In this work, functional plasmonic nanocircuitry is examined as a key of revolutionizing state-of-the-art electronic and photonic circuitry in terms of integration density and transmission bandwidth. In this context, numerical simulations enable the design of dedicated devices, which allow fundamental control of photon flow at the nanometer scale via single or multiple plasmonic eigenmodes. The deterministic synthesis and in situ analysis of these eigenmodes is demonstrated and constitutes an indispensable requirement for the practical use of any device. By exploiting the existence of multiple eigenmodes and coherence - both not accessible in classical electronics - a nanoscale directional coupler for the ultrafast spatial and spatiotemporal coherent control of plasmon propagation is conceived. Future widespread application of plasmonic nanocircuitry in quantum technologies is boosted by the promising demonstrations of spin-optical and quantum plasmonic nanocircuitry. / In dieser Arbeit werden funktionelle plasmonische Schaltkreise als Schlüssel zur Revolutionierung modernster elektronischer und photonischer Schaltkreise in Bezug auf deren Integrationsdichte und Übertragungsbandbreite untersucht. Mit Hilfe numerischer Simulationen werden Bauelemente speziell für die Steuerung des Photonenflusses im Nanometerbereich mittels einzelner bzw. mehrerer plasmonischer Eigenmoden konzipiert. Die deterministische Synthese und Analyse solcher Eigenmoden wird aufgezeigt und stellt eine unverzichtbare Voraussetzung für die praktische Anwendung eines jeden Nanoschaltkreises dar. Durch die Existenz mehrerer Eigenmoden und Kohärenz - beide in der klassischen Elektronik nicht zugänglich - lässt sich ein nanoskaliger Richtkoppler für die ultraschnelle räumliche und räumlich-zeitliche kohärente Kontrolle der Plasmonenausbreitung entwerfen. Künftig werden plasmonische Schaltkreise aufgrund der vielversprechenden Demonstrationen von spinoptischen und quantenplasmonischen Schaltkreisen in Quantentechnologien weite Verbreitung finden.

The purpose of this study was to prepare concentrated and stable gold colloids for the enhancement of the signal response of the SPR technique for detecting small molecules such as progesterone. The gold colloids developed in this study were prepared by hydrazine hydrate, sodium borohydride, and tri-potassium citrate reduction routes. The study revealed that the sodium borohydride reduced gold colloids were extremely stable and it was able to be utilised in the progesterone immunoassay developed previously by Mitchell et al. The experiment was carried out on BIAcore 3000 using two different sensor surfaces (CM5 and SAM). The results showed that the enhancement species prepared from the borohydride-reduced gold colloids were able to improve the SPR signal response by 13 times higher than SPR signal produced without the enhancement species on the CM5 surface. The signal enhancement on the SAM surface using the same enhancement species was even greater at 29 times higher. The sensitivity of the assay was, however, unable to be determined due to time constraint. The limit of detection (LOD) of the progesterone assay using the CM5 chip was estimated to be ca. 5-20 pg/mL. Whilst for the SAM chip, the LOD of the progesterone assay was estimated to be ca. 5-20 fg/mL. Further work is required to confirm these estimated LOD values.

