Dissertations / Theses: 'Nanomaterials - Inorganic Chemistry'

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Alharthi, Fahad Ahmed A. "New inorganic nanomaterials for low-voltage transistor applications." Thesis, University of Hull, 2016. http://hydra.hull.ac.uk/resources/hull:16517.

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This research aims to synthesise and characterise solution-processable high-k dielectric nanorods, which are potentially suitable for use as the dielectric layer in low-voltage Organic Field-Effect Transistor (OFET) applications. Oleic acid-stabilised titanium dioxide nanorods (TiO2-OA), metal-doped anatase titanium oxide (TiO2-OA-M; M=Nb, In, or Nb/In) nanorods, rutile titanium oxide nanorods (TiO2) and barium titanium oxide nanorods (BaTiO3) have been prepared and investigated. Solution processable oleic acid-stabilised titanium dioxide nanorods (TiO2-OA) have been prepared by hydrolysis of titanium (IV) tetraisopropoxide (TTIP) with oleic acid (OA) as surfactant in the presence of trimethylamine N-oxide (TMAO). Furthermore, a series of ligand exchange reactions were carried out to replace the oleic acid bonded on the surface of TiO2-OA with diethyl 2-phenylethyl phosphonate (DEPPNA), octadecylphosphonic acid (ODPA) or octylphosphonic acid (OPA). The ligand exchange rate was characterised by a combination of 31P liquid NMR, ICP, CHN, and FT-IR. The solubility of the ligand-exchanged products in chlorobenzene was also investigated. A novel method based on the co-hydrolysis of titanium (IV) tetraisopropoxide (TTIP) and niobium or/and indium isopropoxide or ethoxide has been investigated to prepare solution-processable, oleic acid- stabilised, niobium- and indium-doped, anatase TiO2 nanorods (TiO2-OA-M; M = Nb, In or Nb/In). The effect of niobium and indium precursors, the molar ratio of Nb or In precursors/TTIP and reaction time on the composition, structure and morphology of the Nb or In doped TiO2 products have been investigated by a combination of XPS, XRD, ICP, CHN, FT-IR and TEM. Furthermore, a series of ligand exchange reactions were carried out to replace the oleic acid, which is bonded on the surface of TiO2-OA-M, with diethyl 2-phenylethyl phosphonate (DEPPNA) or octadecylphosphonic acid (ODPA). The solubility of the products in chlorobenzene was also investigated. Rutile titanium dioxide nanorods with different sizes were prepared by three different approaches. In the first approach,hair-like rutile nanorods TiO2 were prepared by simple hydrolysis of a TiOCl2 solution at low temperature (50, 70 and 90 °C). In the second approach, rutile nanorods TiO2 with a length of 150-200 nm and a width of 25-40 nm were prepared by using a hydrothermal treatment of TiOCl2 at 220 °C. In the third approach, rutile nanorods TiO2 with length of 80 nm and diameter of 20 nm were prepared by using an hydrothermal reaction of TiOCl2 in the presence of 3-hydroxytyramine hydrogen chloride, [(HO)2C6H3CH2CH2NH2·HCl] at 150°C. In order to improve the solubility of the obtained rutile titanium dioxide nanorods in organic solvents, different surface-modification methods have been investigated to coat the surface of the rutile titanium dioxide nanorods with various organic ligands. In the first method, a modification of the TiO2 nanorods with oleic acid (OA) in chlorobenzene was investigated. In the second method, a two-stage treatment of TiO2 nanorods in an acidic medium was studied, using a selection of oleic acid (OA), diethyl 2-phenylethyl phosphonate (DEPPNA), octylphosphonic acid (OPA) and decylphosphonic acid (ODPA) as ligands. In the third method, wet TiO2 nanorods before dry was directly modified with a range of oleic acid and amines, e.g., octylamine, dodecylamine and hexadecylamine, as ligands. All the products were characterized by a combination of XRD, ICP, CHN, FT-IR and TEM. The preparation of barium titanium oxide nanorods (BaTiO3) has been investigated by different approaches. In the first approach, a hydrothermal reaction was carried out to convert the titanium dioxide nanorods prepared in the first and third parts in this research into BaTiO3 nanorods. The effect of the molar ratio of Ba/Ti, the reaction pH, reaction time and temperature on the composition, structure and morphology of the products were fully investigated. In the second approach, a hydrothermal reaction using a single source Ba/Ti precursor, i.e., barium titanium ethylhexano-isoproxide BaTi(O2CC7H15)(OC3H7)5, was carried out to prepare barium titanium oxide nanorods. In the third approach, barium titanium oxide nanorods were prepared by using a hydrothermal reaction between barium chloride (BaCl2) and titanium oxy chloride (TiOCl2) in the presence of ethylene glycol as surfactant. All the products have been characterised by a combination of XRD, ICP, CHN, FT-IR and TEM.

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Tsui, Hei Man. "Synthesis and Characterization of Magnetic Cabides and Oxides Nanomaterials." VCU Scholars Compass, 2018. https://scholarscompass.vcu.edu/etd/5366.

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The design and development of nanoparticles is of great interest in the current energy and electronic industry. However, based on the current materials available the production cost can be high with insignificant magnetic and mechanical properties. Specifically, rare-earth magnetic materials composed of neodymium and samarium are known for their high magnetic performance, however, due to the cost of development there is a need to develop a versatile and cost effective material. Alternatively, cobalt carbide nanomaterials have shown to be a promising alternative for rare-earth free magnets as they exhibit comparable properties as hexaferrite magnetic materials. The primary goal of this dissertation focuses on the development of nanoparticles for permeant magnetic, and magnetic refrigeration applications. The first part of this work focuses on the synthesis of cobalt carbide (CoxC, x=2,3) nanoparticles using a novel polyol synthesis method by introducing a small amount of Ru, Cu, or Au as nucleating agent. It was found that the morphology and magnetic properties of the as-synthesized CoxC nanoparticles change as a result of directional growth of nanoparticles using nucleating agents. Needle-like particle morphology ranges from 20-50 nm in width and as long as 1 µm in length were synthesized using Ru as nucleating agent. These particles exhibit magnetization saturation of 33.5 emu/g with a coercivity of 2870 Oe and a maximum energy product 1.92 MGOe (BHmax) observed. Particle morphology is a critical aspect in the development of magnetic nanoparticles as anisotropic particles have shown increased coercivity and magnetic properties. These CoxC nanomaterials have a higher maximum energy product compared to previous work providing further insight into the development of non-rare earth magnetic material. The second part of this dissertation work focuses on the sol-gel synthesis of perovskite LaCaMnO3 (LCMO) nanomaterials. In this process, various chain lengths of polyethylene glycol (PEG) was added into a solution consisting of La, Ca, and Mn salts. The solution was left for the gelation process, and high temperature sintering to obtain the final product. By varying the polymer chain of the PEG, the size of the as synthesized LaCaMnO3 nanomaterials were altered. The as-synthesized LCMO nanomaterials have shown a maximum change in magnetic entropy (-ΔSM) was found to be 19.3 Jkg-1K-1 at 278 K for a field change of 0-3 T and 8.7 Jkg-1K-1 for a field change of 0-1 T. This is a significant improvement in comparison to current literature of the material suggesting that this is a promising alternative to Gd materials that is prone to oxidation. With additional development, LCMO or related maganites could lead to application in commercial technologies.

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Berestok, Taisiia. "Assembly of colloidal nanocrystals into porous nanomaterials." Doctoral thesis, Universitat de Barcelona, 2018. http://hdl.handle.net/10803/663275.

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This thesis focuses on different aspects of NCs colloidal synthesis, the exploration of the relevant surface chemistries that afford NC assembly and the NC implementation into porous nanomaterials. The work is divided into two blocks. The first block is devoted to developing and optimizing the synthesis of NCs followed by the examination of their suitability for potential applications in catalysis and photocatalysis. The second block is dedicated to establish procedures to fabricate single-component or multicomponent porous nanomaterials from NC building blocks. To embrace the use of the developed strategies in different application fields, several kind of materials were under research. Namely, metals (e.g. Au), metal oxides (e.g. CeO2, TiO2, Fe2O3), metal chalcogenides (e.g. In2S3, ZnS, PbS, CuGaS2 and Cu2ZnSnSe4), and their composites. CeO2 NCs synthesis was deeply investigated with the aim to achieve a proper control on the NCs morphology, facets exposed, crystal phase, composition, etc., required for application. Overall, CeO2 NCs with spherical, octapod-like branched, cubic hyperbranched, and kite-like morphology with sizes in the range 7 to 45 nm were produced by adjusting experimental conditions of the synthetic protocol. Branched and hyperbranched NCs showed higher surface areas, porosities and oxygen capacity storage values compared to quasi-spherical NCs. The NCs morphology-controlled synthesis has been extended to quaternary Cu2ZnSnSe4 (CZTSe). CZTSe NCs with narrow size distribution and controlled composition were produced. It was shown how off-stoichiometric CZTSe compositions were characterized by higher charge carrier concentrations and thus electrical conductivities. The strategy to functionalize the metal oxide NC surface composition by applying different ligands is proposed. This enables to develop a novel approach to assemble metal oxide NCs into porous gel and aerogel structures. Propylene oxide has been found to trigger the gelation process of glutamine functionalized NCs. The detailed investigation of the gelation mechanism is demonstrated for the case of ceria. The method is applied for NCs with different morphologies. Eventually, the versatility of the concept is proved by using of the proposed approach for the TiO2 and Fe2O3 nanocrystals. The assembly method has been extended to metal chalcogenides - In2S3 NCs - starting from the NCs synthesis, with further surface chemistry manipulation and eventually follows by the NC assembly into gels and aerogels. The optimization of NC surface chemistry was achieved by testing different ligand exchange approaches via applying short-chain organic and inorganic ligands. The assembly method based on ligand desorption from the NC surface and chalcogenide-chalcogenide bond formation has been established for In2S3. The comparison of the different ligands impact on the NC performance in colloidal form, when assembled into gels and when supported onto substrate is investigated towards photoelectrocatalysis. The oxidative ligand desorption assembly approach has been extended for multicomponent NCs for the case of CuGaS2 and CuGaS2-ZnS. Optimization of spin-coating process of the formed NCs inks followed by applying of sol-gel chemistry led to formation of highly porous layers from TGA-CuGaS2 and TGA-ZnS. Applied results of CuGaS2/ZnS nanocrystal-based bilayers and CuGaS2–ZnS nanocrystal-based composite layers have been shown by testing their photoelectrochemical energy conversion capabilities. The approach to adjust NC surface chemistry has been proposed and tested for performing multicomponent NC assemblies. Applying of different ligands for NC surface functionalization endows their surface with different charges which usually provides colloidal NCs stabilization. It has been found that mixing of oppositely charged NCs with certain concentration enabled their assembly/gelation via electrostatic interaction. The proposed approach has been applied and optimized to produce multicomponent NC gels and aerogels. The detailed investigation of the gelation mechanism is shown for combination of metal-metal oxide and metal oxide-metal chalcogenide NCs (Au-CeO2, CeO2-PbS). Applied results of the Au-CeO2 aerogels were demonstrated for CO-oxidation.
Esta tesis se centra en la síntesis coloidal de nanocristales (NCs), en la exploración de su química de superficie y en su ensabanado en nanomateriales porosos funcionales. Para demostrar la versatilidad de aplicación de dichas estructuras, en este estudio se han considerado NCs de distintos tipos de materiales: metales (Au), óxidos metálicos (CeO2, TiO2, Fe2O3), calcogenuros metálicos (In2S3, ZnS, PbS, CuGaS2,Cu2ZnSnSe4) y sus materiales compuestos. El trabajo se dividió en dos bloques. En el primero se desarrolló y optimizó la síntesis de NCs de óxidos y calcogenuros metálicos y se evaluó su potencial para aplicaciones de catálisis y fotocatálisis. Se investigó en profundidad la síntesis de NCs de CeO2, poniendo énfasis en controlar su morfología. Se consiguió producir NCs de CeO2 de forma controlada (esférica, octapodo ramificado, cúbico ramificado y romboidal) y con tamaño controlado (7-45 nm). Asimismo, se obtuvieron NCs de Cu2ZnSnSe4 con una fina distribución de tamaños y composición controlada. En el segundo bloque se establecieron y estudiaron procedimientos para fabricar nanomateriales porosos mono- o multicomponentes a partir del ensamblado de NCs. Se desarrolló una estrategia basada en el ajuste de la química de superficie de NCs de óxidos metálicos (CeO2, Fe2O3,TiO2) y de calcogenuros metálicos (In2S3, CuGaS2-ZnS) que permitió su ensamblaje controlado en estructuras porosas de tipo gel y aerogel. En el caso de los óxidos metálicos, se determinó que el ensamblado se inicia con la adición de un epóxido a NCs funcionalizados con glutamina, causando la gelación. La desorción oxidativa de ligandos basada en la formación de enlaces calcogenuro-calcogenuro se propuso como mecanismo de gelación en calcogenuros mono- (In2S3) y multicomponente (CuGaS2-ZnS). Se investigó el impacto del empleo de distintos ligandos en la eficiencia foto-electrocatalítica de NCs en forma coloidal, ensamblados en geles y soportados en sustratos. Se desarrolló y estudió el ajuste de la química de superficie de NCs para la obtención de ensamblajes multicomponente mediante interacción electrostática de coloides en suspensión. El mecanismo de gelación fue investigado al detalle para materiales compuestos de NCs de oxido metálico (CeO2) con NCs de óxido de calcogenuro (PbS-CeO2) y metálicos (Au-CeO2). Los aerogeles de Au-CeO2 demostraron potencial para la oxidación de CO.

