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Les bactéries sont les organismes les plus abondants dans le monde. Des études sur les bactéries peuvent être bénéfiques pour la recherche médicale, la qualité des ressources en eau et l'industrie alimentaire. La détection et le marquage fluorescent est une des méthodes les plus utilisées pour des objectifs bioanalytiques. Dans la recherche de marqueurs luminescents et stables, des nouvelles nanoparticules fluorescentes et auto-stabilisées à base de polymères (FNPs, 60 nm) et des chaînes de polymères fluorescents (FPCs, 5nm) ont été développées. Dans un premier chapitre, une méthodologie pour insérer ces FNPs dans la bactérie E.coli a été développée. Pour contrôler si les FNPs sont en effet internalisé, nous avons développé un protocole basé sur l'extinction de luminescence des FNPs par le bleu de méthylène. Dans un second chapitre, les biotines conjuguées de FNPs peuvent être utilisées pour étudier les protéines membranaires spécifiques. En utilisant un lien streptavidine-biotine, un "sandwich" est formé pour construire un pont entre des particules, des anticorps spécifiques et des bactéries. Les images de fluorescence SPR et les images SEM ont démontré l'interaction de la biotine conjuguée de FNPs avec la bactérie E.coli. Dans un troisième chapitre, les chaînes de polymères fluorescents de couleur verte (GFPCs) peuvent facilement entrer dans des bactéries E.coli. Les GFPCs peuvent marquer le cyctoplasme mais pas l'ADN. Les chaînes de polymères fluorescents de couleur rouge (RFPCs) peuvent marquer facilement et efficacement la membrane de bactérie E.coli. Les deux FPCs sont extrêmement brillantes et non toxiques, les chaînes sont solubles dans l'eau. Ce sont de nouveaux matériaux fluorescents pour le marquage interne et externe des bactéries. Dans le dernier chapitre, il est démontré que les FANPs sont sensibles au pH et peuvent être utilisées pour mesurer la croissance de la bactérie E.coli. Les nano-objets détectent rapidement et précisément la croissance des cellules. En effet, leur fluorescence est sensible au changement de pH résultant du métabolisme cellulaire. De plus, ces particules permettent une surveillance en continu d'un grand nombre d'échantillons pour des applications de criblage à haut débit. Les nanomatériaux présentés dans ce manuscrit sont des outils prometteurs pour les applications en biocapteurs et bioimagerie en raison de leur luminosité/brillance et photostabilité élevées ainsi que les possibilités de post-fonctionnalisation. / Bacteria are the most abundant organisms in the world. Investigations and studies on bacteria can be beneficial to medical research, water resources research and food industry. Fluorescent sensing and labeling are commonly used for bioanalytical purposes. In the quest for very bright and stable labels, novel polymer-based, self-stabilized, fluorescent nanoparticles (FNPs, 60 nm) and fluorescent polymer chains (FPCs, 5 nm) have been developed. In the first part, a methodology to insert these FNPs into E.coli bacteria was developed. To control if the FNPs are indeed internalized, we developed a protocol based upon FNPs luminescence quenching by methylene blue. In the second part, a "sandwich" system is built. By using a streptavidin-biotin link, a bridge between particles (FNP), specific antibodies and bacteria is built. SPR, fluorescent images and SEM images demonstrated the interaction of biotin conjugated FNPs with E.coli bacteria. In the third part, interactions of fluorescent polymer chains with bacteria are investigated. Green fluorescent polymer chains (GFPCs) can easily enter into E.coli bacteria. GFPCs can label the cytoplasm but not the DNA. Red fluorescent polymer chains (RFPCs) can label the membrane of E.coli bacteria easily and efficiently. Both FPCs are highly water-soluble, bright and non-toxic, they are novel fluorescent labels for internal and external biological labeling of bacteria. In the last part, it is demonstrated that pH sensitive FANPs can be used to measure the growth of E.coli. They detect rapidly and accurately bacterial growth by signaling the change of pH resulting from cellular metabolism. Moreover, these particles allow for continuous monitoring a large number of samples for high-throughput screening applications. The studied fluorescent nanomaterials are promising tools for biosensing and bioimaging applications due to their brightness, high photostability and rich functionalisation ability.

The clinical management of cancer has principally relied upon surgery, radiation therapy, and chemotherapy for many decades. Despite recent advances in molecularly-targeted diagnostic and therapeutic agents, the long-term survival rates in patients with solid malignancies including ovarian cancer have improved only incrementally. Nanotechnologies designed to locally interrogate and modulate the tumor microenvironment offer a promising opportunity to enhance existing treatment modalities and establish new therapeutic paradigms. By virtue of their elemental composition, geometry, and surface chemistry, nanomaterials can be engineered with optical and pharmacokinetic properties which permit these agents to localize, fluoresce, and deposit energy within tumors. Nanomaterials therefore provide a clear route towards future approaches for sensitive diagnosis and imaging of tumors and targeted therapeutic delivery.