The interactions of biomolecules and cells at solid-liquid interfaces play a pivotal role in a range of biomedical applications and have hence been studied in detail. An improved understanding of these interactions results in the ability to manipulate biomolecules and concurrently cells spatially and temporally at surfaces with high precision. Spatial control can be achieved using patterned surface chemistries whilst temporal control is achieved by switchable surfaces. The combination of these two surface properties offers unprecedented control over the behaviour of biomolecules and cells at the solid-liquid interface. This is particularly relevant for cell microarray applications, where a range of biological processes must be duly controlled in order to maximise the efficiency and throughput of these devices. Of particular interest are transfected cell microarrays (TCMs), which significantly widen the scope of microarray genomic analysis by enabling the high-throughput analysis of gene function within living cells Initially, this thesis focuses on the spatially controlled, electro-stimulated adsorption and desorption of DNA. Surface modification of a silicon chip with an allylamine plasma polymer (ALAPP) layer resulted in a surface that supported DNA adsorption and sustained cell attachment. Subsequent high density grafting of poly(ethylene glycol) (PEG) formed a layer resistant to biomolecule adsorption and cell attachment. PEG grafted surfaces also showed significantly reduced attachment of DNA with an equilibrium binding constant of 23 ml/mg as compared with 1600 ml/mg for ALAPP modified surfaces. Moreover, both hydrophobic and electrostatic interactions were shown to contribute to the binding of DNA to ALAPP. Spatial control over the surface chemistry was achieved using excimer laser ablation of the PEG coating which enabled the production of patterns of re-exposed ALAPP with high resolution. Preferential electro-stimulated adsorption of DNA to the ALAPP regions and subsequent desorption by the application of a negative bias was observed. Furthermore, this approach was investigated for TCM applications. Cell culture experiments demonstrated efficient and controlled transfection of cells. Electro-stimulated desorption of DNA was shown to yield enhanced solid phase transfection efficiencies with values of up to 30%. The ability to spatially control DNA adsorption combined with the ability to control the binding and release of DNA by application of a controlled voltage enables an advanced level of control over DNA bioactivity on solid substrates and lends itself to biochip applications. As an alternative approach to surface patterning, the fabrication and characterisation of chemical patterns using a technique that can be readily integrated with methods currently used for the formation of microarrays is also presented. Here, phenylazide modified polymers were printed onto low fouling ALAPP-PEG modified surfaces. UV irradiation of these polymer arrays resulted in the crosslinking of the polymer spots and their covalent attachment to the surface. Cell attachment was shown to follow the patterned surface chemistry. Due to the use of a microarray contact printer it was easily possible to deposit DNA on top of the polymer microarray spots. A transfected cell microarray was generated in this way, demonstrating the ability to limit cell attachment to specific regions and the suitability of this approach for high density cell assays. In order to allow for the high-throughput characterisation of the resultant polymer microarrays, surface plasmon resonance imaging was utilised to study the adsorption and desorption of bovine serum albumin, collagen and fibronectin. This analysis enabled insights into the underlying mechanisms of cell attachment to the polymers studied. For the system analysed here, electrostatic interactions were shown to dominate cellular behaviour.

Etude de matériaux nanostructurés préparés par faisceaux d'ions

In this thesis, we present a systematic investigation of the static and dynamic response properties of low-dimensional systems, using a variety of theoretical techniques ranging from time dependent density functional theory to the recursive Green's function method. As typical low-dimensional systems, metal nanostructures can strongly interact with an electric field to support surface plasmons, making their optical properties extremely attractive in both fundamental and applied aspects. We have investigated the energy broadening of surface plasmons in metal structures of reduced dimensionality, where Landau damping is the dominant dissipation channel and presents an intrinsic limitation to plasmonics technology. We show that for every prototype class of systems considered, including nanoshells, coaxial nanotubes, and ultrathin films, Landau damping can be drastically tuned due to energy quantization of the individual electron levels and e-h pairs. Both the generic trend and oscillatory nature of the tunability are in stark contrast with the expectations of the semiclassical surface scattering picture. For a more realistic environment of low-dimensional systems, the effect of a dielectric substrate is considered to mimic the experimental setup. We have studied the dispersion of various plasmon excitations in metal thin films with growth substrates. Our results qualitatively reproduce the experimentally observed plasmon spectra of the Mg/Si systems. The underlying physics for the formation of various absorption peaks can be understood with a simple hybridization concept. Based on this concept, the coexistence of surface and bulk plasmons in experimental observation turns out to be a clear evidence for the existence of multiple-multipole surface plasmons due to the quantum confinement in thin films. To step into more confined worlds, we choose the real two-dimensional material graphene as our representive system, which is a semi-metal with zero band-gap. As the first step, the static electric response of graphene is investigated by exploring its transport properties. We have studied the pseudospin valve effect in bilayer graphene nanoribbons. The pseudospin degree of freedom is associated with the electron density in two layers and can be controlled by external gate electrodes. We find that the conductance of nanoribbons shows different behaviors compared with infinite systems due to the appearance of edge states and quantum confinement. Remarkably, a large on-off ratio can be achieved in nanoribbons with zigzag edges, even when the Fermi energy lies in the bulk energy gap. The influence of possible edge vacancies and interface conditions is also discussed. Finally, we discuss the possibility of using plasmon excitations to detach the graphene from its growth substrate, where the dynamic electric response of the graphene-metal system is expected to play a central role.

