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Functionalizing the Microtubule LumenJoshi, Foram Meghal 03 June 2022 (has links)
The functionalization of the outer lattice of in vitro reconstituted microtubules has paved the way for the development of diverse nano-device applications. The outer lattice has been metallized for the bottom-up synthesis of nanowires composed of various materials. Moreover, a wide range of biomolecules and nanoprobes have been attached to the outer surface for nano-scale transport and detection assays in conjunction with motor proteins. The functionalization of the outer lattice has certain implications: While the nanowires adopt the overall shape of the microtubules, their surface is inhomogeneous due to the absence of any morphological control. The attachment of cargo on the outer lattice creates a ‘roadblock effect’ hindering the transport activity of the motor proteins as they share a common substrate surface. In this project, the utilization of the hollow interior region of the microtubules, called the lumen (∼15 nm in diameter) is proposed to overcome these limitations. A strategy is developed to functionalize the microtubule lumen by targeting molecular cargo conjugated to lumen-binding (anti-acetyl alpha-tubulin lysine-40) antibodies. This would optimize existing motility-based applications as the outer surface would be exclusively available for the activity of the motor proteins. Furthermore, microtubules functionalized with luminal gold nanoparticle ‘seeds’ are utilized for the lumen-templated assembly of gold nanowires.
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Étude des propriétés mécaniques de l'or sous forme de nanofil et de structure nanoporeuse par dynamique moléculaire / Study of the mechanical properties of gold in the form of nanowire and nanoporous structure by molecular dynamicsGuillotte, Maxime 12 November 2019 (has links)
Dans cette thèse nous avons étudié en détail les propriétés mécaniques de l’or sous forme de nanofils et de structures nanoporeuses revêtues ou non de silicium amorphe (a-Si). Ces travaux ont été effectués par dynamique moléculaire. Nous avons dans un premier temps étudié la déformation cyclique de nanofils d’or (NF-Au) et de nanofils cœur-coquille or-silicium amorphe (NF-AuSi). Ces simulations ont montré que le NF-Au est déformé au cours des cycles par deux mécanismes prépondérants : le maclage extensif puis le glissement d’un unique plan atomique. Le cyclage a pour effet d’altérer progressivement la morphologie de la structure en augmentant le nombre et la taille des défauts créés en surface. La déformation cyclique du NF-AuSi montre que le revêtement de a-Si délocalise la plasticité le long de la structure et permet de mieux conserver la morphologie initiale du cœur. Nous avons ensuite développé une méthode originale de génération de l’or nanoporeux. Cette méthode a été validée par la comparaison structurale et mécanique avec des résultats expérimentaux. Puis nous avons étudié la déformation en traction et en compression de différentes structures générées par cette méthode. Nous avons dans les deux cas mis en évidence les mécanismes de déformation des ligaments. En traction, nous avons apporté de nouveaux résultats permettant de mieux comprendre pourquoi l’or nanoporeux est fragile alors que l’or massif est ductile. En particulier, nous avons étudié comment s’opère la fracture en cascade des ligaments par transfert de contrainte entre ceux-ci. En compression nous avons entre autres montré que l’effondrement des pores et la création de joints de grains est responsable de l’augmentation de la contrainte à la transition écoulement-densification. Les simulations de traction et de compression des mêmes structures mais revêtues de silicium amorphe montrent plusieurs résultats intéressants. Par exemple, la résistance des structures est augmentée d’un facteur 2 à 4. De plus, le revêtement a pour effet de délocaliser la plasticité ce qui augmente la ductilité notamment en traction. En compression, la transition écoulement-densification est avancée probablement en raison de la diminution de la taille des pores causée par le revêtement. / In this thesis we have studied in detail the mechanical properties of gold nanowires and nanoporous gold with and without an amorphous silicon coating (a-Si). This work was done using molecular dynamics simulation. We first studied the cyclic deformation of gold nanowires (Au-NW) and gold-silicon core-shell nanowires (AuSi-NW). These simulations showed that the Au-NW is deformed during cyclic loading by two main mechanisms: extensive twinning and the slip of a single atomic plane. Cycling gradually alters the morphology of the structure by increasing the number and size of defects created on the surface. The cyclic deformation of the AuSi-NW shows that the a-Si coating delocalizes the plasticity along the structure and allows to better preserve the initial morphology of the core. We then developed an original method for generating nanoporous gold. This method was validated by structural and mechanical comparison with experimental results. Then we studied the tensile and compressive deformation of different structures generated by this method. In both cases, we have highlighted the deformation mechanisms of ligaments. In tension, our simulations have brought new results to better understand why nanoporous gold is brittle while bulk gold is ductile. In particular, we studied how the catastrophic failure of ligaments occurs by stress transfer between them. In compression we have shown, for example, that pore collapse and the creation of grain boundaries are responsible for the increase of stress at the transition from flow to densification. Tensile and compression tests simulations on the same structures but coated with amorphous silicon show several interesting results. For example, the strength of the structures is increased by a factor of 2 to 4. In addition, the coating has the effect of delocalizing the plasticity, which increases ductility, particularly in tension. In compression, the transition from flow to densification is advanced probably due to the decrease in pore size caused by the coating.
