatures.

碩士
國立清華大學
化學系
95
The thesis is divided into three parts. In the first part, mesoporous carbon materials with rod-like morphology, CMK-3, and those with tube-like morphology, CMK-5, have been synthesized by template synthesis using mesoporous SBA-15 silica as a hard template and sucrose or furfuryl alcohol as carbon precursors. The composition and the structure of these carbon materials were characterized by X-ray diffraction, nitrogen physisorption analysis, thermal analysis and transmission electron microscopy. Based on the data, the synthesis conditions have also been optimized. In the second part, monolithic carbon materials with hierarchically bimodal meso- and macroporosity have been prepared by using a hierarchically meso/macroporous silica monolith as a hard template and phenolic resin as the carbon source. The pore structure of the carbon monoliths were investigated by nitrogen physisorption analysis and scanning electron microsopy. In the third part, carbon-coated magnetic metal nanoparticles have been synthesized by using the carboxylate-functionalized mesoporous SBA-15 silica as a hard template. The magnetic properties of these nanoparticles were studied by Superconducting Quantum Interference Device. In addition, the outer carbon layers on these nanoparticles were oxidized to bear carboxylate groups by the treatment with nitric acid, and Fourier-transformed infrared spectroscopy was applied for characterizations. With these carboxylate groups, the carbon-coated magnetic nanoparticles can be further grafted with a variety of functional groups and other molecules for biomedical applications in the future.

A novel type of nanocrystalline magnetic thin films consisting of ferromagnetic metals and C60 have been developed and investigated. CO-C 60, Fe-C60 and CoFe-C60 with different concentrations of C60 thin films have been manufactured by thermal vapor codeposition. The microstructures and magnetic properties of the films can be significantly enhanced by varying the concentrations of C60 in the films. The stability of C60 and the compatibility of C60 with the metallic matrices are confirmed by mass spectrometry, Raman, WDS, XRD and TEM. Strong metal-C60 interaction is indicated by higher desorption temperatures of C60 in the meta-C60 films than that in pure C60 and the peak shift in Raman spectra. TEM shows that the grain size of the matrix metal decreases proportionally with increasing C60 concentration. Nanosize uniform columnar grains with nanoscale dispersion of C60 on the grain boundaries are commonly observed in the metal-C60 films. A self-assembly grain growth model based on the size effect of C60 and the metal-C60 interaction is proposed to delineate the microstructural evolution by C60. Calculations based on this model are consistent with experimental observations and give a grain size vs. C60 (carbon) concentration relationship. Grain growth retardation by C60 is observed in a CO-C60 film. Out-plane magnetic remanence and coercivity are enhanced in both the CO-C60 and Fe-C60 films. In the in-plane direction, the coercivity deceases in CO-C60 films but increases slightly in Fe-C60 films with increasing C60 concentrations. In-plane magnetic anisotropy is detected in CO-C60 films but not in Fe-C60 films. Strong temperature-dependent magnetization remanence and saturation are found in both the Co-C60 and Fe-C60 films with high C60 concentrations due to the nanosize grain effects. Temperature effects on the coercivity of CO-C60 and Fe-C60 are different and determined by the intrinsic magnetocrystalline anisotropy energy. Coercivity of the CoFe-C60 films increases after annealing above 450°C. An unusual magnetization behavior of the virgin curve intersecting with the major hysteresis loop and fast magnetic switch is observed in a Fe 83C60 film. The magnetic properties are interpreted by MOIF technique and correlated to the film microstructure.

