In this thesis, gas sensors based on on-chip hydrothermally grown 1-D zinc oxide (ZnO) nanostructures are presented, to improve the sensitivity, selectivity, and stability of the gas sensors. Metal-oxide-semiconductor (MOS) gas sensors are well-established tools for the monitoring of air quality indoors and outdoors. In recent years, the use of 1-D metal oxide nanostructures for sensing toxic gases, such as nitrogen dioxide, ammonia, and hydrogen, has gained significant attention. However, low-dimensional nanorod (NR) gas sensors can be enhanced further. Most works synthesize the NRs first and then transfer them onto electrodes to produce gas sensors, thereby resulting in large batch-to-batch difference. Therefore, in this thesis six studies on 1-D ZnO NR gas sensors were carried out. First, ultrathin secondary ZnO nanowires (NWs) were successfully grown on a silicon substrate. Second, an on-chip hydrothermally grown ZnO NR gas sensor was developed on a glass substrate. Its performance with regard to sensing nitrogen dioxide and three reductive gases, namely, ethanol, hydrogen, and ammonia, was tested. Third, three 1-D ZnO nanostructures, namely, ZnO NRs, dense ZnO NWs, and sparse ZnO NWs, were synthesized and tested toward nitrogen dioxide. Fourth, hydrothermally grown ZnO NRs, chemical vapor deposited ZnO NWs, and thermal deposited ZnO nanoparticles (NPs) were tested toward ethanol. Fifth, the effect of annealing on the sensitivity and stability of ZnO NR gas sensors was examined. Sixth, ZnO NRs were decorated with palladium oxide NPs and tested toward hydrogen at high temperature. The following conclusions can be drawn from the work in this thesis: 1) ZnO NWs can be obtained by using a precursor at low concentration, temperature of 90 °C, and long reaction time. 2) ZnO NR gas sensors have better selectivity to nitrogen dioxide compared with ethanol, ammonia, and hydrogen. 3) Sparse ZnO NWs are highly sensitive to nitrogen dioxide compared with dense ZnO NWs and ZnO NRs. 4) ZnO NPs have the highest sensitivity to ethanol compared with dense ZnO NWs and ZnO NRs. The sensitivity of the NPs is due to their small grain sizes and large surface areas. 5) ZnO NRs annealed at 600 °C have lower sensitivity toward nitrogen dioxide but higher long-term stability compared with those annealed at 400 °C. 6) When decorated with palladium oxide, both materials form alloy at a temperature higher than 350 °C and decrease the amount of ZnO, which is the sensing material toward hydrogen. Thus, controlling the amount of palladium oxide on ZnO NRs is necessary.

L’objectif de cette thèse a été axé sur le développement des systèmes capable de répondre à des stimuli externes, basés sur des unités photochromiques. Le but d’une telle quête est d’augmenter la complexité des dispositifs et des machines moléculaires synthétiques. Avec l’objectif de développer des dispositifs et des machines artificiels plus complexes, nous avons réalisé de systèmes comprenant de multiples interrupteurs moléculaires. En vue de la réalisation de cette thèse, des nouveaux systèmes multi-photochromiques, où hybrides photochrome/nanomatériaux contenant des fragments azobenzène, diaryléthène ou spiropyrane ont été réalisés et étudiés. D’abord, on s’est focalisés sur des systèmes multi-azobenzènes capables de subir de grands réarrangements géométriques lors de la photoisomérisation, ils pourraient être utilisés à l'avenir comme éléments constitutifs des matériaux host-guest ou metal-organic frameworks contrôlables par des stimuli lumineux. Dans un second exemple, des commutateurs photochromiques de type dithiényléthène ont été utilisés pour déclencher l'émission d'une porphyrine. Cette dyade à montré une modulation réversible de son émission, affichant un contraste particulièrement élevé. Comme dernier exemple, un dérivé de spiropyrane a été combiné avec des nanoparticules d’or anisotropes. En induisant l'isomérisation de l’interrupteur moléculaire dans les dispersions colloïdales des nanorods d’or en liquide, nous avons visualisé une grande variation du spectre d'extinction des colloïdes, dépendante de la longueur d’onde du mode LSPR et du recouvrement spectrale avec le photoswitch. / The aim of this thesis has been to develop systems capable of responding to external stimuli, based on photochromic units. The goal of such a quest is to increase the complexity of devices and synthetic molecular machines. With the goal of developing more complex artificial devices and machines, we have realised systems containing multiple molecular switches. For the realisation of this thesis, new multi-photochromic systems, or photochromes/nanomaterials hybrids containing azobenzene, diarylethene or spiropyran moieties have been realised and studied. Firstly, we focused on multi-azobenzene systems capable of undergoing large geometric rearrangements during photoisomerisation, as they may be used in the future as constituent elements of host-guest or metal-organic frameworks controllable by luminous stimuli. In a second example, dithienylethene-type photochromic switches have been used to trigger the emission of a porphyrin. This dyad exhibited a reversible modulation of its emission, displaying a particularly highly contrasted response. As a final example, a spiropyran derivative has been combined with anisotropic gold nanoparticles. By inducing the isomerisation of the molecular switch in the AuNR colloidal liquid dispersions, we visualised a large variation of the colloid extinction spectrum, dependent on the LSPR mode wavelength and the spectral overlap with the photoswitch.