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Investigation of Structural and Electronic Aspects of Ultrathin Metal NanowiresRoy, Ahin January 2015 (has links) (PDF)
The constant trend of device miniaturization along with ever-growing list of unusual behaviour of nanoscale materials has fuelled the recent research in fabrication and applications of ultrathin (~2 nm diameter) nanowires. Although semiconductor nanowires of this dimension is well-researched, molecular-scale single-crystalline metal nanowires have not been addressed in details. Such single crystalline Au nanowires are formed by oriented attachment of Au nanoparticles along [111] direction. A very low concentration of extended defects in these wires result in a high electrical conductivity, making them ideal for nanoscale interconnects. Other metal nanowires, e.g. Ag and Cu, have very low absorption co-efficient useful for fabrication of transparent conducting films. On the other hand, because of the reduced dimensions, there exists a tantalizing possibility of dominating quantum effects leading to their application in sensing and actuation. Also, speaking in terms of atomic structure, these systems suffer from intense surface stress, and the atomistic picture can be drastically different from bulk. Thus, although a myriad of applications are possible with ultrathin metal nanowires, a rigorous systematic knowledge of their atomic and electronic structure is not yet available. This thesis is the first one to model such computationally demanding systems with emphasis on their possible applications.
In this thesis, we have explored various structural and electronic aspects of one-dimensional ultrathin nanowires with ab initio density functional theory coupled with experiments. The merit of Au nanowires has been tested as nanoscale interconnects. From atomistic point of view, these FCC Au nanowires exhibit an intriguing relaxation mechanism, which has been explored by both theory and experiment. The primary factor governing the relaxation mechanism was found to be the anisotropic surface stress of the bounding facets, and it is extended to explain the relaxation of other metallic nanowires. Our studies suggest that AuNWs of this dimension show semiconductor-like sensitivity towards small chemical analytes and can be used as nanoscale sensors. Also, we have found that further reducing the diameter of the Au-nanowires leads to opening of a band gap.
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Interfacing Biomolecules with Nanomaterials for Novel ApplicationsLal, Nidhi January 2014 (has links) (PDF)
This thesis deals with the research work carried out for the development of novel applications by integrating biomolecules with various nanostructures. The thesis is organized as follows:
Chapter 1 reviews the properties of nanomaterials which are important to consider while developing them for various biological and other applications. It discusses the factors which affect the cytotoxicity of nanocrystals towards living cells, photocatalytic mechanisms of nanocrystals that work behind the inactivation of bacterial cells and gas sensing properties of
nanocrystals. It also mentions about the integration of biomolecules with nanomaterials which is useful for the development of biosensors, materials that are presently used for fabricating biosensors and the challenges associated with designing successful biosensors.
Chapter 2 presents the antibacterial and anticancer properties of ZnO/Ag nanohybids. In this study a simple route to synthesize ZnO/Ag nanohybrids by microwave synthesis has been established where ZnO/Ag nanohybrids have shown synergistic cytotoxicity towards mammalian cells. The observed synergism in the cytotoxicity of ZnO/Ag nanohybrids could lead to the development of low dose therapeutics for cancer treatment.
Chapter 3 presents photocatalytic inactivation of bacterial cells by pentavalent bismuthates class of materials. AgBiO3 which was obtained from KBiO3 by ion-exchange method was investigated
for its photocatalytic inactivation properties towards E.coli and S.aureus cells under dark and UV illumination conditions.
Chapter 4 presents the integration of DNA molecules with ZnO nanorods for the observation of Mott-Gurney characteristics. In this study, ZnO nanorods were synthesized hydrothermally and were characterized by TEM and XRD analysis. DNA molecules were immobilized over ZnO nanorods which were confirmed by UV-Vis spectroscopy and confocal florescence microscopy.
Solution processed devices were fabricated by using these DNA immobilized nanostructures and I-V characteristics of these devices were taken in dark and under illumination conditions at different wavelengths of light at fixed intensity. Interestingly, Mott-Gurney law was observed in the I-V characteristics of the devices fabricated using DNA immobilized ZnO nanorods.