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Lisowski, Carmen Ellen 1978. "Hybrid organic/inorganic nanomaterials: Development of malonamide-functionalized nanoparticles designed for lanthanide ion detection." Thesis, University of Oregon, 2010. http://hdl.handle.net/1794/10523.

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xviii, 174 p. : ill. (some col.) A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number.
Hybrid nanoscale complexes incorporate the attributes of organic and inorganic components to yield novel multifunctional materials. Because the individual components themselves and the combinations used can be widely varied to tune the properties of the resulting complex, the potential for new properties and practical applications is nearly limitless. However, widespread use of these materials relies on appropriate design, synthesis and characterization strategies to ensure proper function and compositional integrity. This dissertation describes the chemistry of these hybrids, made possible by combining organic ligands, inorganic nanoparticles, and metal ions, and the interesting optical and spectroscopic properties associated with the hybrid nanomaterials. Organic ligands containing Bunte salt and acyclic malonamide functionalities were attached to gold nanoparticles to produce colorimetric sensors for lanthanide ion detection. Bunte salt functionality stabilizes the gold core and malonamide functionality offers selective and sensitive lanthanide ion binding. The binding interaction controls a nanoparticle cross-linking event that changes the color of the nanoparticle solution, resulting in visual, colorimetric lanthanide ion detection. Next, the concentration of malonamide ligand was diluted and replaced with a diluent ligand yielding nanoparticles stabilized with a mixed ligand composition. The mixed ligand environment makes the optical response of the colorimetric sensor reversible. Furthermore, the use of Bunte salt ligands during nanoparticle synthesis has allowed the investigation of the role of reducing agent on nanoparticle stability. In addition to exploring interactions pertaining to gold nanoparticle complexes, a new approach to sensitize europium ion luminescence was developed by fabricating a zinc oxide/europium complex. A molecular linker permits simultaneous zinc oxide nanoparticle functionalization and trivalent europium binding in order to tether the europium ion close to the nanoparticle surface. The zinc oxide nanoparticle can then act as an inorganic antenna, transferring energy to the europium ion and enhancing its luminescence. Finally, a strategy was developed to synthesize bifunctional bicyclic malonamides. Synthesis of these ligands allows the enhanced f-block ion binding affinity of bicyclic malonamides to be incorporated into functional materials to compare their performance to our previously prepared acyclic malonamide hybrid complexes. This dissertation includes my previously published and co-authored materials.
Committee in charge: Darren Johnson, Chairperson, Chemistry; James Hutchison, Advisor, Chemistry; Catherine Page, Member, Chemistry; Michael Haley, Member, Chemistry; Barbara Roy, Outside Member, Biology

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Huba, Zachary. "Synthesis and characterization of cobalt carbide based nanomaterials." VCU Scholars Compass, 2014. http://scholarscompass.vcu.edu/etd/3320.

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Permanent magnets are used heavily for multiple applications in industry and current electronic technologies. However, the current permanent landscape is muddled by high cost of materials and insufficient magnetic or thermal properties. The primary focus of this dissertation work is the synthesis and optimization of a new permanent magnetic material, in the form of cobalt carbide nanomaterials. The optimization revolved around controlling the crystal phase and particle shape of synthesized cobalt carbide particles; these parameters have significant impact on the observed magnetic properties of magnetic nanoparticles. Co3C was identified to be the preferred crystal phase, leading to better magnetic properties. Cobalt Fumarate was found to be the ideal precursor to synthesize anisotropic Co3C particles and enhance magnetic properties of the synthesized cobalt carbide particles. Lastly, an ethanol based reduction system was employed to develop the greener synthesis of Co and Ni magnetic particles.

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Buckley, Hannah C. "Applications of layered double hydroxides as inorganic adjuvants." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:353bd7f3-89ed-4392-9b71-64a27c271522.

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The primary aim of this thesis is to explore the immunostimulatory properties of a family of layered, crystalline, inorganic materials known as layered double hydroxides (LDHs). Chapter One provides an introduction to relevant aspects of the immune system, and the context for investigating the immunostimulatory properties of inorganic materials in terms of vaccine/adjuvant formulations. The possible mechanisms of action of commercial adjuvant materials are also reviewed, and the structure, synthesis methods and applications of LDHs are discussed. Chapter Two details the controlled synthesis and characterisation of LDHs in specific particle sizes. A series of MgAl-CO3 LDHs with precisely controlled particle sizes ranging from 20 to 10000 nm were successfully synthesised, then the techniques used were extended to other compositions to create a panel of LDHs for use in subsequent Chapters. In Chapter Three, the responses of monocyte-derived dendritic cells (Mo-DC) to the LDH particle sizes discussed in Chapter Two are assessed in terms of viability, surface molecule expression, and cytokine secretion. A statistical modelling approach using the physicochemical properties of the LDHs as explanatory variables for immune responses was employed to evaluate the validity of the model formulated in the previous work, and to establish if particle size could be used to improve its predictive ability. It was found that strong relationships between LDH particle size and certain Mo-DC responses exist, and that these responses could be predicted with a high degree of accuracy. Chapter Four is concerned with the investigation of T cell responses to LDH-stimulated allogeneic Mo-DC. Various methods were used for assessing T cell division and proliferation, and a protocol for intracellular cytokine staining was developed to probe T cell polarisation. Five LDHs, which have elicited potentially interesting T cell responses in previous work, were selected for investigation. However, using the assays described, no discernible improvement in proliferation or polarisation was observed with any of the LDHs tested. Chapter Five presents an initial exploration of the interactions between LDH particles and cells. Experiments have shown that LDH particles both adhere to and are internalised by Mo-DC. Variations in the extent of internalisation with both particle size and composition were highlighted by confocal microscopy studies. Through investigations into interactions between LDH particles and the plasma membrane using protease enzymes, it was revealed that adhesion of LDH particles is partly protein-dependent. Further studies have also demonstrated a pH-dependent element to particle association with Mo-DC. Details of the experimental procedures employed are included in Chapter Six. Supplementary information referred to in the main thesis may be found in the Appendices.

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Skowron, Stephen T. "Irradiation induced reactions in carbon nanomaterials in transmission electron microscopy." Thesis, University of Nottingham, 2016. http://eprints.nottingham.ac.uk/34629/.

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Aberration corrected transmission electron microscopy is a powerful tool for the structural characterisation of materials at the atomic scale, but the passage of high velocity electrons through the material can often induce structural changes via the transfer of large amounts of energy from the beam. The work in this thesis theoretically considers the nature of this transfer of energy and its impact upon the material being studied. The computational modelling of molecular species encapsulated inside carbon nanotubes and their response to electron irradiation is compared to results from TEM experiments, and used to explain the experimental observations. The high rate of destruction of C-H bonds under the beam is quantified, and its implications for TEM studies of organic materials considered. An effective solution for mitigating this rate of destruction is found, applied to a model system, and then confirmed experimentally. Using the considerations of stability under the beam, two experimentally witnessed reactions are investigated in detail, and careful comparison to intermediate structures observed in TEM allows full reaction mechanisms to be proposed. The dynamic motion of atomic defects in irradiated graphene is considered with the aid of a large library of experimental TEM images. A novel defect structure is observed, and is seen to undergo structural rearrangements on a quicker time-scale than accessible to TEM imaging. This species enables the very quick migration of defect structures across the graphene lattice, and is attributed to a trivacancy structure. The rates of beam induced reactions are considered in the framework of chemical kinetics, and a method for extracting kinetic parameters of a reaction from the statistics of a large number of TEM observations of it occurring is developed. This is used to obtain the first cross-sections for the formation and healing of the irradiation induced Stone-Wales bond rotation, and the first experimental activation energy for its healing. The latter agrees well with a theoretically predicted mechanism of catalysis, while the former demonstrates that the widely assumed process of direct knock-on damage cannot be responsible for the beam induced reaction. An alternative mechanism is proposed, resulting from the electronic excitation of the defect.

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Di, Pasqua Anthony J. "Carboplatin Exploring mechanism of action and improved drug delivery 1. Role of carbonate in the mechanism of action of carboplatin 2. Cytotoxicity of mesoporous silica nanomaterials /." Related electronic resource: Current Research at SU : database of SU dissertations, recent titles available full text, 2008. http://wwwlib.umi.com/cr/syr/main.

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Ma, Hui. "Nanomaterials for Biological Applications: Drug Delivery and Bio-sensing." ScholarWorks@UNO, 2013. http://scholarworks.uno.edu/td/1647.

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The idea of utilizing nanomaterials in bio-related applications has been extensively practiced during the recent decades. Magnetic nanoparticles (MPs), especially superparamagnetic iron oxide nanoparticles have been demonstrated as promising candidates for biomedicine. A protective coating process with biocompatible materials is commonly performed on MPs to further enhance their colloidal and chemical stability in the physiological environment. Mesoporous hollow silica is another class of important nanomaterials that are extensively studied in drug delivery area for their ability to carry significant amount of guest molecules and release in a controlled manner. In this study, different synthetic approaches that are able to produce hybrid nanomaterials, constituting both mesoporous hollow silica and magnetite nanoparticles, are described. In a two-step approach, pre-synthesized magnetite nanoparticles are either covalently conjugated to the surface of polystyrene beads and coated with silica or embedded/enclosed in the porous shell during a nanosized CaCO3 templated condensation of silica precursors, followed by acid dissolution to generate the hollow structure. It was demonstrated that the hollow interior is able to load large amount of hydrophobic drugs such as ibuprofen while the mesoporous shell is capable of prolonged drug. In order to simplify the fabrication procedure, a novel in-situ method is developed to coat silica surface with magnetite nanoparticles. By refluxing the iron precursor with mesoporous hollow silica nanospheres in polyamine/polyalcohol mixed media, one is able to directly form a high density layer of magnetite nanoparticles on silica surface during the synthesis, leaving reactive amine groups for further surface functionalization such as fluorescence conjugation. This approach provides a convenient synthesis for silica nanostructures with promising potential for drug delivery and multimodal imaging. In addition to nanoparticles, nanowires also benefit the research and development of instruments in clinical diagnosis. Semiconductive nanowires have demonstrated their advantage in the fabrication of lab-on-a-chip devices to detect many charge carrying molecules such as antibody and DNA. In our study, In2O3 and silicon nanowire based field effect transistors were fabricated through bottom-up and top-down approaches, respectively, for ultrasensitive bio- detection of toxins such as ricin. The specific binding and non-specific interaction of nanowires with antibodies were also investigated.

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Yu, Lei. "DECONVOLVING THE STEPS TO CONTROL MORPHOLOGY, COMPOSITION, AND STRUCTURE, IN THE SYNTHESIS OF HIGH-ASPECT-RATIO METAL OXIDE NANOMATERIALS." UKnowledge, 2017. http://uknowledge.uky.edu/chemistry_etds/82.

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Metal oxides are of interest not only because of their huge abundance but also for their many applications such as for electrocatalysts, gas sensors, diodes, solar cells and lithium ion batteries (LIBs). Nano-sized metal oxides are especially desirable since they have larger surface-to-volume ratios advantageous for catalytic properties, and can display size and shape confinement properties such as magnetism. Thus, it is very important to explore the synthetic methods for these materials. It is essential, therefore, to understand the reaction mechanisms to create these materials, both on the nanoscale, and in real-time, to have design control of materials with desired morphologies and functions. This dissertation covers both the design of new syntheses for nanomaterials, as well as real-time methods to understand their synthetic reaction mechanisms. It will focus on two parts: first, the synthesis of 1-dimension (1-D) featured nanomaterials, including manganese-containing spinel nanowires, and tin dioxide and zinc oxide-based negative nanowire arrays; and second, a mechanistic study of the synthetic reactions of nanomaterials using in situ transmission electron microscopy (TEM). The work presented here demonstrates unique synthetic routes to single crystalline “positive” and “negative” metal oxide nanowires, and introduces a new mechanism for the formation of single-crystalline hollow nanorods.

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Huang, Wen-Yen. "Responsive theranostic nanoparticles." Thesis, University of Oxford, 2013. http://ora.ox.ac.uk/objects/uuid:275e12ca-e5a4-4f63-af9e-3c73948f8001.