This thesis described the development of new strategies for the preparation of micro- and nano-structured polymer materials. In particular, this thesis focused on: i) the synthesis of polymer particles in microreactors, and ii) the self-assembly of inorganic nanorods. First, this thesis presented the synthesis of polymer particles and capsules with pre-determined sizes and narrow size distributions (CV<2%) in continuous microfluidic reactors. The method includes (i) the emulsification of monomers in a microfluidic flow-focusing device and (ii) in-situ solidification of droplets via photopolymerization. This microfluidic synthesis provides a novel strategy for the control over the shapes, compositions, and morphologies of polymer particles. In particular, we demonstrated the control over particle shapes by producing polymer ellipsoids, disks, rods, hemispheres, plates, and bowls. We produced polymer particles loaded with dyes, liquid crystals, quantum dots, and magnetic nanoparticles. We generated core-shell particles, microcapsules, Janus and three-phasic polymer particles. Control over the number of cores per droplet was achieved by manipulating the flow rates of liquids in the microchannels. We further investigated the hydrodynamic mechanism underlying the emulsification of droplets, which helps in guiding scientists and engineers to utilize this technique. Second, we described the self-assembly of inorganic nanorods by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polystyrene chains at both ends. We organized metal nanorods in structures with various geometries such as nanorings, nanochains, bundles, bundled nanochains, and nanospheres by tuning solely the quality of solvents. The self-assembly was tunable and reversible. This approach paved the way for the organization of anisotropic nanoparticles by using the strategies that are well-established for the self-assembly of block copolymers. We further described a systematic study of the self-assembly of polymer-tethered gold nanorods as a function of solvent composition in the system and the molecular weight of the polystyrene blocks. We found that the structure of the polymer pom-poms played an important role on the organization of polymer-tethered gold NRs. The 'supramolecular' assembly was governed by the competition between the end-to-end and side-by-side association of NRs and resulted in the controlled variation of the plasmonic properties of NRs, reflected in a 3-D plasmonic graph.

