Collective oscillation of conduction electrons in metallic nanoparticles known as localized surface plasmon resonance has been studied for nano-optics applications. The excitation of localized surface plasmons on nano-structured metal material leads to strong light scattering and absorption. Since the localized surface plasmon resonance is strongly dependent on the shape, size, size distribution, and dielectric property of surrounding environment of nano-structured metal, the dependence can be applied in wide applications. However, the direct and non-destructed observation of nano-structured metal is required to the development of nano-technology, we proposed a real time optical observation due to the optical respons of metal nano-particles system. Furthermore, we proposed a fast and simple method to fabricate a high order metal nano-particles array and used liquid crystal material to directly modulate the surface plasmon effect on the metal nanoparticles. The purpose of this work is to study the surface plasmon effect excited on metal nanoparticles. These works are described as follows: A. The topic of the first work is ¡§Real time absorbance spectra due to optical dynamics of silver nano-particles film¡¨, we report the real time absorbance spectra due to optical dynamics of silver nano-particles film under a heating treatment from 28 to 300 ¢J. A 7nm-thicked sliver film was thermally deposited on an indium tin oxide glass substrate. In the process of heating, the real time absorbance spectra of silver nano-particles film were measured by an optical spectrometer. It was noted that the absorbance spectra of the film varied with the heat-treating temperature and time. The peak position in the spectra curve shifted to shorter wavelength below the temperature of 250 ¢J, then shifted to red band due to higher temperature treatment. With the comparison of scanning electron micrograph analysis, the real time absorbance spectra exhibited a particular optical property confirmed by the dynamic dark-field optical microscopy system. The real-time absorbance spectra and dark-field micrographs analyses lead to a direct and non-destructed observation of growing evolution of metal nano-particles. B. The topic of the second work is ¡§Laser pulse induced gold nanoparticles grating¡¨. We report the results of our experimental investigation of laser induced gold nano-particle gratings and their optical diffraction properties. A single shot of a pair of Nd-YAG laser pulses of the same polarization is directed toward a thin gold film of thickness 6 nm on a substrate of polymethyl methacrylate (PMMA). As a result of the laser illumination, the thin gold film is fragmented into an array of nano-particles. Using scanning electron and dark-field optical micrographs, we discovered that the morphology of the gold nanoparticles grating is dependent on the fluence of laser pulse. The spectrum of first order diffraction shows a spectral dependence, possibly due to the presence of the nano-particles of various sizes. The ablation of thin films of nano-thickness via the use of laser pulses may provide a simple and efficient method for the fabrication of nano-scale structures, including 2D arrays of nano-particles. C. The topic of the second work is ¡§Surface plamons induced extra diffraction band of cholesteric liquid crystal grating¡¨. We investigated the diffraction behavior of cholesteric liquid crystal (CLC) grating with the surface plasmon effect was investigated. One indium-tin-oxide plate of the CLC grating cell was covered with silver nanoparticles. With the application of a proper voltage, a well formed phase grating was constructed in the CLC cell. The CLC grating was probed by a beam of the polarized-monochromatic light, and the wavelength range was from 450 to 700 nm. It was shown that an extra first-order diffraction band was observed around 505 nm. The physical reason of the extra diffraction band could be the surface plasma effect emerged from silver nanoparticles. The extra diffraction band due to the surface plasmon effect can offer potential applications in nano-optics, such as the optical switch function.

SERS

This thesis presents spectroscopic studies of metallic nanoparticle localized surface plasmons and plasmon enhanced fluorescence. We investigated the dielectric sensitivity of silver nanoprisms to an external electric field and gold nanorods to the formation of a self-assembled surface monolayer. Dark field microscopy was used to image plasmonic scattering from single nanoparticles, and a liquid crystal tunable filter was used to construct corresponding spectra. The plasmon resonances of silver nanoprisms displayed both reversible red shifts and irreversible blue shifts along with drastic intensity changes upon exposure to an applied bias. The plasmon resonances of gold nanorods showed sensitivity to the presence of alkanethiol molecules adhered to the particle surface by a moderate red shift. An increase in the effective external dielectric caused a shift toward longer wavelengths. We imaged plasmon enhanced fluorescence in order to optimize experimental parameters for a developing project that can characterize nanoparticle structure on sub-wavelength dimensions. Preliminary controls were performed to account for the effect of O₂ plasma treatment, solvent and alkanethiol monolayer formation on surface plasmon resonances. We found that O₂ plasma treatment for different time intervals did not result in a plasmon shift compared to untreated nanoparticles exposed to N₂; however when exposed to solvent the surface plasmons of the treated particles shifted five times as far toward the red. Interestingly, the solvent effect only resulted in a plasmon shift when the particles were N₂ dried after solvent incubation. Gold nanorods incubated in ethanol showed no wavelength maximum shift in pure solvent over time, but shifted moderately to the red after incubation in a solution of alkanethiol molecules. Conditions for the plasmon enhanced fluorescence study were optimized using a dye conjugate of the same alkanethiol molecule used previously by formation from solution in a monolayer on the gold nanorod surface. The appropriate synthesis for dye functionalization, molecular concentrations, solvents and optical settings were determined. / text