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The development and use of nanotechnology towards theranostics (all-in-one disease diagnostics and therapeutic delivery) have been increasing in popularity in recent years, in particular the use of high capacity of nanomaterials to transport both imaging and therapeutic agents into pathological tissues or abnormal cells. In this work, biocompatible mesoporous silica nanoparticles (MSNs) that can be reliably endocytosed by cells are employed in the investigation of novel cancer treatment and magnetic resonance imaging (MRI). One of the principal aims is to develop T₁ contrast nanoparticles not only with extraordinarily high MRI contrast characteristics, but also tunability through surface chemistry and functional protein conjugation. In coupling paramagnetic Gd³⁺-centres to MSNs, one can effectively marry the advantages afforded by increased molecular bulk with those engendered by confined water environment inside the porous network. Specifically, through exclusively biasing paramagnetic Gd³⁺-centres in the internal spaces of nanoparticles, their mobility and interaction with water protons can be altered, significantly, with beneficial changes in molecular tumbling (τ_R), proton exchange (τ_M) and water diffusion (τ_D) within relaxation dynamics. These MRI nanoparticles with internalised Gd³⁺-centres are additionally used in the development of tunable/responsive contrast agents through vectoring protein conjugation. The relaxivity of MSNs can be tailored depending on the separation distances between proteins and nanoparticles; significantly, the simultaneous retention of both high MRI contrast and protein vectoring is achieved by the insertion of long polyethylene glycol (PEG) chain. The image contrast can also be reversibly gated through the competitive displacement of surface proteins by their partner proteins. Specifically, these responsive nanoparticles possess a low contrast resulting from restricted water accessibility when protein moieties are conjugated on the particles, whereas the removal of proteins causes a transition of contrast from a low to high state. The MSNs synthesised in this work are used not only in diagnostic imaging but also in the delivery of therapeutic agents for cancer therapy. The agents can be either physically encapsulated inside the pores or chemically conjugated on the nanoparticles. For the former, their loading and release efficiencies are tunable by the electrostatic interactions with particle surface functional groups; while in the latter case, their retention on nanoparticles, as opposed to being released, plays an important role in the effectiveness of cancer treatment that is achieved by trigging programmed cell death (apoptosis) in this work. This nanoparticle conjugation secures the proteins’ activity by facilitating their bypass of proteolytic degradation. Significantly, specially designed nanoparticles that demonstrate endo/lysosomal escape capability can reliably deliver therapeutic cytochrome c to cell cytosols for the initiation of a caspase cascade within apoptosis with high efficacy.

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Clifford, Dustin M. "Non-Conventional Approaches to Syntheses of Ferromagnetic Nanomaterials." VCU Scholars Compass, 2016. http://scholarscompass.vcu.edu/etd/4205.

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The work of this dissertation is centered on two non-conventional synthetic approaches to ferromagnetic nanomaterials: high-throughput experimentation (HTE) (polyol process) and continuous flow (CF) synthesis (aqueous reduction and the polyol process). HTE was performed to investigate phase control between FexCo1-x and Co3-xFexOy. Exploration of synthesis limitations based on magnetic properties was achieved by reproducing Ms=210 emu/g. Morphological control of FexCo1-x alloy was achieved by formation of linear chains using an Hext. The final study of the FexCo1-x chains used DoE to determine factors to control FexCo1-x, diameter, crystallite size and morphology. [Ag] with [Metal] provide statistically significant control of crystallite size. [OH]/[Metal] predict 100 % FexCo1-x at > 30. To conclude section 1, a morphological study was performed on synthesis of Co3-xFexOy using the polyol process. Co3-xFexOy micropillars were synthesized at various sizes. The close proximity of the particles in the nanostructure produced an optical anisotropy and was magnetically induced which is evidence for the magneto-birefringence effect. The second non-conventional synthetic approach involves continuous flow (CF) chemistry. Co nanoparticles (Ms=125 emu/g) were newly synthesized by aqueous reduction in a microreactor and had 30 ±10 nm diameter and were produced at >1g/hr, a marker of industrial-scale up viability. The final work was the CF synthesis of FexCo1-x. The FexCo1-x was synthesized with limitation to the composition. The maximum FexCo1-x phase composition at 20 % resulted from the aqueous carrier solvent triggering oxide formation over FexCo1-x.

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Mercurio, James M. "Interlocked host structures for anion recognition and metal nanoparticles for catalysis and sensing applications." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:40178988-4945-4a98-af98-59a1a35a12d5.

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This thesis describes the synthesis and anion recognition properties of a variety of interlocked host receptors and the application of metal nanoparticles in the areas of catalysis and sensing. Chapter One introduces the field of anion supramolecular chemistry, with particular emphasis on areas relevant to the research discussed in later chapters. Following this, the synthesis and applications of metal nanoparticles are outlined. Chapter Two details the synthesis of a range of halo-triazolium based rotaxanes and explores the effects of altering both the halogen bond donor atom and degree of preorganisation on the anion recognition properties of the interlocked host system. A halogen bond containing catenane is also prepared and its anion binding properties investigated. Chapter Three initially reports the anion-templated synthesis of a series of neutral pyridine N-oxide axle containing rotaxanes before their ability to recognise anions in aqueous solvent mixtures is studied. Attempts to enhance anion binding through the incorporation of a positive charge into the macrocyclic component of the rotaxane structure are also explored. Chapter Four outlines the preparation of β-cyclodextrin functionalised metal nanoparticles and investigations of their catalytic and sensing properties. Chapter Five describes in detail the synthetic and analytical procedures discussed in chapters two to four. Chapter Six summarises the conclusions of this thesis.

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Korir, Daniel Kiplangat. "Design, Synthesis and Characterization of Polymer and Protein Coated Hybrid Nanomaterials: Investigation of Prototypes for Antimicrobial and Anticancer Applications." Thesis, University of North Texas, 2019. https://digital.library.unt.edu/ark:/67531/metadc1505197/.

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This work involves synthesis and characterization of isotropic and anisotropic noble metal nanoparticles for applications ranging from antimicrobial uses to anticancer applications. These nanomaterials are stabilized in genuinely benign biomaterials ranging from polymers to cross linked proteins for targeted cancer treatments. The nanoparticles are found to have tunable optical properties.

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Huh, Seong. "Morphological Control of Multifunctional Mesoporous Silica Nanomaterials for Catalysis Applications." Ames, Iowa : Oak Ridge, Tenn. : Ames Laboratory ; distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy, 2004. http://www.osti.gov/servlets/purl/837271-xREJ4t/webviewable/.

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Thesis (Ph.D.); Submitted to Iowa State Univ., Ames, IA (US); 19 Dec 2004.
Published through the Information Bridge: DOE Scientific and Technical Information. "IS-T 2397" Seong Huh. US Department of Energy 12/19/2004. Report is also available in paper and microfiche from NTIS.

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Zhang, Baofang. "Examination Of The Solution Behaviors Of The Giant Inorganic-Organic Amphiphilic Hybrids." University of Akron / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1460369559.

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17

Ballentine, Michael Drake. "Imidazolium Ionic Liquids as Multifunctional Solvents, Ligands, and Reducing Agents for Noble Metal Deposition onto Well-Defined Heterostructures and the Effect of Synthetic History on Catalytic Performance." TopSCHOLAR®, 2018. https://digitalcommons.wku.edu/theses/2101.

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1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM]Tf2N) was investigated as a multifunctional solvent, ligand, and reducing agent for platinum deposition onto well-defined CdSe@CdS nanorods. Platinum deposition was carried out thermally and photochemically using Pt(acac)2 as the metal precursor. Thermal deposition was investigated in [BMIM]Tf2N with and without addition of a sacrificial reducing agent, and product topology was compared with the products obtained from polyol reduction using 1,2-hexadecanediol, oleic acid, and oleylamine in diphenyl ether. Photochemically induced platinum deposition was carried out at room temperature in [BMIM]Tf2N, and product topology was compared with the photodeposition products obtained from a toluene dispersion. Thermal deposition of platinum in ionic liquid showed rods of broken morphology and small platinum nanoparticles speckled across the rods’ surface, while photodeposition of platinum exhibited particles decorated throughout the nanorod surface but larger in size than those exhibited by thermal means. Photocatalytic reduction of methylene blue was studied using these Pt-CdSe@CdS heterostructured nanoparticles, and catalytic performance was correlated with topology and synthetic history. Initial findings of catalytic performance suggest that there in an advantage of depositing platinum nanoparticles onto the CdSe@CdS in the ionic liquid system. Methylene blue dye was degraded using each system and the results show and there is an increased performance of the nanorods synthesized in the ionic system.

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Parkinson, Patrick. "Ultrafast electronic processes at nanoscale organic-inorganic semiconductor interfaces." Thesis, University of Oxford, 2009. http://ora.ox.ac.uk/objects/uuid:e68168c6-bcc0-437d-9133-1bfaf955c80a.

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This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within both organic and inorganic semiconductors. Photoluminescent polymers, highly conducting polymers and nanoscale inorganic semiconductors have been investigated using state-of-the-art ultrafast optical techniques, to provide information on the sub-picosecond photoexcitation dynamics in these systems. The influence of dimensionality on the excitation transfer dynamics in a conjugated polymer blend is studied. Using time-resolved photoluminescence spectroscopy, the transfer transients both for a three-dimensional blend film, and for quasi-two-dimensional monolayers formed through intercalation of the polymer blend between the crystal planes of a SnS2 matrix have been measured. A comparison of the experimental data with a simple, dimensionality-dependent model is presented, based on point dipole electronic coupling between electronic transition moments. Within this approximation, the energy transfer dynamics are found to adopt a three-dimensional character in the solid film, and a two-dimensional nature in the monolayers present in the SnS2 -polymer nanocomposite. The time-resolved conductivity of isolated GaAs nanowires has been investigated by optical-pump terahertz-probe time-domain spectroscopy. The electronic response exhibits a pronounced surface plasmon mode that forms within 300 fs, before decaying within 10 ps as a result of charge trapping at the nanowire surface. The mobility has been extracted using the Drude model for a plasmon and is found to be remarkably high, being roughly one third of that typical for bulk GaAs at room-temperature and indicating the high quality and low bulk defect density in the nanowires studied. Finally, the time-resolved conductivity dynamics of photoexcited polymer-fullerene bulk heterojunction blends for two model polymers, P3HT and MDMO-PPV, blended with PCBM are presented. The observed terahertz-frequency conductivity is characteristic of dispersive charge transport for photoexcitation both at the π−π* absorption peak (560 nm for P3HT), and significantly below it (800 nm). The photoconductivity at 800 nm is unexpectedly high, which is attributed to the presence of a charge transfer complex. In addition, the excitation-fluence dependence of the photoconductivity is studied over more than four orders of magnitude. The time-averaged photoconductivity of the P3HT:PCBM blend is over 20 times larger than that of P3HT, indicating that long-lived positive polarons are responsible for the high photovoltaic efficiency of polymer:fullerene blends. At early times (~ ps) the linear dependence of photoconductivity upon fluence indicates that interfacial charge transfer dominates as an exciton decay pathway, generating charges with mobility of at least ~0.1cm2 V−1 s−1. At later times, a sub-linear relationship shows that carrier-carrier recombination effects influence the conductivity on a longer timescale (> 1 μs).

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Kong, Liang. "Bismuth oxybromide-based photocatalysts for solar energy utilisation and environmental remediation." Thesis, University of Oxford, 2013. http://ora.ox.ac.uk/objects/uuid:c95ee3cc-b276-4c69-8b3f-eb60cc64e1c0.

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This thesis reports the investigation of Bismuth oxybromide (BiOBr) semiconductor material as an efficient photocatalyst for the sunlight harvesting as well as environmental cleanup. I have utilised different synthetic methodologies to obtain BiOBr and its derivatives, such as co-precipitation, ultrasonification, and photo-deposition; and have studied their structural and optical properties by X-ray diffraction and surface analysis techniques. I report the synthesis and characterisation of two new p-n heterojunction systems, AgBr-BiOBr and BiOBr-ZnFe₂O₄, and have performed initial studies on photocatalytic reaction and their catalytic decomposition mechanisms. I have also reported the surface modification method including the deposition of noble metal on BiOBr to investigate the role played by the noble metal and the interactions between semiconductor and metal using various characterisation measurements. Furthermore, a continuous series of BiOBr-BiOI solid solutions were synthesised, characterised and the photocatalytic degradation was performed on the as-obtained semiconductors, to study the band structure properties of the solid solutions.

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Woolerton, Thomas William. "Development of enzymatic H2 production and CO2 reduction systems." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:393741ac-94b1-4d56-b680-d9a434db77e2.

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One of today’s most pressing scientific challenges is the conception, development and deployment of renewable energy technologies that will meet the demands of a rapidly increasing population. The motivation is not only dwindling fossil fuel reserves, but also the necessary curtailment of emissions of the greenhouse gas carbon dioxide (a product of burning fossil fuels). The sun provides a vast amount of energy (120,000 TW globally), and one major challenge is the conversion of a fraction of this energy into chemical energy, thereby allowing it to be stored. Dihydrogen (H₂) that is produced from water is an attractive candidate to store solar energy (a ‘solar fuel’), as are high energy carbon-containing molecules (such as CO) that are formed directly from carbon dioxide. One key aspect is the development of catalysts that are able to offer high rates and efficiencies. In biology, some microbes acquire energy from the metabolism of H₂ and CO. The biological catalysts - enzymes - that are responsible are hydrogenases (for the oxidation of H₂ to protons); and carbon monoxide dehydrogenases (CODHs, for the oxidation of CO to CO₂). These redox enzymes, containing nickel and iron as the only metals, are extraordinary in terms of their catalytic characteristics: many are fully reversible catalysts and offer very high turnover frequencies (thousands per second are common), with only tiny energy input requirements. This Thesis uses a hydrogenase from the bacterium Escherichia coli, and two CODHs from the bacterium Carboxydothermus hydrogenoformans, as the catalysts in H2 production and CO₂ reduction systems. Chapter 3 describes the concept and development not of a solar fuel system, but of a device that catalyses the water-gas shift reaction (the reaction between CO and water to form H₂ and CO₂) - a process of major industrial importance for the production of high purity H₂. Chapters 4, 5 and 6 detail photochemical CO₂ reduction systems that are driven by visible light. These systems, operating under mild, aqueous conditions, involve CODHs attached either to TiO₂ nanoparticles that are sensitised to visible light by the co-attachment of a ruthenium-based dye complex, or to cadmium sulfide nanomaterials that, having a narrow band gap, are inherently photoexcitable by visible light. The motivation here is not the construction of technological devices; indeed, the enzymes that are used are fragile, highly sensitive to oxygen, and impossible to scale to industrial levels. Rather, the drivers are those of scientific curiosity (can the incorporation of these remarkable biological catalysts enable the creation of outstanding solar fuel devices?), and of producing systems that serve as benchmarks and inspiration for the development of fully synthetic systems that are robust and scalable.