Chapter 5 presents the chemical synthesis of molecular scale ultrathin Au nanowires. These
nanostructures were then used for fabricating electronic biosensors. In this study, the devices were fabricated over Au nanowires by e-beam lithography and a methodology to functionalize
Au nanowires and then characterize them by florescence microscopy as well as AFM has been established. The fabricated biosensors were employed for the label free, electrical detection of DNA hybridization process.
Chapter 6 presents a simple, cost effective and solution processed route to fabricate devices using ultrathin Au nanowires. The devices were then used for sensing ethanol, H2 and NH3. An important property of these devices is that they can sense these gases at room temperature which reduce their operation cost and makes them desirable to use under explosive conditions.
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Croissance par voie chimique et propriétés de transport électronique de nanofils d'or / Chemical growth and electronic transport properties of gold nanowiresLoubat, Anais 31 March 2014 (has links)
Les nanofils d’or ultrafins sont des objets fascinants présentant une morphologie quasi 1D, leur diamètre n’excédant par 2 nm pour une longueur micrométrique. Les quelques 30 atomes qui composent la section de ses fils sont principalement des atomes de surface, permettant d’envisager des applications de type capteurs. De plus, l’anisotropie de forme unique pourrait permettre un confinement électronique unidimensionnel, menant à de nouvelles propriétés physiques. Nous avons réalisé une étude fondamentale de la synthèse et réaliser une première étude de transport sur une assemblée de nanofils.La première partie du manuscrit, divisée en quatre chapitres, consiste en l’étude du mécanisme de croissance de ces nanofils ultrafins. Suite à une analyse détaillée des modèles proposés, nous introduisons la technique de diffusion des rayons X aux petits angles (SAXS) utilisée pour nos études mécanistiques. Le chapitre 3 est consacré à l’étude de la synthèse de nanofils en milieu confiné. Contrairement aux postulats précédents, un suivi cinétique in-situ par SAXS nous a permis de montrer que la phase lamellaire n’intervenait pas dans la croissance des objets, voir même qu’elle était détrimentaire à leur formation. Le dernier chapitre présente la synthèse en milieu isotrope. Un mécanisme de croissance efficace où les sphères jouent le rôle de germe est avancé. L’auto-organisation des fils en solution suivant une phase hexagonale appuie l’hypothèse d’une stabilisation des fils par une double couche d’oleylamine et de chlorure d’ammonium. Un mécanisme de croissance analogue aux mécanismes proposés pour les bâtonnets d’or dans l’eau est donc proposé.La deuxième partie du manuscrit, divisée en trois chapitres, consiste en une caractérisation des propriétés de transport électronique dans ces nanofils d’or ultrafins. Nous dressons, dans un premier temps, un bilan des différents régimes de transport observés au sein de nano-objets de basse dimensionnalité. Suite aux étapes indispensables de dépôt et de connexion, le troisième chapitre présente les premières mesures de transport effectuées sur des assemblées de nanofils d’or faiblement couplées. Nous mettons ainsi en évidence, grâce à une étude sur une large gamme de températures et de tensions de polarisation, un transport de charge coopératif dans le cadre d’un régime de blocage de Coulomb. / Ultra-narrow gold nanowires are captivating objects with a quasi-1D morphology, with a diameter lower than 2 nm and a micrometric length. The few 30 atoms which compose the wire section are mainly surface atoms, allowing to consider applications such as sensors. Moreover, the unique anisotropic shape may permit a one-dimensional electronic confinement, leading to new physical properties. We conducted a fundamental study of the synthesis and a preliminary transport study on an assembly of nanowires.The first part of the manuscript, divided into four chapters, consist of the growth mechanism study of these ultra-narrow gold nanowires. Further to a detail analysis of the proposed models, we present the small angle X-rays scattering (SAXS) technique used for our mechanistic studies. The third chapter deals with the study of the nanowires synthesis in a confined environment. Unlike the previous postulates, a in-situ kinetic monitoring by SAXS allow us to point out that the lamellar phase was not involved in the objects’ growth, even more that it was detrimental for their formation. The last chapter presents the synthesis in an isotropic system. An efficient growth mechanism where the spheres act as seeds is advanced. The wires’ self-assembly in solution in a hexagonal super-lattice supports the hypothesis of wire stabilization by a bilayer of oleylamine and oleylammonium chloride. Therefore, a growth mechanism similar to the one proposed in the case of gold nanorods in water is proposed.The second part of the manuscript, divided into three chapters, consist in a characterization of the electronic transport properties in these ultra-narrow gold nanowires. At first, we report on the different types of transport observed low-dimensionality nano-objects. Further to the necessary deposit and connection steps, the third chapter presents the first transport measurements performed weakly coupled assemblies of gold nanowires. We highlight, through a study on a wide range of temperatures and bias voltages, a cooperative charges transport through a Coulomb blockade regime.
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