With a number of advantages newly recognized, use of surface-coated nanoparticles is being proposed for various upstream oil applications, such as for Enhanced Oil Recovery or as nanosensors. The first requirement for many of these applications is the ability to transport the nanoparticles a desired distance from the injection well. It means the particles should exhibit little retention in sedimentary rocks and minimal formation damage. Also, a certain amount of particles should adsorb at target locations such as water/oil interfaces for response measurement, if they are used as nanosensors. Three kinds of nanoparticle dispersions are tested for coreflood experiment in sedimentary rock cores: silica nanoparticles, commercial iron-oxide nanoparticles, and in-house synthesized paramagnetic nanoparticles. The quantitative retention measurements from corefloods offer insight into the mechanisms for nanoparticle transport in various sedimentary rocks (Boise sandstone, layered-Berea sandstone and Texas Cream limestone), and also with and without oil in the core. The coreflood experiments helped to develop a procedure to identify efficiently a surface coating to a given nanoparticle, that will allow both long-term dispersion stability and long-distance transportability in a given reservoir rock. To achieve this objective, seventy-six coreflood experiments were conducted to investigate transport of nanoparticles at rock grain surface and at water/oil interface. The parameters analyzed in this dissertation are: dialysis of the nanoparticle dispersion; cross-linking of polymer on coating; hydrophobicity/hydrophilicity of surface coating; oil type; nanocluster size; flow velocity; pH; ionic strength; rock lithology; and injected nanoparticle concentration. Our results show that surface coating, ionic strength, and specific surface/interfacial area were dominant factors for nanoparticle retention at rock grain surface and water/oil interface. Nanoparticle retention concentration (adsorption density) at rock grain surface decreases with decrease in nanocluster size and increase in flow velocity. Some retained nanoparticles can be recovered by increasing flow velocity or decreasing ionic strength. It indicates that the nanoparticle retention at the rock grain surface is unlike the generally irreversible adsorption of surfactant or polymer molecules. Ionic strength affects both reversible and irreversible adsorption of nanoparticles at rock grain surface; in these corefloods the irreversible retention is mainly due to the instability of nanoparticle dispersion and subsequent aggregation under high salinity conditions. The nanoparticle synthesis method, whether dialyzed or not, and cross-linking of coating polymer, all have significant impact on dispersion stability, especially for aqueous dispersion with high ionic strength. Nanoparticle adsorption at water/oil interface can be increased by increasing hydrophobicity of surface coating, or to a certain extent by increasing ionic strength of dispersion. / text

We present experimentally determined photodisruption enhancement of 50 nm gold spheres irradiated with 780 nm 180 fs pulses using a pump-probe scattering system. Our results indicate a 300 nm cavitation bubble threshold reduction of 31 times when compared to an ultra-pure water base control solution. We utilize a method of matching time between bubble initiation in a continually circulated nanoparticle solution with theoretical focal volume size dependent time between particle-focal volume collision events based on simple particle kinetics. We propose the observed photodisruption is due to electrostatic particle ablation kinetics due to electron photoemission. We apply the Fowler-Dubridge theory for photoemission to nanospheres experiencing strong near-field enhancement to describe particle electric fields induced by non-zero particle charge densities resulting from emitted electrons. An apparent ultra-energy efficient photodisruption mechanism results from multiphoton emission processes in the sub 100 femtosecond pulse regime exceeding typical methods utilizing explosive boiling. In the process of explaining experimental results, we develop a near complete picture of nanoparticle mediated photodisruption as a function of identified relevant system non-dimensional groups and particle enhancement. These results may be used to guide the selection of laser and particle parameters for imaging and different photodisruption regimes. / text