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Jones, Simon Philip. "Influence of modifiers on Palladium based nanoparticles for room temperature formic acid decomposition." Thesis, University of Oxford, 2013. http://ora.ox.ac.uk/objects/uuid:873277f2-c4f7-45b7-a16d-bba064e24bee.

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Heterogeneous catalysts form a highly important part of everyday life, ranging from the production of fertiliser enabling the growth of crops that sustain much of the world's population to the production of synthetic fuels. They constitute a key part of the chemical industry and contribute towards substantial economic and environmental benefits. Heterogeneous catalysts are also believed to have an important role to play in a future hydrogen economy, reducing our requirements for fossil fuels. To this end, formic acid has been proposed as a potential hydrogen storage material for small portable devices. Additionally, formic acid has historically been used as a probe molecule to study catalyst materials and recent developments in the knowledge of its decomposition pathways and the preferred sites of these reactions, establish a good foundation for further study. This work explores a range of novel modification techniques that alter the activity of Pd nanoparticles to decompose formic acid to H₂ and CO₂. The methods used are the addition of polymers, attaching various functional groups to the surface of the catalyst support and decoration of nanoparticles with sub-monolayer coverages of another metal. Using a range of characterisation methods including FTIR of an adsorbed CO probe, XRD and XPS coupled with computational modelling, it is found that these methods result in some significant electronic and/or geometric alterations to the Pd nanoparticles. For polymer modification, the nature of the pendent group is highly important in determining the effects of the polymer on the Pd particles, with all the tested polymers resulting in varying degrees of electronic donation to the Pd surface. The geometric modifications caused by the polymers also varied with pendent groups; with amine containing pendent groups found to selectively block low coordinate sites, preventing the undesired dehydration of formic acid which results in poisoning of the Pd catalyst by the resulting CO. Attachment of amine groups to the surface of metal oxide catalyst supports, is demonstrated to result in dramatic electronic promotional effects to the supported Pd nanoparticles, and when an amine polymer is attached to the support surface the geometric modification is again observed. Finally decoration of Pd nanoparticles with a sub-monolayer coverage of a second metal is examined, resulting in some similar electronic and geometric effects on Pd nanoparticle surfaces to those observed with polymer modification with corresponding changes in formic acid decomposition activity. Overall, a number of methods are displayed to tune the catalytic activity and selectivity of Pd nanoparticles for formic acid decomposition, resulting in catalysts with some of the highest reported TOF's at room temperature. These modification methods are believed to be potentially applicable to a wide range of other catalytic reactions that operate under mild conditions.

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22

Pryor, Donald Edward. "Synthesis and Bioactivity Studies of Nanoparticles Based on Simple Inorganic and Coordination Gallium Compounds as Cellular Delivering Vehicles of Ga(III) Ions for Potential Therapeutic Applications." Kent State University / OhioLINK, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=kent1543554532063877.

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23

Belding, Stephen Richard. "Computational electrochemistry." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:e997642f-fbaa-469c-98a3-f359b0996f03.

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Electrochemistry is the science of electron transfer. The subject is of great importance and appeal because detailed information can be obtained using relatively simple experimental techniques. In general, the raw data is sufficiently complicated to preclude direct interpretation, yet is readily rationalised using numerical procedures. Computational analysis is therefore central to electrochemistry and is the main topic of this thesis. Chapters 1 and 2 provide an introductory account to electrochemistry and numerical analysis respectively. Chapter 1 explains the origin of the potential difference and describes its relevance to the thermodynamic and kinetic properties of a redox process. Voltammetry is introduced as an experimental means of studying electrode dynamics. Chapter 2 explains the numerical methods used in later chapters. Chapter 3 presents a review of the use of nanoparticles in electrochemistry. Chapter 4 presents the simulation of a random array of spherical nanoparticles. Conclusions obtained theoretically are experimentally confirmed using the Cr³⁺/Cr²⁺ redox couple on a random array of silver nanoparticles. Chapter 5 presents an investigation into the concentration of supporting electrolyte required to make a voltammetric experiment quantitatively diffusional. This study looks at a wide range of experimental conditions. Chapter 6 presents an investigation into the deliberate addition of insufficient supporting electrolyte to an electrochemical experiment. It is shown that this technique can be used to fully study a stepwise two electron transfer. Conclusions obtained theoretically are experimentally confirmed using the reduction of anthracene in acetonitrile. Chapter 7 presents a new method for simulating voltammetry at disc shaped electrodes in the presence of insufficient supporting electrolyte. It is shown that, under certain conditions, the results obtained from this complicated simulation can be quantitatively obtained by means of a much simpler ‘hemispherical approximation’. Conclusions obtained theoretically are experimentally confirmed using the hexammineruthenium ([Ru(NH₃)₆]³⁺/[Ru(NH₃)₆]²⁺) and hexachloroiridate ([IrCl₆]²⁻/[IrCl₆]³⁻) redox couples. Chapter 8 presents an investigation into the voltammetry of stepwise two electron processes using ionic liquids as solvents. It is shown that these solvents can be used to fully study a stepwise two electron transfer. Conclusions obtained theoretically are experimentally confirmed using the oxidation of N,N-dimethyl-p-phenylenediamine in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([C₄ mim][BF₄]). The work presented in this thesis has been published as 7 scientific papers.

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Chan, Chun Wong Aaron. "Ultraselective nanocatalysts in fine chemical and pharmaceutical synthesis." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:866296af-5296-4d2e-8e52-6499dacaef0f.

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Surface catalysed reactions play an important role in chemical productions. Developments of catalyst requiring high activity whilst improving on product selectivity can potentially have a profound effect in the chemical industry. Traditional catalyst modifications were focused on tuning the size, shape and foreign metal doping to form well defined metal nanoparticles of unique functionalities. Here, we show new approach to engineering of metal nanocatalysts via a subsurface approach can modify the chemisorption strength of adsorbates on the surface. Carbon modified nanoparticles were synthesised using glucose to stabilise Pd nanoparticles at a molecular level. Upon heat treatment, the carbonised glucose encapsulated the Pd nanoparticles with carbon atoms take residence in the octahedral holes (15 at.%). These materials were tested in liquid phase stereoselective hydrogenations of 3-hexyn-1-ol and 4-octyne. The former has importance in the fragrance industry towards the production of leaf fragrance alcohol. It was shown for the first time that the geometrically and electronically modified Pd with interstitial carbon atoms reduced the adsorption energy of alkenes, ultimately leading to higher reaction selectivity. Boron modified Pd nanoparticles was synthesised using BH₃.THF in the liquid phase. The material possess high B interstitial saturation (20 at.%), which can be synthesised for the first time below 100°C. These materials were tested in the liquid phase selective hydrogenation of various alkynes and 2-chloronitrobenzene, of which the latter has importance in the pesticides industry. Kinetic modelling on the hydrogenation of 4-octyne suggests these subsurface occupied B does play a pivotal role on increasing the reaction selectivity, as removal of these species lead to decreased selectivity. Au nanoparticles were synthesised and characterised using H¹³COOH NMR. The new liquid NMR characterisation method is successfully applied to examine the chemisorption strength of metal nanoparticles. An attempt to synthesise PVP capped B modified Pd nanoparticles with the above NMR characterisation was investigated. It is believed the examples of subsurface atom modifications as shown here may offer future catalyst developments in this area.

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Al-Saadi, Ali. "Preparation and characterisation of encapsulation magnetic metal iron oxide nanoparticles." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:57bdcf38-9d45-48ab-a971-a2d60e2e4391.

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One of the most challenging goals in nanoparticle research is to develop successful protocols for the large-scale, simple and possibly low-cost preparation of morphologically pure nanoparticles with enhanced properties. The work presented in this thesis was focused on the synthesis, characterisation and testing of magnetic nanoparticles and their potential applications. There are a number of magnetic nano-materials prepared for specific applications such as metal oxide nanoparticles encapsulated with various porous materials including Fe₃O₄/Fe₂O₃ coated with soft bio-organic materials such as glycol chitosan and bovine serum albumin and hard materials such as silica (SiO₂) and zinc sulphide (ZnS). The preparation of these materials was achieved principally by bottom-up methods with different approaches including micro-emulsion, precipitation, electrostatic and thermolysis processes. The thesis also presents the uses of various analytical techniques for characterising different types of nano-materials including Attenuated Total Reflection Fourier Transformer Infrared Vibrational Spectroscopy (ATR-FTIR), Ultraviolet Visible- Near Infrared (UV-Vis-NIR) Spectroscopy, Zeta Potentiometric Surface Charge Analysis, Superconducting Quantum Interference Device (SQUID) and Vibration Sample Magnetometry (VSM) for magnetic analysis and powder X-Ray Diffraction (XRD) for crystallographic pattern analysis. There are many applications of magnetic nanoparticles, including nano-carriers for biological and catalytic reagents. The magnetic nanoparticles can facilitate separation in order to isolate the carriers from solution mixtures as compared to many inefficient and expensive classic methods, which include dialysis membrane, electrophoresis, ultracentrifugation, precipitation and column separation methods. There are six key chapters in this thesis: the first chapter introduces the up-to-date literature regarding magnetic nano-materials. The uses of magnetic nano-materials in drug binding and for protein separation are discussed in the second and third chapters. The fourth chapter presents the use of magnetic nanoparticle in conjunction with a photo-catalytic porous overlayer for the photo-catalytic reduction of organic molecules. The fifth chapter describes different analytical techniques used for the characterisation of nanoparticles and the underlying principles and the experimental details are also given. The sixth chapter summarises the results and provides an overview of the work in a wider context of future applications of magnetic nanoparticles.

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Bludin, Alexey O. "Peptide-Porphyrin Self-Assembled Materials." Bowling Green State University / OhioLINK, 2011. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1308097842.

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27

Liyanage, Geethika Kaushalya. "Infrared Emitting PbS Nanocrystals through Matrix Encapsulation." Bowling Green State University / OhioLINK, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1403953924.

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28

Agostini, Alessandro. "Supramolecular and heterosupramolecar chemistry in controlled release and molecular recognition processes." Doctoral thesis, Universitat Politècnica de València, 2013. http://hdl.handle.net/10251/29397.

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La presente tesis doctoral titulada ¿Supramolecular and heterosupramolecular chemistry in controlled release and molecular recognition processes¿ está centrada en los dos aspectos principales de la química supramolecular que han experimentado un gran auge en los últimos años: el reconocimiento molecular y los procesos de liberación controlada. En particular la primera parte de la tesis se focaliza en el diseño y síntesis de moléculas orgánicas que pueden ser empleados cómo sensores para especies aniónicas y neutras. El paradigma seleccionado para los procesos de reconocimiento molecular fue la aproximación del dosimetro químico. Esta aproximación presenta ventajas con respecto a los otros dos métodos de determinación de aniones (desplazamiento y unidad coordinanteunidad indicadora), cómo, por ejemplo, la posibilidad de determinar los analitos en disolución acuosa. Así se sintetizaron dos sensores selectivos, uno para el anión fluoruro (F-) y el otro para glutatión (GSH). El sensor selectivo para la determinación de F- está basado en un colorante azoico funcionalizado, en su ¿OH fenólico, cómo silileter. Esta molécula presenta una banda de absroción muy intensa centrada a 350 nm que, después de la adición de F- , sufre un efecto hipocrómico significativo y un desplazamiento batocromico ligero (de ca. 10 nm), mientras aparece una nueva banda a 470 nm, determinando un cambio de incoloro a amarillorojo. Para obtener un sensor selectivo para GSH se sintetizó una sonda químico basado en una sal de 2,6-difenilpirilio. Sucesivamente se preparó una disolución de este compuesto en agua/CTAB, que se caracterizaba por un intenso color azul. En este caso, la adición de GSH produce una disminución significativa de la banda del visible, acompañada por la consecuente decoloración. Además la adicón de GSH induce la aparición de Resumen vi una intensa banda de emisión centrada a 485 nm (después de la irradiación a 350 nm). La segunda parte de esta tesis doctoral se basa en el diseño y síntesis de nuevos sistemas híbridos orgánicos-inorgánicos para procesos de liberación controlada en ambiente celular. Estos materiales híbridos se componen en general, de dos unidades: una matriz inorgánica mesoporosa de base silícea, capaz de almacenar moléculas orgánicas (colorantes, farmacos...) y un compuesto orgánico anclado covalentemente a la superficie externa del soporte inorgánico mesoporoso, que actúa cómo puerta molecular. La aplicación de un estímulo externo puede modificar la conformación de la puerta molecular permitiendo o bien impidiendo la difusión de la carga almacenada en los mesoporos hacía el exterior (disolución o citoplasma). El primer sistema sintetizado y estudiado se compone de una matriz inorgánica mesoporosa (MCM-41), cargada con el colorante Ru(bipy)3 2+ y funcionalizada en la superficie con un oligoetilen glicol mediante un grupo ester. La adición de la enzima esterasa determinaba la hidrólisis del grupo ester y la consecuente reducción del tamaño de la puerta molecular, acompañada por la liberación del colorante previamente cargado. Otro sistema de liberación preparado consiste en el uso de la misma matriz MCM-41 nanoscópica y el mismo colorante Ru(bipy)3 2+, pero se funcionalizó la superficie con una puerta molecular fotolabil. La irradiación en el maximo de absorción de la puerta molecular inducía la fotodegradación de la misma y la consecuente liberación del colorante. Un tercer ejemplo de sistema de liberación consiste en una puerta molecular caracterizada por la presencia de dos grupos funcionales hidrolizables con enzimas diferentes: grupos urea y amida. vii El material final, caracterizado por la presencia del mismo esqueleto inorgánico, y cargado con Ru(bipy)3 2+, era capaz de liberar selectivamente cantidades distintas de colorante, dependiendo del enzima empleado. Así se podían conseguir dos tipos de perfiles de liberación: uno muy rápido y poco intenso y otro más lento pero mucho mas intenso. Finalmente se sintetizó un material híbrido siempre basado en la misma matriz de MCM- 41, cargado con rodamina-B y funcionalizado en la superficie con galactooligosacáridos. Con este material se podía conseguir una liberación controlada del colorante selectivamente en células senescentes, debido a que estas sobreexpresan el enzima ß-galactosidasa que es capaz de hidrolizar los galactooligosacáridos.
Agostini, A. (2013). Supramolecular and heterosupramolecar chemistry in controlled release and molecular recognition processes [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/29397
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Vono, Lucas Lucchiari Ribeiro. "Estudo da imobilização de fotossensibilizadores em nanomateriais magnéticos." Universidade de São Paulo, 2010. http://www.teses.usp.br/teses/disponiveis/46/46134/tde-13122010-104924/.