碩士
東海大學
環境科學與工程學系
102
Carbon nanotubes (CNTs) had been receiving intensive investigation towards the development of their application due to their unique electronic, chemical, mechanical and structural properties. Because magnetic carbon nanotubes (MCNTs) can retains properties of magnetic material and CNTs that can be effectively separated under an external magnetic in aqueous solution. In this reason, MCNTs is suit to apply to waste water treatment. In this research, we use anodic aluminium oxide (AAO) template immersing in magnetic fluid for 12 hours. After drying, the magnetic fluid -loaded AAO templates were put into chemical vapor deposition (CVD) reactor. The temperature in the reactor was then increased up to700-800◦C under a constant flow of Ar and C2H2 with flow rates are 160 sccm and 5 sccm. After remove the AAO by sodium hydroxide solution and dry in the oven. Then the obtained MCNTs have been characterized by TEM, SQUID, XRD, TGA and Raman spectra. Two-parameter models of Langmuir and Freundlich isotherm were used to describe the adsorption of Cd (II) and Ni (II) on the MCNTs in aqueous solution. The results showed that the diameter of MCNTs is 250nm. The characteristic peaks at 1358cm-1 and 1594cm-1 obtained from Raman spectra were attributed to CNTs. The XRD analyses of the MCNTs confirmed the crystal phase of Fe3O4, Fe2O3 and graphene. The saturation magnetism of MCNTs is 7.298 emu g-1. Cd (II) and Ni (II) remove by MCNTs were in good agreement with the Langmuir isotherm model. This study demonstrated that MCNTs were successfully synthesized by AAO/CVD methods which were feasible to be applied on the adsorption removal of Cd (II) and Ni (II).

博士
國立成功大學
物理學系碩博士班
93
Zero-dimensional carbon tori and one-dimensional carbon nanotubes are studied for their electronic and magnetic properties. The effects due to the direction and the magnitude of the magnetic field, the transverse electric field, the height, the radius, the chiral angle, and the temperature are investigated in detail. The nearest-neighbor tight-binding model with the curvature effects are used to calculate electronic structures. The magnetic field might destroy state degeneracy, lead to semiconductor-metal transitions, modulate energy spacings, cause Aharonov-Bohm (AB) oscillations, alter edge states, and change subband curvatures or effective masses. The transverse electric field in carbon tori could induce similar effects except the AB oscillations. Due to the quantum size effect, there are certain important differences between carbon tori and carbon nanotubes in electronic properties, such as density of states, state degeneracy, and energy gap. The main features of electronic properties are directly reflected in magnetic properties. Magnetism and strength of magnetic response are mainly determined by the geometric structures and the magnitude and the direction of magnetic field. Carbon tori quite differ from carbon nanotubes in magnetic properties, e.g., the paramagnetic or diamagnetic behavior at small magnetic field, the magnetic susceptibility, and the critical magnetic field in changing magnetism.

Studies on charge transport properties in carbon nanotubes (CNTs) have been a subject of great interest for a long time not only as an important topic in fundamental science, but also as a basic requirement for the application of CNTs for nanoelectronics. CNTs show a wide range of transport behavior that varies from ballistic to hopping regime, depending on the dimensionality and nature of disorder in the system. Minute variations in disorder can lead from weak to strong localization, and this yields complex and intriguing features in the analysis of transport data. It is particularly important to carry out such a study for multiwall carbon nanotubes (MWCNTs), in which both dimensionality and disorder play an important role and the nature of localization is non-trivial as wave functions are extended along the tube or bundle of tubes. A proper understanding of the mechanisms of charge transport and their quantitative knowledge is an essential requirement for any possible application of CNTs in nanodevices. Such studies not only yield information on the transport parameters crucial for applications but can also provide a test for any possible microscopic theories of transport. Main focus of the current thesis is to understand the mechanism of charge transport in iron-embedded MWCNTs and to gain more knowledge on the transport behavior. Magnetically functionalized CNTs, in particular the CNTs filled with ferromagnetic materials are of profound interest for the basic scientific research as well as for technological application. Iron-embedded MWCNTs are synthesized by one step pyrolysis method. This method gives a proper route to synthesize the magnetic particles encapsulated CNTs. Beyond the geometrical advantage of a cylinder-shaped nanostructure