This thesis presents an experimental study of the effect that particle size and shape have on nanoparticle magination and adhesion propensity in micro-capillaries. With the use of half elliptical cross-section microfluidic channels that were fabricated using photolithography as well as wet and dry etching techniques and geometrically mimetic of human microcirculation, particles ranging from 93 to 970 nm were flown and imaged individually adhering to the channel walls. The results show a significant increase in particle adhesion below 200 nm as well as the emergence of a critical particle diameter above which no particle adherence was observed. The volume delivery efficiency was also shown to increase below 200 nm, providing insight for the rational design of nanocarriers for targeted cancer therapeutics. / text

DNA vaccines offer unique promise as a means of generating immunity against infectious and malignant disease. Unfortunately a number of obstacles, including rapid degradation of naked plasmid DNA (pDNA), poor cellular uptake by antigen presenting cells (APCs) and subsequent low levels of gene expression have limited the ability of DNA vaccines to raise sufficient immune responses towards the target antigen. This thesis is focused on investigating the immunostimulatory potential of liposomal nanoparticulate (LN) formulations of pDNA (stabilized plasmid lipid particles; SPLP) and cytosine-guanine oligodeoxynucleotides (CpG-ODN; LN CpG-ODN), and examining their ability to act together as a non-viral DNA vaccine in attempt to address the shortcomings of current DNA vaccine approaches. One focus of this thesis concerns investigating the immunostimulatory activity of LN formulations of CpG-ODN and pDNA. It is shown that despite dramatic differences in pharmacokinetics and biodistribution of LN CpG-ODN following intravenous (i.v.) and subcutaneous (s.c.) administration the resultant immune response is very similar, which is concluded to be due to the intrinsic ability of APCs to sequester LN CpG- ODN. In addition, it is demonstrated that lipid encapsulation dramatically enhances the immunostimulatory potential of pDNA and it is observed that SPLP maintains immunostimulatory activity in Toll-like receptor 9 (TLR9) knock-out mice. Together theses findings highlight the need for DNA-based therapies to consider both TLR9-dependent and -independent immunostimulatory activities of pDNA when constructing non-viral vectors. Furthermore, a new role for SPLP as a non-viral gene delivery vehicle for the generation of a systemically administered genetic vaccine in the presence of LN CpG-ODN is introduced. The ability of vaccination with SPLP to act prophylactically, to protect mice from tumour challenge, and therapeutically, in a novel vaccination strategy where the antigen is expressed at the tumour site as a result of SPLP-mediated transfection, is explored, demonstrating that in the presence of LN CpG-ODN SPLP possesses potential as a non-viral delivery system for DNA-based cancer vaccines. In summary, this work represents a substantial advance in the understanding of the immunostimulatory potential of both SPLP and LN CpG-ODN and provides insight into their ability to work together as a non-viral DNA vaccine.

Nanomaterial toxicity is a major concern and could potentially hamper the progress of biomedical nanotechnology development. Dispelling these concerns requires that the consequences of nanomaterial exposure are evaluated, and the findings will determine whether developmental hurdles can be overcome. This thesis evaluates the both in vivo and in vitro impact of quantum dots (QD , zinc sulphide capped cadmium selenide semiconductor nanocrystals) a fluorescent nanoparticle label with potential as an optical in vivo imaging agent. This work reviews nanoparticle characterization techniques and their importance to biological responses, and surveys QD interactions both in vivo and in vitro. We collected pharmacokinetic and toxicity data by a) quantitatively surveying the in vivo absorption, distribution , metabolism and excretion of QDs, and b) measuring the impacts of QDs on relevant organs (in vivo) and cells (in vitro). Neither of these areas had been explored when this thesis was started. In vivo, intravenous QD dosing in Sprague-Dawley rats showed uptake into reticuloendothelial cells with surface coating dependent kinetics, slow degradation, no excretion detected in feces or urine, and no indications of toxicity. The liver took up the majority of dose after 90 minutes and small amounts of QDs appeared in the spleen, kidney, and bone marrow. After 30 days, the cadmium concentration in the kidneys increased to 3µg/g without a proportional amount of zinc, indicating QD breakdown. In vitro we noted phagocytic capacity comparable to in vivo results, QD breakdown, and a retention of normal macrophage function thereby demonstrating that primary rat liver macrophages (Kupffer cells) are an appropriate in vitro system with which to investigate the cellular responses to quantum dots. Such an in vitro model will facilitate faster evaluation of individual nanotechnologies intended for in vivo use. This dissertation addresses a lack of in vivo background information needed to understand the consequences of QD exposure; though QD fail to demonstrate pharmacokinetics desirable for in vivo imaging agents, they are not toxic. Importantly, we provide in vitro data that will lead to the development of accurate and efficient in vitro primary screening methods that will be central to the further development of biomedical nanotechnologies.