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A imobilização de fotossensibilizadores (FS) em materiais nanométricos tem se mostrado uma excelente alternativa ao seu emprego na forma molecular para terapia fotodinâmica (PDT). O presente trabalho descreve uma série de estratégias sintéticas desenvolvidas para a imobilização de FS em nanoesferas de sílica contendo núcleos magnéticos, bem como o estudo das propriedades foto-químicas, foto-físicas e morfológicas dos nanomateriais obtidos. Os FS utilizados foram o azul de metileno, tionina, azure A, protoporfirina IX, hematoporfirina IX e clorofilina. As metodologias de imobilização empregadas envolveram a adição do FS durante o crescimento da camada de sílica ou a ligação do FS na superfície do nanomaterial já formado. Em alguns casos foi necessário modificar previamente o FS com organossilanos. Os núcleos magnéticos foram preparados por co-precipitação de sais de ferro(II) e ferro(III) em meio básico e o revestimento com sílica foi realizado utilizando-se tetraetilortossilicato em uma microemulsão. Os núcleos magnéticos revestidos com uma camada de sílica mantiveram o comportamento superparamagnético. Para a tionina e o azul de metileno não foi detectada geração de oxigênio singlete após a imobilização. Para o azure A, protoporfirina IX e clorofilina imobilizados, a geração de oxigênio singlete foi detectada e caracterizada por métodos químicos e físicos. O material contendo clorofilina mostrou-se bastante promissor e foi empregado em estudos preliminares com células HeLa, levando à morte celular após irradiação, o que comprova o potencial para PDT. O comportamento do fotossensibilizador imobilizado e a possível proteção extra fornecida pela camada de sílica foram estudados pela supressão de fluorescência com íons brometo e supressão da geração de oxigênio singlete com albumina de soro bovino. Hematoporfirina IX é mais afetada na forma livre do que imobilizada em nanoesferas de sílica, o que indica que o FS imobilizado é capaz de gerar oxigênio singlete e está mais protegido de interferentes.
The immobilization of photosensitizers (PS) in nanometric materials is an excellent alternative to their use in molecular forms for photodynamic therapy (PDT). The present work describes a series of synthetic strategies for the immobilization of PS on silica nanospheres containing magnetic nucleous, as well as the studies of the photochemical, photophysical and morphological properties of the obtained materials. The studied PS were methylene blue, thionin, azure A, protoporphyrin IX, hematoporphyrin IX and chlorophyllin. The immobilization methodologies involve the addition of PS during the growth of the silica shell or the attachment of PS to the material surface. Often, a previous modification of the PS with organosilanes was necessary. The magnetic cores were prepared by co-precipitation of iron(II) and iron(III) salts in basic media and the coating with silica was performed by a microemulsion using TEOS. After coating with silica, the magnetic nanomaterial maintained the superparamagnetic behavior. The generation of singlet oxygen by thionin and methylene blue was not detect after immobilization. The generation of singlet oxygen by immobilized azure A, protoporphyrin IX and chlorophyllin was detected and characterized by chemical and physical methods. The material containing chlorophyllin is promising for PDT and was applied in preliminary studies with HeLa cells, causing cell death after irradiation. The behavior of the immobilized PS and the possible extra protection given by the silica shell were investigated by fluorescence quenching with bromide ions and by suppression of singlet oxygen generation with bovine serum albumin. Hematoporphyrin IX was more affected in the free form than immobilized in silica nanospheres, which indicates that the immobilized FS still generates singlet oxygen and is more protected against interfering species

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Gunathilake, Chamila Asanka. "SOFT-TEMPLATING SYNTHESIS OF MESOPOROUS SILICA-BASED MATERIALS FOR ENVIRONMENTAL APPLICATIONS." Kent State University / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=kent1471543020.

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Zuin, André. "Desenvolvimento de nanomateriais superparamagnéticos funcionais para uma química sustentável." Universidade de São Paulo, 2011. http://www.teses.usp.br/teses/disponiveis/46/46136/tde-06092012-131954/.

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Através do uso de reagentes ambientalmente corretos, foram desenvolvidos métodos mais simples que os tradicionais para obtenção de diversos tipos de nanopartículas de magnetita (MagNP) funcionalizadas. Em todos os casos foi confirmado um comportamento superparamagnético consistente com a presença de monodomínios magnéticos de Fe3O4, com diâmetros médios de partícula inferiores a 100 nm, além de histerese nula acima de 280 K, Tb=90K em H=500 Oe e magnetização de saturação em torno de 90 emu g-1. Os métodos de síntese das MagNP foram conduzidos em solventes derivados do biodiesel de soja/mamona, em substituição ao insumos importados, permitindo uma redução significativa nos custos de produção desse tipo de nanomaterial, e viabilizando sua produção em larga escala. Os nanomateriais foram voltados inicialmente para captura, separação e reciclagem de insumos e produtos químicos, incluindo poluentes, catalisadores e enzimas, utilizando ímãs externos. Os procedimentos desenvolvidos proporcionaram uma alternativa verde para os processos convencionais que fazem uso extensivo de solventes, geram muito descarte, e utilizam processos com alta demanda de energia, como centrifugação, extração por solventes e filtração sob altas pressões. As MagNP foram especialmente projetadas para serem dispersas em diversos meios polares e apolares, de acordo com o tipo de funcionalização química na superfície, utilizando principalmente moléculas orgânicas anfifílicas capazes de se ligar na superfície do Fe3O4 por meio de grupos polares, e com matrizes carbonáceas por meio de interações hidrofóbicas. Dessa forma foram gerados novos nanomateriais superparamagnéticos incorporando diversos tipos de matrizes que foram testadas para a remoção de óleo e de compostos orgânicos responsáveis por odores e cores indesejadas em efluentes industriais, bem como para a captura, transporte, recuperação, análise de espécies metálicas ou orgânicas. Foram testadas janelas ópticas e displays nos quais a intensidade de luz transmitida ou refletida pode ser modulada com ímãs externos. O projeto, financiado pela PETROBRÁS contemplou ainda outras aplicações sigilosas, que foram omitidas desta tese. Seu andamento abriu uma importante janela em prol da sustentabilidade, levando ao início do desenvolvimento no Laboratório, da nanomagneto-hidrometalurgia verde para obtenção e reciclagem de metais estratégicos, e de trabalhos de despoluição magnética de ambientes contaminados.
New routes for low cost production of functionalized magnetic nanoparticles (MagNP) have been pursued in this Thesis, by employing environmentally compatible chemicals and resources. The nanomaterials exhibited typical superparamagnetic behavior consistent with the presence of magnetic monodomains, revealing no hysteresis above 280 K, Tb = 90 K at H = 500 Oe, and saturation magnetization as high as 90 emu g-1. The synthetic procedures were carried out using biocompatible solvents derived from biodiesel of soybean and Brazilian mamona seeds, leading to substantial reduction of cost for large-scale production. The superparamagnetic nanoparticles were initially designed for capturing, transporting and recycling chemicals or drugs, including pollutants, catalysts and enzymes, using external magnets. They provide a green alternative strategy for conventional processes that make extensive use of solvents, generate too much waste, and proceeds through highly energetic demanding steps such as centrifugation, solvent extraction and high-pressure filtration. In our work, the MagNPs were appropriately modified for working in polar and non-polar media, employing for instance, amphiphilic species for interacting with Fe3O4 using the available polar groups, and also with carbon surfaces by means of hydrophobic interactions. Accordingly, new superparamagnetic nanomaterials incorporating several types of materials carbon based. It was observed that the carbon materials containing 15 to 20% of magnetic nanoparticles could be completely removed from the media with the use of a magnet. In this way, the functionalized superparamagnetic nanoparticles proved useful for the removal of oil spills and of organic pollutants from industrial processing water, as well as for the capture, removal and recovery of metallic elements and organic species from the effluents. In addition, as a proof of concept, smart windows and displays were elaborated based on the modulation of the transmitted or reflected light by the external magnet. This work was sponsored by PETROBRÁS, and also covered missing, non-authorized aspects involved in two patent applications. Finally, an important consequence to be mentioned is the contribution of this project for launching new chemical routes towards sustainability, such as the development in this Laboratory, of green, magnetic nano-hydrometalurgy for processing and recycling strategic metals, and of the magnetic remediation of polluted environments using the functionalized nanomaterials.

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Wu, Yimin A. "Towards large area single crystalline two dimensional atomic crystals for nanotechnology applications." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:bdb827e5-f3fd-4806-8085-0206e67c7144.

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Nanomaterials have attracted great interest due to the unique physical properties and great potential in the applications of nanoscale devices. Two dimensional atomic crystals, which are atomic thickness, especially graphene, have triggered the gold rush recently due to the fascinating high mobility at room temperature for future electronics. The crystal structure of nanomaterials will have great influence on their physical properties. Thus, this thesis is focused on developing the methods to control the crystal structure of nanomaterials, namely quantum dots as semiconductor, boron nitride (BN) as insulator, graphene as semimetal, with low cost for their applications in photonics, structural support and electronics. In this thesis, firstly, Mn doped ZnSe quantum dots have been synthesized using colloidal synthesis. The shape control of Mn doped ZnSe quantum dots has been achieved from branched to spherical by switching the injection temperature from kinetics to thermodynamics region. Injection rates have been found to have effect on controlling the crystal phase from zinc blende to wurtzite. The structural-property relationship has been investigated. It is found that the spherical wurtzite Mn doped ZnSe quantum dots have the highest quantum yield comparing with other shape or crystal phase of the dots. Then, the Mn doped ZnSe quantum dots were deposited onto the BN sheets, which were micron-sized and fabricated by chemical exfoliation, for high resolution imaging. It is the first demonstration of utilizing ultrathin carbon free 2D atomic crystal as support for high resolution imaging. Phase contrast images reveal moiré interference patterns between nanocrystals and BN substrate that are used to determine the relative orientation of the nanocrystals with respect to the BN sheets and interference lattice planes using a newly developed equation method. Double diffraction is observed and has been analyzed using a vector method. As only a few microns sized 2D atomic crystal, like BN, can be fabricated by the chemical exfoliation. Chemical vapour deposition (CVD) is as used as an alternative to fabricate large area graphene. The mechanism and growth dynamics of graphene domains have been investigated using Cu catalyzed atmospheric pressure CVD. Rectangular few layer graphene domains were synthesized for the first time. It only grows on the Cu grains with (111) orientation due to the interplay between atomic structure of Cu lattice and graphene domains. Hexagonal graphene domains can form on nearly all non-(111) Cu surfaces. The few layer hexagonal single crystal graphene domains were aligned in their crystallographic orientation over millimetre scale. In order to improve the alignment and reduce the layer of graphene domains, a novel method is invented to perform the CVD reaction above the melting point of copper (1090 ºC) and using molybdenum or tungsten to prevent the balling of the copper from dewetting. By controlling the amount of hydrogen during the growth, individual single crystal domains of monolayer over 200 µm are produced determined by electron diffraction mapping. Raman mapping shows the monolayer nature of graphene grown by this method. This graphene exhibits a linear dispersion relationship and no sign of doping. The large scale alignment of monolayer hexagonal graphene domains with epitaxial relationship on Cu is the key to get wafer-sized single crystal monolayer graphene films. This paves the way for industry scale production of 2D single crystal graphene.