This thesis described the development of new strategies for the preparation of micro- and nano-structured polymer materials. In particular, this thesis focused on: i) the synthesis of polymer particles in microreactors, and ii) the self-assembly of inorganic nanorods. First, this thesis presented the synthesis of polymer particles and capsules with pre-determined sizes and narrow size distributions (CV<2%) in continuous microfluidic reactors. The method includes (i) the emulsification of monomers in a microfluidic flow-focusing device and (ii) in-situ solidification of droplets via photopolymerization. This microfluidic synthesis provides a novel strategy for the control over the shapes, compositions, and morphologies of polymer particles. In particular, we demonstrated the control over particle shapes by producing polymer ellipsoids, disks, rods, hemispheres, plates, and bowls. We produced polymer particles loaded with dyes, liquid crystals, quantum dots, and magnetic nanoparticles. We generated core-shell particles, microcapsules, Janus and three-phasic polymer particles. Control over the number of cores per droplet was achieved by manipulating the flow rates of liquids in the microchannels. We further investigated the hydrodynamic mechanism underlying the emulsification of droplets, which helps in guiding scientists and engineers to utilize this technique. Second, we described the self-assembly of inorganic nanorods by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polystyrene chains at both ends. We organized metal nanorods in structures with various geometries such as nanorings, nanochains, bundles, bundled nanochains, and nanospheres by tuning solely the quality of solvents. The self-assembly was tunable and reversible. This approach paved the way for the organization of anisotropic nanoparticles by using the strategies that are well-established for the self-assembly of block copolymers. We further described a systematic study of the self-assembly of polymer-tethered gold nanorods as a function of solvent composition in the system and the molecular weight of the polystyrene blocks. We found that the structure of the polymer pom-poms played an important role on the organization of polymer-tethered gold NRs. The 'supramolecular' assembly was governed by the competition between the end-to-end and side-by-side association of NRs and resulted in the controlled variation of the plasmonic properties of NRs, reflected in a 3-D plasmonic graph.

In this study, silver nanorods and nanospheroids were prepared both in aqueous solution and on the surface of glass slides through seed-mediated growth approach at room temperature and used as a surface enhanced Raman scattering (SERS) substrate. The synthesis of metallic nanorods was started with the production of silver nanospheres as seed utilizing sodium borohydride and trisodium citrate as reducing and capping agents, respectively. These seeds were then added to a growth solution containing additional silver salt, ascorbic acid and cetyltrimethylammonium bromide (CTAB.) Nanorod preparation conditions were first optimized in solution phase. The plasmon absorption of the formed nanocrystals was monitored by UV-Visible spectrometry. The largest red shift in the longitudinal plasmon resonance absorption of silver nanostructures was tried to be achieved in order to realize the highest electromagnetic enhancement in Raman measurements. The images of the formed nanorods were recorded using field emission scanning electron microscopy (FE-SEM). The optimized colloidal growth conditions were adopted for the growth of nanorods on the surface of the glass substrate. Sol-gel coated glass slides were used in order to increase the porosity on the surface for an effective seeding process. We reported the development of a novel SERS substrate prepared by growing silver nanorods directly on the surface of glass surface without using any linker molecule. The SERS performances of the nanorod growth surfaces were evaluated with crystal violet (CV), brilliant cresyl blue (BCB) and benzoic acid (BA). Some modifications such as the increase in the AgNO3 concentration in the growth solution and the addition of hydrocarbons to the growth solution were investigated for the enhancement of the SERS signal. The intense spectra obtained for the model compounds demonstrated the efficiency of the prepared substrate for the SERS enhancement and its potential as a SERS detection probe for chemical and biological analysis.