design, the carbon shells provide an effective protection against oxidation of magnetic nanoparticles. The iron-embedded MWCNTs exhibit excellent magnetic properties like the uniaxial magnetic anisotropy, and the high coercivity, which is larger than the coercivity of bulk iron. Thus, they have significant potential for data storage devices and biomedical applications. Vertical alignment of CNTs is an important issue for device applications such as field electron emitters and flat-panel displays. Vertically aligned MWCNTs are grown on various substrates in the present work and the role of catalyst particles in vertical alignment is discussed. This thesis also reports the investigations on the magnetic properties including magnetotransport studies. The thesis is organized in seven chapters and a brief summary of each chapter is given below. Chapter 1 presents an introduction of the CNTs and its structural and electronic properties. Charge transport in CNTs is then discussed in terms of the fundamental aspects of conduction regimes and transport length scales. The synthesis and characterization of iron-embedded MWCNTs is described in chapter 2. It is important to get good quality CNTs in a scalable way. The various methods available for CNT synthesis are arc discharge, laser ablation, chemical vapor deposition etc. A one-step thermally assisted pyrolysis method employed for synthesizing MWCNTs is a simple and cost-effective method. Benzene is used as a precursor and ferrocene as a catalyst in the present case. Good quality CNTs are obtained from this method, which are of multiwall in nature (outer diameter in the range of 10-25 nm). Vertically aligned mats of MWCNTs are also obtained on the quartz substrate. The thickness of the mats is several tens of microns. The prepared MWCNTs are characterized by electron microscopic studies for its structure and surface morphology. Many iron particles are seen inside the tubes. Energy dispersive x-ray (EDX) spectra taken from the small region of the sample under TEM show the presence of iron. Raman spectra of the sample suggest good quality of the tubes. Prominent G-peak in this spectrum shows that the sample is of well-graphitic nature. X-ray diffraction pattern of MWCNT material shows the presence of -Fe and Fe3C apart from the graphitic peak. Chapter 3 describes the growth of vertically aligned MWCNTs (v-MWCNTs) on various substrates and role of catalyst particles in the alignment. The v-MWCNTs are grown on sapphire, quartz and thermally oxidized silicon substrates without pre-deposition of any catalyst. The grown MWCNT mats had a thickness of several tens of microns. Surface elemental analysis shows the presence of catalyst particles on the substrate which is essential for vertical alignment of the tubes. It is found that the order in which the precursor and the catalyst were introduced during chemical vapor deposition determines the orientation of the nanotubes. When there were no catalyst particles on the substrate in the beginning, random alignment of CNTs took place instead of vertical alignment. Base growth mode of CNTs is proposed in the present case from the results obtained. Chapter 4 deals with the magnetic properties of the as-synthesized MWCNTs. The CNTs in pristine form are of diamagnetic in nature. The ferromagnetic-like behavior arises from the iron particles embedded in MWCNTs. These ferromagnetic particles are retained in the MWCNTs automatically, as the catalyst in this case contains iron. MWCNTs of different iron weight percentage are prepared by taking different amount of ferrocene as a precursor. These particles exhibit a magnetic moment up to 98 emu/g and coercivity in the range of 500–2000 Oe. Reduced magnetization is attributed to the formation of surface shell with spin disorder and to the presence of Fe3C phase. Large coercivity compared to the bulk vale of few orested is due to the complex state of interactions, which can create strong pinning centers for the core moments during the demagnetization. In addition the observed dependence of the magnetoresistance on the direction of applied field, is correlated with the shape anisotropy of the Fe particles. The trend of saturation of magnetization at higher fields suggests that exchange coupling in the present case is one-dimensional. The charge transport properties of MWCNT mats are discussed in chapter 5. Many of the transport parameters are often affected by the presence of magnetic field. In order to gain a deeper insight into the conduction mechanism, the study of the electrical transport in presence of magnetic field is highly useful. The temperature and magnetic field dependence of the conductivity of MWCNT mat is studied in the temperature range of 1.4-150 K in the magnetic field up to 10 T. The charge transport in the system is governed by Mott’s variable-range hopping (VRH) of three-dimensional