Philosophiae Doctor - PhD / There has been extensive growth in nanoscale technology in the last few decades to such a degree that nanomaterials (NMs) have become a constituent in a wide range of manufactured commercial and domestic products. This surge has resulted in uncertainties regarding their environmental impact, due to the significant increases in the amount of NMs released into the environment (Dowling et al., 2004) through intentional and unintentional releases. Like many other toxins, the aquatic environment is particularly vulnerable as it acts as a sink for nanoparticles (NPs) (Scown et al., 2010). The escalating growth of NMs has not advanced without efforts to understand its properties. Despite the dramatic advances in both the production and application of NMs, very little is known regarding their interaction with and effects on environmental and human health. Given the lack in scientific knowledge, particularly under various environmental conditions, it is often difficult to accurately assess the potential exposure pathways to ecological receptors of all NMs, silver nanoparticles (AgNPs) are the most widely used NPs, present in several consumer products mainly because of their anti-bacterial properties. It is estimated that the annual production exceeds 1000 tons/year (Piccinno et al., 2012). The increase uses of AgNPs in consumer products (e.g. textiles, cosmetics and personal hygiene), household appliances (e.g. washing machines and vacuum cleaners) and medical equipment have led to their increase release into the environment, thereby posing an environmental risk and human health concern. Silver NPs are known to induce the production of Reactive Oxygen Species (ROS) (Ahamed et al., 2010; Levard et al., 2012; Piao et al., 2011). Also since AgNPs are oxidized to ionic Ag (Ag+), it is still unclear whether the effects of ROS can be attributed to Ag+ release or to the AgNP itself (Fabrega et al., 2009; Miao et al., 2009). The behaviour of AgNPs is collectively influenced by inherent (nanoparticle size, shape, surface area, surface charge, crystal structure, coating, solubility/dissolution) and environmental factors (temperature, pH, ionic strength, salinity, organic matter). Climate change predictions indicate that the frequency, intensity and duration of extreme natural events (such as temperature elevations) will increase in the future (IPCC, 2001; IPCC, 2007). Global warming and climate change could increase atmospheric temperatures by 2.4 – 6.4 °C (IPCC, 2001; IPCC, 2007). The main feature associated with global climate change is the anticipation of wetter winters (i.e. increased flood events) and drier, warmer summers (i.e.extreme temperatures). These changes are likely to affect the inputs of contaminants into the environment as well as affect their behaviour, fate and transport, and toxicity in aquatic environments. It is known that the current temperature predictions in climate change scenarios could directly affect aquatic ecosystem communities (Carpenter et al., 1992), since temperature is also regarded as an important abiotic factor influencing growth and production of primary producers (i.e. algae, macrophytes etc.), and may also affect species distribution. For example, Liu et al. (2010) reported higher dissolution rates of AgNPs with increased temperature. Similarly, sudden hydrographic activity like high flood conditions may cause resuspension and redistribution of sediments. Few studies have linked the foreseeable climate change with contaminant release and ecosystem impacts. Similarly, few studies have analyzed the behaviour of NMs in the environment considering these predicted changes in mean temperatures. This thesis focuses on the effects of AgNPs on oxidative stress responses in the Cape River crab Potamonautes perlatus. The present work was undertaken to interpret the biological effects of AgNPs (< 100 nm) on P. perlatus, as well as to assess its effects under different environmental conditions. To understand the uptake, accumulation and biological effects of AgNPs, freshwater microcosms were produced to mimic a typical aquatic environment and temperature manipulated microcosms to which a commercially-available AgNP powder was added. Nanoparticles were characterized in the dry state and in suspension under different environmental conditions. Dissolution of total Ag was measured by inductively coupled plasma mass spectrometry (ICP-OES). Nanoparticle toxicity was assessed by measuring mortality and biomarkers of oxidative stress (CYP450, SOD, CAT, GST) evaluated in crab tissues. The overall results demonstrated that: (1) AgNPs may be transformed in both size and state under variable environmental conditions. The formation of smaller aggregates at higher temperatures suggests higher toxicity, (2) the release of free metal ions from NPs and NPs aggregates contribute to a higher toxicity towards aquatic organisms, (3) oxidative stress is a significant mechanism of AgNP toxicity and consequently enzymatic activation/inhibition with increasing AgNP concentration and temperatures, (4) oxidative stress responses to AgNPs particles were significantly modulated by temperature stress in P. perlatus, (5) mortality was observed from day 2 with maximum mortality achieved at day 7, (6) enzymes involved in detoxification, i.e. CYP450, has functional significance in the haemocytes, (7) P. perlatus has proved to be a significant target for AgNP exposure and, furthermore, has proved to be a suitable species to assess the ecotoxicity of AgNP in the aquatic environment, (8) antioxidant enzymes activities (are valuable tools to assess the oxidative status of crab tissues co-exposed to AgNPs and temperature. Furthermore, the results obtained in this study contributed to the understanding of the behaviour, bioavailability, uptake and toxicity of AgNPs under variable temperatures. / National Research Foundation (NRF) Thuthuka Fund and CSIR