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Amsarajan, S. "Chemistry of carbonized metallic nanomaterials." Thesis, 2018. https://etd.iisc.ac.in/handle/2005/5381.

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Magnetic nanomaterials have received significant attention because of their remarkable properties enabling applications in various fields such as catalysis, as contrast agents for magnetic resonance imaging, in sensing applications, as environmental catalysts and as adsorbents. Magnetic properties of materials depend on certain factors such as size, shape, crystallinity, composition, crystal structure, and synthetic methodology. Most of the pristine magnetic nanoparticles are highly pyrophoric in nature which poses difficulties in handling these materials. In addition, the ease of oxidation and potential toxicity of these materials preclude their practical applications. Further, these magnetic nanoparticles have strong magnetic interactions between them which leads to the aggregation of particles. These features affect the magnetic behaviour as well as the other characteristics of the material. In this context, fabricating magnetic nanomaterials with desired magnetic properties, chemical stability and surface chemistry is quite challenging. Similarly, plasmonic metal nanoparticles such as Ag and Cu also suffer from issues pertaining to oxidative instability upon air exposure under ambient conditions. Therefore, it is crucial to develop protection strategies to stabilize nanoparticles surface against oxidation. This thesis describes the synthesis of carbon encapsulated mono- and bi-metallic nanoparticles using solvated metal atom dispersion method in conjunction with digestive ripening approach followed by thermal annealing. The aim of the work is to understand the effect of size, shape, composition, and the nature of surface on the properties of these metallic nanomaterials. In this direction, nanosystems of Fe, Ag, Cu, Fe3C, and FeCo have been studied.

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O'Brien, Evan S. "The Development of Functionally Tunable Hierarchical Nanomaterials." Thesis, 2018. https://doi.org/10.7916/D8D80V70.

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Superatomic crystals (SACs) with tunable physical properties offer a new approach to the design of inorganic nanomaterials. Very little is known about how these systems function, or how their properties can be transformed. Here I describe work that helps to develop an understanding of how functional properties behave in SACs, and how they can be altered through superatomic intercalation or with phase transitions. Chapter 1 describes work characterizing the thermal transport behavior of SACs. We find that heat transfer is dominated by coherent inter-cluster phonons with vibrational frequencies determined by the periodicity of the SAC superstructure. We also demonstrate a transformation from amorphous to crystalline thermal transport behavior through manipulation of the vibrational landscape and orientational order of the superatoms. Chapters 2 and 3 describe the intercalation of a porous superatomic host, [Co6Te8(PnPr3)6][C60]3. We find that guests can be inserted into the superstructure through single-crystal-to-single-crystal transformations, dramatically transforming the electronic properties of the SAC. Using electronic absorption spectroscopy, electrical transport measurements and electronic structure calculations, we demonstrate that the intercalation is driven by the exchange of charge between the host, establishing an exciting design space for the preparation of superatomic materials. Chapter 4 describes a hierarchical solid, [Co6Te8(PEt3)6][C70]2, in which the delicate balance of interactions between constituent building blocks produces two separate phase transitions: one affecting thermal transport properties, the other transforming the electronic and magnetic behavior of the SAC. We use a wide range of structural and spectroscopic characterization tools to understand the mechanism of each transformation. This work establishes a new ability to program functional phase transitions into cluster-assembled materials. In a completely different area of study, chapter 5 describes a new covalent organic framework (COF) whose unique structure enables a post-synthetic topochemical polymerization of the framework’s linker fragments. The polymerization of the 1-3 butadiyne into a polydiacetylene backbone covalently crosslinks the material without compromising its original crystallinity. This work not only enables the preparation of more structurally resilient COFs, but also diversifies the design space for this emerging class of materials.

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35

"Synthesis, characterization, and functionalization of transition metal phosphide nanomaterials from single source molecular precursors." Thesis, 2010. http://hdl.handle.net/1911/62022.

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This thesis details the synthesis, characterization, and functionalization of transition metal phosphide nanomaterials from single source molecular precursors. The decomposition of the organometallic cluster, H2Fe3(CO) 9PtBu, yielded iron phosphide (Fe2P) nanomaterials of various morphologies depending on the surfactants used for the decomposition. Branched nanostructures were observed as a result of crystal splitting in a few of the surfactant systems. Cross-shaped structures were also observed and attributed to the twinning of two individual bundles during growth as the result of an interrupted growth process. The role of the solvents in particular the use of oleic acid for the formation of nanorods, in the formation of Fe2P nanoparticles will be discussed. Magnetic measurements taken of a variety of different morphologies of these iron phosphide nanoparticles will also be presented. Fe2P nanoparticles were also isolated via the decomposition of other clusters, including Fe3(CO) (P tBu)2, Fe2(CO)6(PHtBu) 2, Fe4(CO)11PtBu2, and Fe3(CO)10PtBu. In order to study the mechanism by which the clusters decompose, the decompositions were monitored using infrared spectroscopy. For all of the systems studied, the clusters rearranged in the surfactant solutions, ultimately resulting in Fe2(CO) 6(PHtBu)2 prior to decomposition. This rearrangement is believed to be a result of the interaction of the clusters with the surfactants employed, suppored by the finding that the solid state decomposition of H 2Fe3(CO)pPtBu was found to result in a combination of Fe 3P, Fe2P, and Fe3O4. In addition to the formation of the binary phases of transition metal phosphide nanomaterials, investigation into the formation of mixed metal phosphides of iron and manganese were also performed. For these experiments, H2 Fe3(CO)9PtBu with a manganese source, either Mn2(CO)10 or Mn(CO)5Br, were decomposed in a variety of surfactant systems. The resulting nanoparticles were only doped with manganese; pure stoichiometric phases were not isolated. Finally the functionalization of Fe2P split rods, T-shapes, and crosses with a gold shell was performed. Their optical properties were studied, and a redshift in the extinction maximum was seen as the shell thickness increased. This plasmon peak shift, as opposed to the trends seen in silica-Au core-shell structures as shell thickness increases, is attributed to the high permittivity of the Fe2P core.

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Ghosh, Sandeep. "Investigation Of Inorganic Nanomaterials & Polymer Films." Thesis, 2011. https://etd.iisc.ac.in/handle/2005/2349.

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The thesis is divided into two parts. The first part deals with the research work carried out on the synthesis and chemical modification of nanomaterials whereas the second part describes the preparation and characterisation of polymer films and their use as separation membranes. Part I of the thesis describing the synthetic strategies and chemical manipulation schemes employed on various types of nanomaterials is divided into six chapters. Chapter 1 describes a chemist’s approach towards synthesizing and tuning the properties of different classes of nanomaterials along with a brief account of their potential applications. Chapter 2 of the thesis describes the synthesis and characterization of various metal nanostructures (viz. nanoparticles, nanorods, nanosheets etc.) of nickel, ruthenium, rhodium and iridium using a solvothermal procedure. Chapter 3 deals with the nanoparticles of the novel oxide metal ReO3. ReO3@Au, ReO3@Ag, ReO3@SiO2 and ReO3@TiO2 core-shell nanostructures with ReO3 as the core nanoparticle have been synthesized through a two-step process and characterized. Dependence of the plasmon band of the ReO3 nanoparticles on the interparticle separation has been examined by incorporating the nanoparticles in various polymer matrices and the results compared with those obtained with gold nanoparticles. Chapter 4 presents the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity (water, DMF and toluene) in the presence of several surfactants. In Chapter 5 of the thesis, fluorous chemical method of separation of metallic and semiconducting single-walled carbon nanotubes is described. This method involves the selective reaction of the diazonium salt of a ﬂuorous aniline with the metallic nanotubes in an aqueous medium and subsequent extraction of the same in a fluorous solvent leaving the semiconducting nanotubes in the aqueous layer. Chapter 6 presents the studies on the interaction of single walled nanotubes and graphene with various halogen molecules (I2, IBr, ICl and Br2) of varying electron affinity probed by employing Raman spectroscopy and electronic absorption spectroscopy. Part II of the thesis describes a general method of fabricating ultrathin free-standing cross-linked polymer films and their subsequent use as separation membranes. A particular class of 1-D nanomaterials namely cadmium hydroxide nanostrands were used in this method throughout, to generate a sacrificial layer upon which the polymer films were generated.

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37

Ghosh, Sandeep. "Investigation Of Inorganic Nanomaterials & Polymer Films." Thesis, 2011. http://hdl.handle.net/2005/2349.

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The thesis is divided into two parts. The first part deals with the research work carried out on the synthesis and chemical modification of nanomaterials whereas the second part describes the preparation and characterisation of polymer films and their use as separation membranes. Part I of the thesis describing the synthetic strategies and chemical manipulation schemes employed on various types of nanomaterials is divided into six chapters. Chapter 1 describes a chemist’s approach towards synthesizing and tuning the properties of different classes of nanomaterials along with a brief account of their potential applications. Chapter 2 of the thesis describes the synthesis and characterization of various metal nanostructures (viz. nanoparticles, nanorods, nanosheets etc.) of nickel, ruthenium, rhodium and iridium using a solvothermal procedure. Chapter 3 deals with the nanoparticles of the novel oxide metal ReO3. ReO3@Au, ReO3@Ag, ReO3@SiO2 and ReO3@TiO2 core-shell nanostructures with ReO3 as the core nanoparticle have been synthesized through a two-step process and characterized. Dependence of the plasmon band of the ReO3 nanoparticles on the interparticle separation has been examined by incorporating the nanoparticles in various polymer matrices and the results compared with those obtained with gold nanoparticles. Chapter 4 presents the dispersion of nanostructures of metal oxides such as TiO2, Fe3O4 and ZnO in solvents of differing polarity (water, DMF and toluene) in the presence of several surfactants. In Chapter 5 of the thesis, fluorous chemical method of separation of metallic and semiconducting single-walled carbon nanotubes is described. This method involves the selective reaction of the diazonium salt of a ﬂuorous aniline with the metallic nanotubes in an aqueous medium and subsequent extraction of the same in a fluorous solvent leaving the semiconducting nanotubes in the aqueous layer. Chapter 6 presents the studies on the interaction of single walled nanotubes and graphene with various halogen molecules (I2, IBr, ICl and Br2) of varying electron affinity probed by employing Raman spectroscopy and electronic absorption spectroscopy. Part II of the thesis describes a general method of fabricating ultrathin free-standing cross-linked polymer films and their subsequent use as separation membranes. A particular class of 1-D nanomaterials namely cadmium hydroxide nanostrands were used in this method throughout, to generate a sacrificial layer upon which the polymer films were generated.

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Biswas, Kanishka. "Synthesis, Characterization, Properties And Growth Of Inorganic Nanomaterials." Thesis, 2008. https://etd.iisc.ac.in/handle/2005/706.

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The thesis consists of eight chapters of which the first chapter presents a brief overview of inorganic nanostructures. Synthesis and magnetic properties of MnO and NiO nanocrystals are described in Chapter 2, with emphasis on the low-temperature ferromagnetic interactions in these antiferromagnetic oxides. Chapter 3 deals with the synthesis and characterizations of nanocrystals of ReO3, RuO2 and IrO2 which are oxides with metallic properties. Pressure-induced phase transitions of ReO3 nanocrystals and the use of the nanocrystals for carrying out surface-enhanced Raman spectroscopy of the molecules form Chapter 4. Use of ionic liquids to synthesize different nanostructures of semiconducting metal sulfides and selenides is described in Chapter 5. Synthesis of Mn-doped GaN nanocrystals and their magnetic properties are described in Chapter 6. A detailed investigation has been carried out on the growth kinetics of nanostructures of a few inorganic materials by using small-angle X-ray scattering and other techniques (Chapter 7). The study includes the growth kinetics of nanocrystals of Au, CdS and CdSe as well as of nanorods of ZnO. Results of a synchrotron X-ray study of the formation of nanocrystalline gold films at the organic-aqueous interface are also included in this chapter. Chapter 8 discuses the use of the organic-aqueous interface to generate Janus nanocrystalline films of inorganic materials where one side of the film is hydrophobic and other side is hydrophilic. This chapter also includes the formation of nanostructured peptide fibrils at the organic-aqueous interface and their use as templates to prepare inorganic nanotubes.

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39

Biswas, Kanishka. "Synthesis, Characterization, Properties And Growth Of Inorganic Nanomaterials." Thesis, 2008. http://hdl.handle.net/2005/706.

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The thesis consists of eight chapters of which the first chapter presents a brief overview of inorganic nanostructures. Synthesis and magnetic properties of MnO and NiO nanocrystals are described in Chapter 2, with emphasis on the low-temperature ferromagnetic interactions in these antiferromagnetic oxides. Chapter 3 deals with the synthesis and characterizations of nanocrystals of ReO3, RuO2 and IrO2 which are oxides with metallic properties. Pressure-induced phase transitions of ReO3 nanocrystals and the use of the nanocrystals for carrying out surface-enhanced Raman spectroscopy of the molecules form Chapter 4. Use of ionic liquids to synthesize different nanostructures of semiconducting metal sulfides and selenides is described in Chapter 5. Synthesis of Mn-doped GaN nanocrystals and their magnetic properties are described in Chapter 6. A detailed investigation has been carried out on the growth kinetics of nanostructures of a few inorganic materials by using small-angle X-ray scattering and other techniques (Chapter 7). The study includes the growth kinetics of nanocrystals of Au, CdS and CdSe as well as of nanorods of ZnO. Results of a synchrotron X-ray study of the formation of nanocrystalline gold films at the organic-aqueous interface are also included in this chapter. Chapter 8 discuses the use of the organic-aqueous interface to generate Janus nanocrystalline films of inorganic materials where one side of the film is hydrophobic and other side is hydrophilic. This chapter also includes the formation of nanostructured peptide fibrils at the organic-aqueous interface and their use as templates to prepare inorganic nanotubes.