Existing methods of treating glioma are not effective for eradicating the disease. Therefore, new and innovative methods of treatment alone or in combination with existing therapies are necessary. Delivery of therapeutic agents through delivery carriers such as liposomes diminishes the harmful effects of the agent in healthy tissues and allows increased accumulation in the tumor. In addition, targeted chemotherapy using liposomes provides the opportunity for further increase in drug accumulation in tumor. However, the current targeting strategies suffer accelerated plasma clearance and are not advantageous in improving efficacy. The search for new tumor targets, novel ligands, new strategies for targeting, and particle stabilization will advance our ability to improve delivery at the tumor level while decreasing toxicity to normal tissues. The global objective of this thesis was to improve the status of current liposomal therapy to achieve higher efficacy in tumors. Here, we show a novel mechanism to increase targeting to tumor while uncompromising on the long circulation of stealth liposomes. Long circulation is essential for passive accumulation of the nanocarriers due to EPR effect, in order to see benefits of targeting. Using phage display technique, a variety of tumor specific peptides were identified for use as targeting moieties. One potential advantage of the approach proposed here is the rapid identification of patient tumor specific peptide that evades the RES. This could lead to the development of a nanocarrier system with high avidity and selectivity for tumors. Therefore, tumor accumulation of the targeted formulations will be higher than that of non‐targeted liposomes due to increased drug retention at the tumor site and uncompromised blood residence time.In addition, it has been shown that the distribution of nanocarriers, spatially within the tumor, is limited that might further hinder the distribution of the encapsulated drug, thereby limiting efficacy. It is necessary to release the drug from within the nanocarrier to promote increased efficacy. Here, we were able to address the problem of drug diffusion within the tumor interstitium using a combination therapy employing a remotely triggered thermosensitive liposomal chemotherapeutic. We fabricated a thermosensitive liposomal nanocarrier that maintained its stability at physiological temperature to minimize toxicity to healthy cells. We, then, showed a remote triggering mechanism mediated by gold nanorods heated via NIR can help in achieving precise control over the desired site for drug release. These strategies enabled increased drug availability at the tumor site and contributed to tumor retardation. Additionally, we show that the synergistic therapy employing gold nanorods and thermosensitive liposomes may have great potential to be translated to the clinic.

This work describes multiband photon detection techniques based on novel semiconductor device concepts and detector designs with simultaneous detection of dierent wavelength radiation such as UV and IR. One aim of this investigation is to examine UV and IR detection concepts with a view to resolve some of the issues of existing IR detectors such as high dark current, non uniformity, and low operating temperature and to avoid having additional optical components such as filters in multiband detection. Structures were fabricated to demonstrate the UV and IR detection concepts and determine detector parameters: (i) UV/IR detection based on GaN/AlGaN heterostructures, (ii) Optical characterization of p-type InP thin films were carried out with the idea of developing InP based detectors, (iii) Intervalence band transitions in InGaAsP/InP heterojunction interfacial workfunction internal photoemission (HEIWIP) detectors. Device concepts, detector structures, and experimental results are discussed. In order to reduce reflection, TiO2 and SiO2 nanostructured thin film characterization and application of these as anti-reflection coatings on above mentioned detectors is also discussed.

A novel localized surface plasmon resonance (LSPR) sensor that differentiates between background refractive index changes and surface-binding of a target analyte (e.g. a target molecule, protein, or bacterium) is presented. Standard, single channel LSPR sensors cannot differentiate these two effects as their design allows only one mode to be coupled. This novel technique uses two surface plasmon modes to simultaneously measure surface binding and solution refractive index changes. This increases the sensitivity of the sensor. Different channels or modes can be created in sensors with the introduction of gold nanospheres or gold nanorods that act as receptor mechanisms. Once immobilization was achieved on gold nanospheres, the technique was optimized to achieve the same immobilization for gold nanorods to get the expected dual mode spectrum. Intricate fabrication methods are illustrated with using chemically terminated self assembled monolayers. Then the fabrication process advances from chemically silanized nanoparticles, on to specific and systematic patterns generated with the use of Electron Beam Lithography. Comparisons are made within the different methods used, and guidelines are set to create possible room for improvement. Some methods implemented failed, but there was a lot to learn from these unsuccessful outcomes. Finally, the applications of the dual mode sensor are introduced, and current venues where the sensors can be used in chemical and biological settings are discussed.