Nanoscience and nanotechnology offer potential routes towards addressing critical issues such as clean and sustainable energy, environmental protection and human health. Specifically, metal and metal oxide nanomaterials are found in a wide range of applications and therefore hold a greater potential of possible release into the environment or for the human to be exposed. Understanding the aqueous phase behavior of metal and metal oxide nanomaterials is a key factor in the safe design of these materials because their interactions with living systems are always mediated through the aqueous phase. Broadly the transformations in the aqueous phase can be classified as dissolution, aggregation and adsorption which are dependent and linked processes to one another. The complexity of these processes at the liquid-solid interface has therefore been one of the grand challenges that has persisted since the beginning of nanotechnology. Although classical models provide guidance for understanding dissolution and aggregation of nanoparticles in water, there are many uncertainties associated with the recent findings. This is often due to a lack of fundamental knowledge of the surface structure and surface energetics for very small particles. Therefore currently the environmental health and safety studies related to nanomaterials are more focused on understanding the surface chemistry that governs the overall processes in the liquid-solid interfacial region at the molecular level. The metal based nanomaterials focused on in this dissertation include TiO2, ZnO, Cu and CuO. These are among the most heavily used in a number of applications ranging from uses in the construction industry to cosmetic formulation. Therefore they are produced in large scale and have been detected in the environment. There is debate within the scientific community related to their safety as a result of the lack of understanding on the surface interactions that arise from the detailed nature of the surfaces. Specifically, the interactions of these metal and metal oxide nanoparticles with environmental and biological ligands in the solutions have demonstrated dramatic alterations in their aqueous phase behavior in terms of dissolution and aggregation. Dissolution and aggregation are among the determining factors of nanoparticle uptake and toxicity. Furthermore, solution conditions such as ionic strength and pH can act as controlling parameters for surface ligand adsorption while adsorbed ligands themselves undergo surface induced structural and conformational changes. Because, nanomaterials in both the environment and in biological systems are subjected to a wide range of matrix conditions they are in fact dynamic and not static entities. Thus monitoring and tracking these nanomaterials in real systems can be extremely challenging which requires a thorough understanding of the surface chemistry governing their transformations. The work presented in this dissertation attempts to bridge the gap between the dynamic processing of these nanomaterials, the details of the molecular level processes that occur at the liquid-solid interfacial region and potential environmental and biological interactions. Extensive nanomaterial characterization is an integral part of these investigations and all the materials presented here are thoroughly analyzed for particle size, shape, surface area, bulk and surface compositions. Detailed spectroscopic analysis was used to acquire molecular information of the processes in the liquid-solid interfacial region and the outcomes are linked with the macroscopic analysis with the aid of dynamic and static light scattering techniques. Furthermore, emphasis is given to the size dependent behavior and theoretical modeling is adapted giving careful consideration to the details of the physicochemical characterization and molecular information unique to the nanomaterials.

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.

Transition metals complexes have been involved in various catalytic, biomedical and industrial applications, but only lately they have been associated with nanomaterials to produce innovative and well-defined new hybrid systems. The introduction of transition metals into nanomaterials is important to bear the advantages of metals to nanoscale and also to raise the stability of nanomaterials. In this dissertation, we study two approaches of associating transition metals into nanomaterials. The first approach is via spontaneous self-organization based assembly of small molecule amphiphiles and bulky hydrophilic polymers to produce organic-inorganic hybrid materials that have nanoscale features and can be precisely controlled depending on the experimental conditions used. These hybrid materials can successfully act as templates to design new porous material with interesting architecture. The second approach studied is via electroless reduction of transition metals on the surface of nanocarbons (nanotubes and nanodiamonds) without using any reducing agents or catalysts. The synthesis of these systems is highly efficient and facile resulting in stable and mechanically robust new materials with promising applications in catalysis.