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40

Huang, Yimin. "Functional nano-bio interfaces for cell modulation." Thesis, 2020. https://hdl.handle.net/2144/41113.

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Interacting cellular systems with nano-interfaces has shown great promise in promoting differentiation, regeneration, and stimulation. Functionalized nanostructures can serve as topological cues to mimic the extracellular matrix network to support cellular growth. Nanostructures can also generate signals, such as thermal, electrical, and mechanical stimulus, to trigger cellular stimulation. At this stage, the main challenges of applying nanostructures with biological systems are: (1) how to mimic the hierarchical structure of the ECM network in a 3D format and (2) how to improve the efficiency of the nanostructures while decreasing its invasiveness. To enable functional neuron regeneration after injuries, we have developed a 2D nanoladder scaffold, composed of micron size fibers and nanoscale protrusions, to mimic the ECM in the spinal cord. We have demonstrated that directional guidance during neuronal regeneration is critical for functional reconnection. We further transferred the nanoladder pattern onto biocompatible silk films. We established a self-folding strategy to fabricate 3D silk rolls, which is an even closer system to mimic the ECM of the spinal cord. As demonstrated by in vitro and in vivo experiments, such a scaffold can serve as a grafting bridge to guide axonal regeneration to desired targets for functional reconnection after spinal cord injuries. Benefited from the robust self-folding techniques, silk rolls can also be used for heterogeneous cell culture, providing a potential therapeutic approach for multiple tissue regeneration directions, such as bones, muscles, and tendons. For achieving neurostimulation, we have developed photoacoustic nanotransducers (PANs), which generate ultrasound upon excitation of NIR II nanosecond laser light. By surface functionalize PAN to bind to neurons, we have achieved an optoacoustic neuron stimulation process with a high spatial and temporal resolution, proved by in-vitro and in-vivo experiments. Such an application can enable non-invasive, optogenetics free and MRI compatible neurostimulation, which provides a new direction of gene-transfection free neuromodulation. Collectively, in this thesis, we have developed two systems to promote functional regeneration after injuries and stimulate neurons in a minimally invasive manner. By integrating those two functions, a potential new generation of the bioengineered scaffold can be investigated to enable functional and programmable control during the regeneration process.

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41

Malik, Shahid A. "Protein-Nanomaterial Interactions: Structural And Dynamic Aspects." Thesis, 2019. https://etd.iisc.ac.in/handle/2005/4428.

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Owing to their unique properties, the noble metallic nanoparticles and graphenic nanomaterials find their applications in diverse fields of science. Particularly in the field of biomedicine, nanomaterials are being used in drug delivery, tumor targeting, bio-sensing, tissue engineering and photo thermal therapy. The accidental or the intentional exposure of human body towards these nanomaterials paves their way into the body. But at the same time, the knowledge about the exposure risks and the biocompatibility of these nanomaterials remains largely unknown. Some of the studies have found that the nanomaterials show adverse effects towards the biological systems under in vitro and in vivo conditions. When these nanomaterials come in contact with biomolecules, such as peptides and proteins, layers of biomolecules cover their surfaces, leading to the formation of a dynamic and competitive protein corona. The formation of protein corona has the potential to affect the properties of both the nanoparticles (e.g., cellular uptake, accumulation, degradation and clearance from the body) and the protein adsorbed on the surface (e.g., protein conformation and function). Hence, unexpected biological responses and toxicity may be induced. It therefore becomes important to probe the nature of interactions of biomolecules at their individual residual level with nanomaterials. Depending upon the surface charges of both; the nanomaterials and the proteins, there may either be strong and irreversible or weaker and reversible interactions between proteins and nanomaterials involving electrostatic or covalent interactions. Thus, the understanding of such protein-nanomaterial interactions can be exploited for the generation of the safe and biocompatible nanomaterials with optimized surface properties in a biological milieu. The main aim of our work is to probe into the residual level conformational changes in the proteins in presence of nanomaterials and the dynamic aspects of such interactions. Using two-dimensional NMR spectroscopy in combination with other biophysical techniques we report that the citrate capped silver nanoparticles (AgNPs) have the ability to stabilize an intrinsically disordered protein (IDP) against the proteolysis by masking the proteolytic prone sites on the protein thereby rendering it stable for a month against proteolytic degradation. Our studies reveal the extent and nature of residue-specific interactions of the IDP with AgNPs. This study will be helpful in designing the appropriate nanoparticles targeting IDPs and for storage, stabilization and delivery of IDPs into cells in a stable form. Our other findings show that human ubiquitin (a globular protein) interacts electrostatically with the different graphene oxides (GOs) having varying amounts of defects, oxidation levels, and surface chemistry. The protein undergoes a dynamic and reversible exchange (fast exchange regime) on the surface of the GOs. The interaction does not involve any change in the secondary structure of the protein. We further investigated the aggregation tendency of human alpha synuclein in presence of the gold nanoparticles and graphene oxide. Our results show that the gold nanoparticles act as the catalysts in the aggregation process of human alpha synuclein while as the GO shows inhibitory actions on the aggregation tendency of the same protein under the similar conditions by effecting the main phases (nucleation and growth) amyloid kinetics. Furthermore, we show here that the protein-nanoparticle interaction is largely electrostatic in nature and the binding affinity of the human alpha synuclein for the citrate capped gold nanoparticles is lower than that of the GO. Hence the nature of interactions and the binding affinity of the protein towards the nanomaterials decide the path of the protein aggregation (enhanced aggregation or inhibited aggregation). Our results help in exploring the mechanism of protein aggregation at the individual residue level and the respective catalytic and inhibitory effects of gold nanoparticles and GO in protein aggregation and hence will prove to be fruitful in devising the potential therapeutic reagents against Parkinson’s and other neurodegeneratory diseases.

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Bhatia, Geetanjali. "Chemistry of bimetallic, chalcogenide and highly reactive metal nanoparticles." Thesis, 2023. https://etd.iisc.ac.in/handle/2005/6207.

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The remarkable modifications in the characteristics of materials on a nanoscale, caused by surface effects, quantum confinement, and dependence on shape, leads to diverse applications of nanomaterials, such as in catalysis, environmental applications, energy conversion and storage, etc. Research on nanomaterials is extensively concentrated on metal nanoparticles, particularly those made of noble metals and various transition metal elements, as well as systems that utilize these metals. However, research on systems based on post-transition elements, such as Sn, has remained relatively underdeveloped. This is because these elements have a strong affinity for oxygen and a low affinity towards most surfactants, making controlled synthesis of their size and shape challenging. Besides that, researchers have also been drawn to various other types of nanomaterials, including alloys, intermetallics, chalcogenides, and more. In addition, the synthesis of nanomaterials with a particular emphasis on their usage in energy storage applications is a significant area of research. Achieving a controlled and scalable synthesis of nanomaterials is the primary challenge in the field of nanoscience. Out of the many techniques available, solution-based chemical synthesis strategies provide an effective and straightforward approach to producing nanomaterials. The solution-based synthesis offers control over size and shape of nanomaterials by providing a convenient medium for their growth and carries the advantage of greater flexibility compared to the dry synthetic routes. In this direction, the digestive ripening technique in combination with solvated metal atom dispersion method (SMAD) is one of the exceptional solution-based synthesis methods for creating nanomaterials. This thesis is dedicated to demonstrating a solution-based synthesis of a broad range of nanomaterials, including alloys, intermetallics, and chalcogenides, and to investigate their potential for various applications. The research also delves into the synthesis and characterization of highly reactive nanomaterials, such as magnesium-carbon composites, which are essential for hydrogen energy storage.

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Arunachalam, Vaishali. "Aqueous and Non-aqueous Dispersions of Graphene and Boron Nitride Nanosheets : NMR Measurements and Molecular Dynamics Simulations." Thesis, 2017. http://etd.iisc.ac.in/handle/2005/4306.

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Preface Ever since the discovery of graphene in 2004, there has been considerable interest in two dimensional (2D) nanomaterials due to their distinctive properties and the prospect of potential applications. A 2D-nanomaterial may be obtained from the bulk layered material by procedures that can overcome the van der Waals attractive force that hold adjacent layers together. Historically this was first achieved by micro-mechanical cleavage by the deceptively simple procedure of peeling atomically thin single layers from the bulk material using scotch tape. The procedure, unfortunately, is not scalable and consequently alternate procedures, both top-down as well as bottom-up, have been extensively explored. One of the simplest methods to obtain defect-free 2D nanosheets is the sonication assisted liquid phase exfoliation of the bulk layered material in a suitable solvent. The role of the solvent is crucial to the liquid phase exfoliation process, as the formation of stable dispersions require that the exfoliated sheets, produced on sonication, be prevented from re-aggregating. A wide range of solvents, solvent mixtures and surfactant solutions have been investigated and solvent systems that favour formation of stable dispersions identified. Much of the current understanding of the role of the solvent is based on phenomenological models, matching surface energies of the solvent and the layered material so as to minimize the surface tension between the two. What has remained elusive, however, is a molecular perspective of the nature of interactions between the solvent and the exfoliated nanosheet. This the focus of the present study. This thesis reports results of investigations on dispersions of graphene in aqueous and non-aqueous media as well as dispersions of boron nitride in water using solution and solid-state Nuclear Magnetic Resonance (NMR) spectroscopy aided by Molecular Dynamics (MD) simulations for interpreting the experimental observations. The thesis is organized as five chapters with Chapter 1 providing a brief overview of 2D nanomaterials with focus on graphene and boron nitride (BN); their properties and applications. The chapter discusses the methods for obtaining graphene and BN nanosheets with emphasis on the sonication assisted liquid phase exfoliation approach. The chapter also provides a brief review of the phenomenological models that have been advanced to understand the stability of dispersions of 2D nanomaterials in different solvents. The stability of the nanosheet dispersions require that solvent or ligand molecules be in close association with the nanosheets with properties and mobilities quite different from those of the bulk solvent molecules. The challenge for in-situ measurements is to be able to probe the bound or associated solvent/ ligand molecules in the presence of a large excess of the bulk. NMR methods from the solution chemists toolbox are known to provide methodologies that can distinguish bound ligand molecules from those in the bulk and are, therefore, ideal techniques for investigating nanosheet dispersions. In particular transfer Nuclear Overhauser Effect Spectroscopy (tr-NOESY) as well as Rotating-frame Overhauser Effect Spectroscopy (ROESY) are well suited for systems where bound and free solvent/ ligand molecules are in continuous exchange. This chapter also provides a brief overview of the NMR experiments used in studying nanosystem-ligand interactions. The results from NMR measurements provide a spectroscopic signature of solvent nanosheet interactions in the dispersions and in conjunction with Molecular Dynamics (MD) simulations provide a molecular level understanding of the stability of the dispersions and the role of the solvent. The MD simulation methodology used in this study are discussed in Chapter 2 along with the computational tools employed in the thesis. Graphene is perhaps the most studied 2D nanomaterial and its distinctive properties has paved the way for the commercial use of graphene-based materials in a variety of applications. Sonication of bulk graphite in an organic solvent or aqueous surfactant solutions has been considered a simple and scalable route for the production of defect free graphene nanosheets. In aqueous solutions the interaction of surfactant chains with the graphene sheets is crucial to the stability of the dispersion. In Chapter 3, 1H two-dimensional Nuclear Overhauser Effect spectroscopy (NOESY) and classical MD simulations have been used to probe these interactions in graphene dispersions stabilized by the cationic surfactant cetyltrimethylammonium bromide (CTAB). It is shown from the presence of intense negative transfer-NOESY cross peaks that the surfactant chains are quasi-bound to the graphene sheets and undergo rapid exchange with free surfactant ligands present in the dispersion. A surprising feature of the NOESY is the presence of cross-peaks between groups that are separated by more than 5_A along the chain even between protons of the `head' group of the CTA surfactant chain and protons of the `tail' methyl group. This observation of apparent very short separation of protons of distal groups of the surfactant chain corroborated reects the arrangement adopted by the surfactant chains in the quasi-bound state in the dispersion. Classical MD simulations of the dispersion provides a simple interpretation of these observations. The simulations show that surfactant CTA chains lie at on the graphene sheets adopting a random arrangement with the head of one chain in close proximity to the tail of another chain. This arrangement can give rise to cross peaks in the NOESY between groups that are apparently far separated along the chain. One of the most efficient organic solvents for the sonication assisted liquid phase exfoliation of graphite is N-methyl-2-pyrrolidone (NMP). Much of the success of phenomenological models based on surface energies has been correctly predicting that NMP would be good solvent because its surface energy and that of graphite are comparable. A molecular level understanding of the interaction of NMP and graphene sheets in the dispersion is, however, not available. In Chapter 4, it is shown that NMR methods can provide a spectroscopic signature for these interactions. The 2D ROESY NMR shows significant differences in the spectra of graphene dispersions in NMP and the pure solvent. MD simulations of a graphene sheet immersed in NMP solvent molecules show that these differences arise because of induced layering of solvent molecules in the vicinity of the sheet. The arrangement facilitates lowering of the rotational correlation time of the NMP molecules near the surface of the graphene sheet that are easily captured in the experimental two-dimensional ROESY NMR and which manifests as enhanced cross-peak intensities as compared to the bulk solvent. Among the graphene analogues boron nitride nanosheets has been considered the closest because of the similarities in structures of hexagonal BN and graphite as well as the positions of the respective elements in the periodic table. Their aqueous dispersibilities are, however, very different. While graphene does not exfoliate or form stable dispersions in water the hydrophobic BN forms stable dispersions on sonication in water, without the need for surfactants or stabilizers. In Chapter 5, it is shown from zeta potential measurements that the sheets are positively charged and the stability of the dispersions are electrostatic in origin. The observations indicate that BN reacts with water on sonication. Ab initio (Car-Parinello) MD simulations and reactive force-field (ReaxFF) MD simulations were performed to understand the reactivity, and the origin of the stability of the aqueous dispersions of BN. The simulations showed that water molecules dissociate at the edges of the BN sheets leading to the to the formation of NH bonds with the release of OH into the bulk. The simulations explain why the dispersions are basic and the exfoliated BN nanosheets in the dispersion positively charged. 1H and 11B solid-state NMR spectroscopy were used to identify the chemical species as predicted by the MD simulations. The combination of MD simulations and NMR measurements are able to provide a comprehensive understanding of the origin of the aqueous dispersibility of the hydrophobic BN nanosheets. The results are summarized in Chapter 6.