type in the higher temperature range and two-dimensional type in the lower temperature range. Mott’s various parameters like localization length, hopping length, hopping energy, and density of states at the Fermi level are deduced from the VRH fit. The hopping length decreases from 13.2 to 12.2 nm, as temperature increases from 110 to 150 K. The obtained value of hopping length around ~13 nm is within the range of nanotube diameters of 10 to 25 nm. This is the main component of the hopping length, which indicates that VRH takes place on the tube scale. The localization lengths observed in the case of 3D VRH and 2D VRH conduction are well within the range of outer diameter of MWCNTs, which indicates that the localization takes place at the tube scale along the boundaries of the tubes. If the charges are localized at the tube boundaries, then the localization length gives an average diameter of the tubes and the results obtained supports this argument. It is also important to note that the defects present in the nanotubes in the form of structural defects and bad matching of chirality gives rise to localization. There are not many reports on the effect of a magnetic field on the VRH process for MWCNT systems. The resistance of the sample decreases with the magnetic field in the direction of tube axis of the nanotubes. The magnetic field gives rise to delocalization of states as evident from the values of localization lengths at different fields. The application of magnetic field lowers the crossover temperature, at which three-dimensional VRH turns to two-dimensional VRH. The conductivity at the lower temperature side is governed by the weak localization (WL) give rise to positive magnetoconductance (MC). Here a phase diagram with temperature and magnetic field is proposed, showing different regions for different kind of transport mechanisms. This may be applicable for other class of disordered material as well. Chapter 6 deals with the magnetotransport studies on disordered MWCNT mat. The electrical conductivity and MC data are analyzed in the temperature range of 1.4-150 K and in the magnetic fields up to 11 T. The system is in the critical regime obeying conductivity of metallic systems as suggested in weak localization-electron electron interaction model. The MC is positive for the whole temperature range except at temperature below 4.2 K. Results are analyzed in the terms of weak localization, electron-electron interaction and VRH. The H 2 dependence at lower magnetic fields and H dependence at higher magnetic fields is found supporting weak localization. Inelastic scattering lengths are also deduced from the low temperature MC data and its temperature dependence shows that the dominant dephasing mechanism in the present case is inelastic electron-electron scattering in the dirty limit. Chapter 7 describes measurements on individual MWCNTs and subsequent charge transport studies. After many trials a suitable method was devised to isolate single tubes and to put contacts on it for the four probe measurement. For electrical measurements on isolated single tube, it is found that the joule heating due to excess current is an important issue. A current of the order of few µA burns the sample immediately. I-V characteristics of the MWCNTs show that the electrical contacts are ohmic and the resistance is few k. Initial electrical measurements show that there is slight decrease in resistance with increase of temperature and MR is approximately negative. This behavior suggests that signature of weak localization is present in the sample. Further studies are required in order to gain the insight into the transport mechanism for individual MWCNT. Finally, the thesis concludes with a general conclusion and future directions for this work.

Carbon nanotubes (CNTs) have special characteristics that made them good agents especially for biomedical applications. In this study, Fe3O4 nanoparticles were incorporated onto the surface of CNTs followed by polyethylene glycol (PEG) grafting forming CNTs-Fe3O4-PEG hybrids. The PEGylation improves their biocompatibility, water solubility, and increases blood circulation. CNTs-Fe3O4-PEG was used as T2-contrat agent for magnetic resonance imaging (MRI). In addition, doxorubicin (DOX) was loaded onto CNTs-Fe3O4-PEG. The release of DOX from DOX-loaded CNTs-Fe3O4-PEG was tested under different pH conditions (7.4, 6.3 and 5.2). The release increased at acidic pH compared to neutral pH, which shows the sensitivity of the system to pH change. Triggering the release by Near Infra-Red (NIR) irradiation was furthermore investigated. The release increased after irradiation with NIR compared to control sample. These result prove that the designed system can be triggered by an internal stimuli (pH) and external stimuli (NIR irradiation) making it a promising candidate to be used for biomedical applications.