Nanomaterial toxicity is a major concern and could potentially hamper the progress of biomedical nanotechnology development. Dispelling these concerns requires that the consequences of nanomaterial exposure are evaluated, and the findings will determine whether developmental hurdles can be overcome. This thesis evaluates the both in vivo and in vitro impact of quantum dots (QD , zinc sulphide capped cadmium selenide semiconductor nanocrystals) a fluorescent nanoparticle label with potential as an optical in vivo imaging agent. This work reviews nanoparticle characterization techniques and their importance to biological responses, and surveys QD interactions both in vivo and in vitro. We collected pharmacokinetic and toxicity data by a) quantitatively surveying the in vivo absorption, distribution , metabolism and excretion of QDs, and b) measuring the impacts of QDs on relevant organs (in vivo) and cells (in vitro). Neither of these areas had been explored when this thesis was started. In vivo, intravenous QD dosing in Sprague-Dawley rats showed uptake into reticuloendothelial cells with surface coating dependent kinetics, slow degradation, no excretion detected in feces or urine, and no indications of toxicity. The liver took up the majority of dose after 90 minutes and small amounts of QDs appeared in the spleen, kidney, and bone marrow. After 30 days, the cadmium concentration in the kidneys increased to 3µg/g without a proportional amount of zinc, indicating QD breakdown. In vitro we noted phagocytic capacity comparable to in vivo results, QD breakdown, and a retention of normal macrophage function thereby demonstrating that primary rat liver macrophages (Kupffer cells) are an appropriate in vitro system with which to investigate the cellular responses to quantum dots. Such an in vitro model will facilitate faster evaluation of individual nanotechnologies intended for in vivo use. This dissertation addresses a lack of in vivo background information needed to understand the consequences of QD exposure; though QD fail to demonstrate pharmacokinetics desirable for in vivo imaging agents, they are not toxic. Importantly, we provide in vitro data that will lead to the development of accurate and efficient in vitro primary screening methods that will be central to the further development of biomedical nanotechnologies.

In this thesis, three different read-out techniques for biomolecular recognition have been studied. All three techniques rely on the change in dynamic behaviour of probe functionalised magnetic beads after binding to a biomolecular target complementary to the probe. In the first technique presented, the sample is exposed to an AC magnetic field while the response to this field is probed using a laser source and a photodetector positioned at opposite sides of the sample. Beads bound to the target entity will experience an increase in their hydrodynamic volume, and will not be able to respond as rapidly to an alternating field as free beads. Here, the target entity is either DNA coils formed by rolling circle amplification or biotinylated bovine serum albumin (bBSA). The change in dynamic behaviour is measured as a frequency dependent modulation of transmitted light. Limit of detections (LODs) of 5 pM DNA coils originating from a V. cholerae target and 100 pM of bBSA have been achieved. In the second technique presented, the beads are magnetically transported across a probe functionalised detection area on a microchip. Beads bound to a target will be blocked from interaction with the detection area probes, whereas in the absence of a target, beads will be immobilised on the detection area. The LOD of biotin for this system proved to be in the range of 20 to 50 ng/ml. In the third technique presented, the sample is microfluidically transported to a detection area on a microchip. The read-out is performed using a planar Hall effect bridge sensor. A sinusoidal current is applied to the bridge in one direction and the sensor output voltage is measured across the sensor in the perpendicular direction. The AC current induced bead magnetisation contributing to the sensor output will appear different for free beads compared to beads bound to a target. LODs of 500 B. globigii spores and 2 pM of V. cholerae DNA coils were achieved. From a lab-on-a-chip point of view, all three techniques considered in this thesis show promising results with regards to sensitivity and integrability.