The main objective of nanotechnology is to build self-powered nanosystems that are ultrasmall in size, exhibit super sensitivity, extraordinary multi functionality, and extremely low power consumption. As we all know that 21st century has brought two most important challenges for us. One is energy shortage and the other is global warming. Now to overcome these challenges, it is highly desirable to develop nanotechnology that harvests energy from the environment to fabricate self-power and low-carbon nanodevices. Therefore a self-power nanosystem that harvests its operating energy from the environment is an attractive proposition. This is also feasible for nanodevices owing to their extremely low power consumption. One advantageous approach towards harvesting energy from the environment is the utilization of semiconducting piezoelectric materials, which facilitate the conversion of mechanical energy into electrical energy. Among many piezoelectric materials ZnO has the rare attribute of possessing both piezoelectric and semiconducting properties. But most applications of ZnO utilize either the semiconducting or piezoelectric property, and now it’s time to fully employ the coupled semiconducting-piezoelectric properties to form  the basis for electromechanically coupled nanodevices. Since wurtzite zinc oxide (ZnO) is structurally noncentral symmetric and has the highest piezoelectric tensor among tetrahedrally bonded semiconductors, therefore it becomes a promising candidate for energy harvesting applications. ZnO is relatively biosafe and biocompatible as well, so it can be used at large scale without any harm to the living environment. The synthesis of another transition metal oxide known as Co3O4 is also important due to its potential usage in the material science, physics and chemistry fields. Co3O4 has been studied extensively due to low cost, low toxicity, the most naturally abundant, high surface area, good redox, easily tunable surface and structural properties. These significant properties enable Co3O4 fruitful for developing variety of nanodevices. Co3O4 nanostructures have been focused considerably in the past decade due to their high electro-chemical performance, which is essential for developing highly sensitive sensor devices. I started my work with the synthesis of ZnO nanostructures with a focus to improve the amount of harvested energy by utilizing oxygen plasma treatment. Then I grow ZnO nanorods on different flexible substrates, in order to observe the effect of substrate on the amount of harvested energy. After that I worked on understanding the mechanism and causes of variation in the resulting output potential generated from ZnO nanorods. My next target belongs to an innovative approach in which AFM tip decorated with ZnO nanorods was utilized to improve the output energy. Then I investigated Co3O4 nanostructures though the effect of anions and utilized one of the nanostructure to develop a fast and reliable pH sensor. Finally to take the advantage of higher degree of redox chemistry of NiCo0O4 compared to the single phase of nickel oxide and cobalt oxide, a sensitive glucose sensor is developed by immobilizing glucose oxidase. However, there were problems with the mechanical robustness, lifetime, output stability and environmental adaptability of such devices, therefore more work is going on to find out new ways and means in order to improve the performance of fabricated nanogenerators and sensors.

[Truncated abstract] This work was concerned with investigations into the synthesis of Ce(OH)4, Sm(OH)3 and hydrated Ce-Sm mixed oxide nanoparticles with anisotropic morphologies via a chemical precipitation technique. The effect of various experimental parameters including temperature, aging time, ionic environment and thermal treatment on the morphology, structure of nanoparticles as well as elemental homogeneity of the mixed oxide nanoparticles was emphasised. It was shown that different experimental conditions resulted in different particle morphologies. This suggested that by tuning experimental parameters an ultimate goal of nanotechnology, the formation of nanoparticles with desired morphologies and sizes, may be achieved. It was found that by modifying experimental parameters it was possible to influence the development of various morphological and structural characteristics of Ce(OH)4 nanoparticles. The resulting morphologies were fibrous needle-like, rod-like and nanowire particles of various sizes. Characterisation of the nanoparticles was conducted through analysis by X-ray diffraction, surface area analysis and transmission electron microscopy techniques. Investigations into the structure of the hydrated CeO2 nanoparticles were undertaken since it is considered to be a key to the relevant properties of the material. The structure was found to exhibit multiple twinning phenomenon with 5-fold symmetry, with a consequence that atomic planes formed the particle surface. However, upon thermal treatment of needle-like particles, structural transformation was observed that possibly led to the development of more reactive and particle circumferential facets. A structural model and formation mechanism of such structures was proposed. ... A preliminary study into suitability of particle anisotropic morphology for compaction and densification processes was undertaken. Investigations into the sintering behaviour of the particles with anisotropic morphology were conducted on ceria nanoneedles. It was found that these particles displayed favourable sintering characteristics. The final densities of the hydrated ceria needle-like particle samples were achieved as high as 94.1% of the theoretical density after sintering at 1100°C for 5 hours.