Carbon nanotubes (CNTs) have been recognized as potential candidates for mainstream device fabrication and technologies. CNTs have become a topic of interest worldwide due to their unique mechanical and electrical properties. In addition, CNTs possess high aspect ratio and low density that make them an important material for various technological applications. The field of carbon nanotube devices is rapidly evolving and attempts have been made to use CNTs in the fabrication of devices like field emitters, gas sensors, flow meters, batteries, CNT-field effect transistors etc. These molecular nanostructures are proposed to be an efficient hydrogen storage material. CNT cylindrical membranes are reported to be used as filters for the elimination of multiple components of heavy hydrocarbons from petroleum and for the filtration of bacterial contaminants of size less than 25 nm from water. Recently, CNT bundles have been proposed to be a good material for low-temperature sensing. CNTs have also been considered as promising filler materials due to extraordinary characteristics mentioned above. Fabrication of nanocomposites using CNTs as reinforcing material has completely renewed the research interest in polymer composites. The conductive and absorptive properties of insulating polymer doped with conducting filler are sensitive to the exposure to gas vapors and hence they can be used in monitoring various gases. The application of fiibre reinforced polymer composites in aeronautic industry are well known due to their high mechanical strength and light weight. Also, the conductive composite materials can be used for electromagnetic shielding. Desired properties in CNT-composites can be attained by adding small amount of CNTs in comparison to traditional filler materials. Due to high aspect ratio and low density of CNTs, percolation threshold in CNT-polymer composites can be achieved at 0.1 vol % as compared to ~16 vol. % in case of carbon particles. The research work ׽0.1 vol. %, as compared to reported in this thesis includes the preparation of multiwall carbon nanotube (MWNTs) and MWNT-polystyrene composites, experimental investigations on low temperature charge transport, and magnetic properties in these systems. This thesis contains 7 chapters. Chapter 1 provides an overview of CNTs and CNT-polymer composites. This chapter briefly describes the methods for synthesizing CNTs and fabricating CNT-polymer composites, charge transport mechanisms in CNTs and composites, and their magnetic properties as well. Chapter 2 deals with the concise introduction of various structural characterization tools and experimental techniques employed in the present work. An adequate knowledge of the strengths and limitations of experimental equipment can help in gathering necessary information about the sample, which helps in studying and interpreting its physical properties correctly. Chapter 3 describes the synthesis of MWNTs and their use as filler material for the fabrication of composites with polystyrene (PS). The characterization results of as-prepared MWNT and composites show that MWNTs possess high aspect ratio (~4000), and are well dispersed in the composite samples (thickness ~50-70 µm). The composite samples are prepared by varying the MWNT concentration from 0.1 to 15 wt %. The as¬fabricated composites are electrically conductive and expected to display novel magnetic properties since MWNTs are embedded with iron (Fe) nanoparticles. Chapter 4 presents the study of charge transport properties of aligned and random MWNTs in the temperature range 300-1.4 K. The low temperature electrical conductivity follows the weak localization (WL) and electron-electron (e-e) interaction model in both samples. The dominance of WL and e-e interaction is further verified by magneto-conductance (MC) measurements in the perpendicular magnetic field up to 11 T at low temperatures. The MC data of these samples consists of both positive and negative contributions, which originates from WL (at lower fields and higher temperatures) and e-e interaction (at higher fields and lower temperatures). Chapter 5 contains the results of charge transport studies in MWNT-PS composite near the percolation threshold (~0.4 wt %) at low temperatures down to 1.4 K. Metallic-like transport behavior is observed in composite sample of 0.4 wt %, which is quite unusual. In general, the usual activated transport is observed for systems near the percolation threshold. The unusual weak temperature dependence of conductivity in MWNT-PS sample at percolation threshold is further verified from the negligible frequency dependence of conductivity, in the temperature range from 300 to 5 K. Chapter 6 accounts on the experimental results of magnetization studies of MWNTs and MWNT-PS composites. The observation of maxima in coercivity and squareness ratio at 1 wt % of Fe-MWNT in a polymer matrix show the dominance of dipolar interactions among the encapsulated Fe-nanorods within MWNTs. The hysteresis loop of 0.1 wt % sample shows anomalous narrowing at low temperatures, which is due to significant contribution from shape anisotropy of Fe-nanorods. Chapter 7 presents brief summary and future perspectives of the research work reported in the thesis.