<div>Multifunctional characteristics of Bismuth-based oxides offer great opportunities to design a variety of devices exploiting either a single functionality or the synergistic multifunctionalities. In the past decades, strain engineering of thin films arose as a solution for fabrication of novel structures with highly desired properties. In this thesis, strain engineering has been applied to Bismuth-based oxides to explore the strain effect on thin film structures and functionalities.</div><div>BiFeO₃ (BFO) servers as the first study platform, because of its strain-induced phase transition and the corresponding diverse polarization properties. The strain effect of SrRuO₃ (SRO)-buffered substrates on ferroelectric and optical properties of BFO thin films has been investigated. A wide range of strain states have been achieved in BFO films. The ferroelectricity and bandgap have been effectively tuned even with partial strain relaxation. However, pure BFO suffers from high leakage current and large coercive field. To overcome these limitations, Sm-doped BFO (BSFO) systems emerged and has been used in controlling the microstructure and properties of BFO. Our detailed structure analysis proves the Sm doping amount in BSFO thin films can be tuned effectively via deposition temperature. Consequently, the Sm dopant influences phase formation of BSFO and the macroscopic ferroelectric properties. </div><div>Another member in Bismuth-based oxide family, Bi₂WO₆ (BWO), has been selected as the base material for the design of the two-phase nanocomposites, because of its unique layered structure and ferroelectric property. To introduce ferromagnetic component into BWO, two methods have been explored. The first method incorporates Mn cations into the BWO matrix (BWMO), and the second method couples CoFe2O4 (CFO) as secondary phase with BWO to form a vertically aligned nanocomposite (VAN) system. Both systems exhibit robust ferromagnetic and ferroelectric response at room temperature and demonstrate their promise as room temperature multiferroics for future spintronics and memory applications. </div><div>The studies in this dissertation demonstrate the great structure flexibility and tunable functionalities of BFO and BWO systems. It shows the potential structure modification and property control of other Bi-based oxides. In the last chapter, new experimental plans and directions are proposed. The connections between the strain engineering and the tunable material properties are being built for various applications. </div><div><br></div>

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The demand for energy storage technologies is rapidly increasing in portable electronics, transportation, and renewable energy systems. Thus, the objective of this research is to develop and enhance the performance of Ni-based electrochemical supercapacitors by optimizing synthesis conditions and design of the electrode materials. Conventional and on-chip supercapacitors were developed with notable performance enhancement. For conventional supercapacitors, a uniform and conformal coating process was developed to deposit Ni(OH)2 nanoflakes on carbon microfibers in-situ by a simple chemical bath deposition at room temperature. The microfibers conformally-coated with Ni(OH)2 make direct physical contacts with essentially every single nanoflakes, leading to more efficient electron transport. Using this strategy, we have achieved devices that exhibit five times higher specific capacitance compared to planar (non-conformal) Ni(OH)2 nanoflakes electrodes prepared by drop casting of Ni(OH)2 on the carbon microfibers (1416 F/g vs. 275 F/g). For on-chip storage applications, microfabricated supercapacitors were developed using a combination of top-down photolithography and bottom-up CBD. The resulting Ni(OH)2 micro-supercapacitors show high-rate redox activity up to 500 V/s and an areal cell capacitance of 16 mF/cm2 corresponding to a volumetric stack capacitance of 325 F/cm3. This volumetric capacitance is 2-fold higher than carbon and metal oxide based micro-supercapacitors. Furthermore, these micro-supercapacitors show a maximum energy density of 21 mWh/cm3, which is superior to the Li-based thin film batteries. To enhance cycling stability, Ni-Cu-OH and Ni-Co-OH ternary electrodes have been prepared with different Ni:Cu and Ni:Co ratios by CBD at room temperature on carbon microfibers. It is observed that the electrodes with Ni:Cu and Ni:Co composition ratio of 100:10 results in an optimum capacitance and cycling stability. For the optimum composition, Ni-Co-OH with graphene and carbon nanofibers electrode was tested, with resultant improvement in electrode potential window, equivalent series resistance, and cyclic stability. To further increase energy density, Ni(OH)2//Graphene asymmetric supercapacitor were fabricated with areal capacitance of 253 mF/cm2 at 5 mA/cm2 which is higher than NiO//rGO prepared by hydrothermal method. Ni-Co-OH/G-CNF//Graphene asymmetric supercapacitor results in a maximum power of 23 mW within an operating voltage of 2.2 V which are higher than of Ni(OH)2//Graphene (15.94 mW within 1.8 V). Our asymmetric supercapacitors have flexible-electrodes, low-cost fabrication process and environmentally friendly materials.