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44

Maity, Mitasree. "Bile Acid based Supramolecular Gels, Soft Hybrid Materials and their Applications." Thesis, 2016. http://etd.iisc.ac.in/handle/2005/2928.

Full text

Abstract:

Chapter 1. Supramolecular Gels and their Applications Supramolecular gels are viscoelastic materials composed of a solid like three dimensional fibrillary network that is embedded in a liquid. Supramolecular gels are derived from low molecular weight compounds (typically MW < 3000). In the 1990s, the investigations on gels were mainly focused on designing new gelator molecules. However, during the last decade, research focus shifted towards designing functional gels and their applications. As a result of extensive work in this area, gels have been found to have varied applications in the templated synthesis of inorganic nanomaterials, hybrid materials, light harvesting systems, as responsive system and sensors, and also in drug delivery, tissue engineering etc. This chapter gives an introduction to supramolecular hydrogels/organogels and relevant bile acid chemistry touching upon the gelation properties of the bile acid derivatives. Diverse applications of the supramolecular gels are also illustrated with several examples. Scheme 1. Various applications of functional supramolecular gels Chapter 2. Bile Acid derived novel Hydrogelators Part 1. Hydrogelation of Bile acid protected Amino acids and Hybrid Materials Hydrogels from low molecular weight molecules have significant importance in biomedical applications. In this chapter, we report injectable hydrogel formation from bile acid conjugates of various amino acids. Hydrogel formation was found to be dependent on multiple factors such as bile acid backbone structure, linkage between the bile acid and the amino acid, pH etc. Single crystal structures of lithocholyl phenylalanine, lithocholyl-glycine, lithocholyl-L valine and lithocholyl-L alanine were also determined. Finally, the hydrogel frameworks were utilized to produce hybrid materials with Gold and ZnO nanoparticles. Scheme 2. (a) Crystal structure of LC-LF-OH gelator molecule, (b) photograph of gel, (c) SEM and (d) AFM image of LC-LF-OH xerogel Part 2. Hydrogelation of bile acid-dipeptide conjugates and in situ synthesis of silver and gold nanoparticles in the hydrogel matrix Fabricating supramolecular hydrogels with embedded metal nanostructures are important for the design of novel hybrid nanocomposite materials for diverse applications such as bio sensing and chemo sensing platforms, catalytic and antibacterial functional materials etc. Supramolecular self-assembly of bile acid-dipeptide conjugates have led to the formation of new supramolecular hydrogels. Gelation of these molecules depends strongly on the hydrophobic character of the bile acids. Ag+ and Au3+ salts were incorporated in the hydrogels, and photo reduction and chemical reduction led to the in situ generation of Ag and Au NPs in these supramolecular hydrogels without the addition of any external stabilizing agent. The color, size and shape of silver nanoparticles formed by photo reduction depended on the amino acid residue on the side chain. Furthermore, the hydrogel-Ag nanocomposite was tested for its antimicrobial activity. Scheme 3. Bile acid based dipeptide hydrogelators and soft hybrid materials Chapter 3. Sonogels of bile salts of In(III): use in the formation of self-templated indium sulfide nanostructures In this chapter, facile hydrogel formation by Indium(III) cholate and deoxy cholate are reported. When In(III) solution was added to aqueous solutions of sodium cholate and sodium deoxy cholate and sonicated, the mixtures formed gels. The gels thus obtained were translucent/turbid and thermos irreversible. Rheological measurements showed that all of them could be classified as viscoelastic soft solids. Scanning electron microscopy and atomic force microscopy showed typical entangled three dimensional fibrous networks. The In-Ch hydrogel were further used to prepare nanostructured In2S3 in which the cholate units possibly acted as a surfactant to confine the growth of the Nano flakes. Scheme 4. In-Ch hydrogel (Photograph and SEM image of In-Ch gel) Chapter 4. Palladium-Hydrogel Nanocomposite for C-C Coupling Reactions Supported metallic nanoparticles are important composite materials owing to their enormous potential for applications in various fields. This chapter describes the in situ formation of palladium nanoparticles in a calcium-cholate (Ca-Ch) hydrogel by reduction with sodium cyan borohydride. The hydrogel matrix appeared to assist the controlled growth as well as stabilization of palladium nanoparticles. The palladium nanoparticle/Ca-Ch hydrogel hybrid was characterized by scanning and transmission electron microscopy, atomic force microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. Furthermore, PdNP/Ca-Ch hybrid xerogel was shown to act as an active catalyst for Suzuki reaction under aqueous aerobic conditions, up to 4 cycles. This PdNP/Ca-Ch xerogel retained its catalytic activities on storage for several months. Scheme 5. Palladium-hydrogel nanocomposite for C-C coupling reactions in water Chapter 5. Sensitization of Terbium/Europium in self-assembled cholate hydrogel: An approach towards the detection of amine vapours "Luminescent" lanthanides have intrinsic low molar absorptivity, although this problem can be addressed by complexing the lanthanide ion with suitable chelating ligands which improve the luminescence properties drastically. However the design of such systems often involves careful planning and laborious synthetic steps. It is therefore desirable to have a simpler way to sensitize lanthanides with high efficiency. It was observed in our group that trivalent lanthanides formed hydrogels on the addition of sodium cholate. This chapter describes the discovery of the several biphenyl derivatives (such as 4-biphenylcarbaxaldehyde, 4-acetylbiphenyl) for sensitization of Tb(III) and Eu(III) in lanthanide hydrogels. Sensitization of Tb(III) and Eu(III) were observed by doping was characterized by scanning and transmission electron microscopy, atomic force microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. Furthermore, PdNP/Ca-Ch hybrid xerogel was shown to act as an active catalyst for Suzuki reaction under aqueous aerobic conditions, up to 4 cycles. This PdNP/Ca-Ch xerogel retained its catalytic activities on storage for several months. Scheme 6. Schematic representation of the sensitization process (the arrangement of themolecules in the gel fiber is arbitrary)(For figures pl refer the abstract pdf file)

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45

Maity, Mitasree. "Bile Acid based Supramolecular Gels, Soft Hybrid Materials and their Applications." Thesis, 2016. http://hdl.handle.net/2005/2928.

Full text

Abstract:

Chapter 1. Supramolecular Gels and their Applications Supramolecular gels are viscoelastic materials composed of a solid like three dimensional fibrillary network that is embedded in a liquid. Supramolecular gels are derived from low molecular weight compounds (typically MW < 3000). In the 1990s, the investigations on gels were mainly focused on designing new gelator molecules. However, during the last decade, research focus shifted towards designing functional gels and their applications. As a result of extensive work in this area, gels have been found to have varied applications in the templated synthesis of inorganic nanomaterials, hybrid materials, light harvesting systems, as responsive system and sensors, and also in drug delivery, tissue engineering etc. This chapter gives an introduction to supramolecular hydrogels/organogels and relevant bile acid chemistry touching upon the gelation properties of the bile acid derivatives. Diverse applications of the supramolecular gels are also illustrated with several examples. Scheme 1. Various applications of functional supramolecular gels Chapter 2. Bile Acid derived novel Hydrogelators Part 1. Hydrogelation of Bile acid protected Amino acids and Hybrid Materials Hydrogels from low molecular weight molecules have significant importance in biomedical applications. In this chapter, we report injectable hydrogel formation from bile acid conjugates of various amino acids. Hydrogel formation was found to be dependent on multiple factors such as bile acid backbone structure, linkage between the bile acid and the amino acid, pH etc. Single crystal structures of lithocholyl phenylalanine, lithocholyl-glycine, lithocholyl-L valine and lithocholyl-L alanine were also determined. Finally, the hydrogel frameworks were utilized to produce hybrid materials with Gold and ZnO nanoparticles. Scheme 2. (a) Crystal structure of LC-LF-OH gelator molecule, (b) photograph of gel, (c) SEM and (d) AFM image of LC-LF-OH xerogel Part 2. Hydrogelation of bile acid-dipeptide conjugates and in situ synthesis of silver and gold nanoparticles in the hydrogel matrix Fabricating supramolecular hydrogels with embedded metal nanostructures are important for the design of novel hybrid nanocomposite materials for diverse applications such as bio sensing and chemo sensing platforms, catalytic and antibacterial functional materials etc. Supramolecular self-assembly of bile acid-dipeptide conjugates have led to the formation of new supramolecular hydrogels. Gelation of these molecules depends strongly on the hydrophobic character of the bile acids. Ag+ and Au3+ salts were incorporated in the hydrogels, and photo reduction and chemical reduction led to the in situ generation of Ag and Au NPs in these supramolecular hydrogels without the addition of any external stabilizing agent. The color, size and shape of silver nanoparticles formed by photo reduction depended on the amino acid residue on the side chain. Furthermore, the hydrogel-Ag nanocomposite was tested for its antimicrobial activity. Scheme 3. Bile acid based dipeptide hydrogelators and soft hybrid materials Chapter 3. Sonogels of bile salts of In(III): use in the formation of self-templated indium sulfide nanostructures In this chapter, facile hydrogel formation by Indium(III) cholate and deoxy cholate are reported. When In(III) solution was added to aqueous solutions of sodium cholate and sodium deoxy cholate and sonicated, the mixtures formed gels. The gels thus obtained were translucent/turbid and thermos irreversible. Rheological measurements showed that all of them could be classified as viscoelastic soft solids. Scanning electron microscopy and atomic force microscopy showed typical entangled three dimensional fibrous networks. The In-Ch hydrogel were further used to prepare nanostructured In2S3 in which the cholate units possibly acted as a surfactant to confine the growth of the Nano flakes. Scheme 4. In-Ch hydrogel (Photograph and SEM image of In-Ch gel) Chapter 4. Palladium-Hydrogel Nanocomposite for C-C Coupling Reactions Supported metallic nanoparticles are important composite materials owing to their enormous potential for applications in various fields. This chapter describes the in situ formation of palladium nanoparticles in a calcium-cholate (Ca-Ch) hydrogel by reduction with sodium cyan borohydride. The hydrogel matrix appeared to assist the controlled growth as well as stabilization of palladium nanoparticles. The palladium nanoparticle/Ca-Ch hydrogel hybrid was characterized by scanning and transmission electron microscopy, atomic force microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. Furthermore, PdNP/Ca-Ch hybrid xerogel was shown to act as an active catalyst for Suzuki reaction under aqueous aerobic conditions, up to 4 cycles. This PdNP/Ca-Ch xerogel retained its catalytic activities on storage for several months. Scheme 5. Palladium-hydrogel nanocomposite for C-C coupling reactions in water Chapter 5. Sensitization of Terbium/Europium in self-assembled cholate hydrogel: An approach towards the detection of amine vapours "Luminescent" lanthanides have intrinsic low molar absorptivity, although this problem can be addressed by complexing the lanthanide ion with suitable chelating ligands which improve the luminescence properties drastically. However the design of such systems often involves careful planning and laborious synthetic steps. It is therefore desirable to have a simpler way to sensitize lanthanides with high efficiency. It was observed in our group that trivalent lanthanides formed hydrogels on the addition of sodium cholate. This chapter describes the discovery of the several biphenyl derivatives (such as 4-biphenylcarbaxaldehyde, 4-acetylbiphenyl) for sensitization of Tb(III) and Eu(III) in lanthanide hydrogels. Sensitization of Tb(III) and Eu(III) were observed by doping was characterized by scanning and transmission electron microscopy, atomic force microscopy, X-ray diffraction, and energy-dispersive X-ray spectroscopy. Furthermore, PdNP/Ca-Ch hybrid xerogel was shown to act as an active catalyst for Suzuki reaction under aqueous aerobic conditions, up to 4 cycles. This PdNP/Ca-Ch xerogel retained its catalytic activities on storage for several months. Scheme 6. Schematic representation of the sensitization process (the arrangement of themolecules in the gel fiber is arbitrary)(For figures pl refer the abstract pdf file)

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