Antithrombin (AT) is one of the most important anticoagulant factors in the blood, and its effects are increased by the interaction with glycosaminoglycans, especially heparin. AT appears in two additional variants, other than the native form, and those variants have antiangiogenic properties and also bind to heparin. AT is found in two distinct isoforms (alfa, beta) where the difference lie in the degree of glycosylation. This project has shown interesting results regarding the dependence of calcium ions on the binding between heparin and antithrombin. The results show that the beta-isoform increases its affinity for heparin in the presence of calcium in contrast to the alfa-isoform, which shows a decrease in the heparin affinity under the same conditions. This project has also given results that after further investigation and development could be used for an improved set-up of the immobilisation of AT variants in a surface plasmon resonance system. The results show that immobilisation of a protein in the reference channel gives a better shielding effect between the negatively charged heparin molecules and the negatively charged dextran matrix. Furthermore a more significant difference was seen between the two heparin moieties used during binding affinity studies, especially for native AT.

Heat shock protein 70 (HSP70) is an important health related biomarker, being implicated as an early stage cancer marker and as an indicator of cardiac health. It also has important implications in wildlife environmental monitoring, as its levels can be affected by food deprivation, elevated temperatures, and pollution. Therefore, the use of HSP70 as a biomarker is highly desirable, yet the current methods of quantifying HSP70 are time consuming, expensive, and require dedicated labs. In order to facilitate widespread use of the HSP70 biomarker, a quantification tool that can be used at the point-of-care is needed. This implies the development of a simple and inexpensive HSP70 biosensing technique that is highly sensitive and selective. Therefore, in this work a label-free HSP70 biosensor has been designed based on the optical properties of gold nanoparticles (NPs). Gold NPs exhibit a large absorbance peak in the visible spectrum due to localized surface plasmon resonance (LSPR). The peak position is dependent on the local refractive index, which can be employed as a biosensor by selectively capturing the target analyte to the NP surface. To design an LSPR HSP70 sensor, optical and fluidic simulations were developed to determine optimal NP geometries and microchannel dimensions. The results showed optimal response when using 100nmx5nm gold nanotriangles inside of a 100μmx100μm microchannel. Simulations of the sensor performance showed HSP70 detection from 0.92-4000ng/ml with a resolution of 1.1ng/ml, all of which satisfied the design requirements. An LSPR sensor was experimentally tested at the benchtop scale to prove the concept. Gold NPs were fabricated by electron beam lithography and enclosed in a polymer flow cell. For initial testing of the LSPR sensor, the NPs were functionalized with biotin for selective capture of streptavidin. Streptavidin was detected in real time over the range 55-500,000ng/ml. The use of bovine serum albumin (BSA) was shown to be necessary to block non-specific binding sites to ensure a streptavidin-specific response. The LSPR sensor was then demonstrated to detect salmon HSP70 at 4600ng/ml using its synthetic antibody. Overall, these results demonstrate that LSPR can be used to realize an HSP70 biosensor suitable for point-of-care applications.

Structure-specific recognition of nucleic acids is a promising method to reduce the size of the recognition unit required to achieve the necessary selectivity and binding affinity for small molecules. It has been demonstrated recently that G-quadruplex DNA structures can be targeted by organic cations in a structure-specific manner. Structural targets of quadruplexes include the planar end surfaces of the G-tetrad stacked columns as well as four grooves. The significant structural differences between quadruplex DNA and duplex DNA make quadruplex DNA a very attractive target for highly selective, structure-specific drug design. We have used a variety of biophysical techniques including circular dichroism, surface plasmon resonance, thermal melting and absorbance spectroscopy to investigate small molecules that can selectively bind to the ends of human telomeric DNA as well as the ends of the G-quadruplex structure formed by the purine-rich promoter region of the c-MYC oncogene. We have also screened a library of heterocyclic diamidines, and identified one that binds selectively in the grooves of human telomeric quadruplex DNA. This compound is an excellent starting point for the design of new anti-cancer and anti-parasitic compounds with high affinity and selectivity for human telomeric DNA.

Surface plasmon polaritons are electromagnetic surface waves coupled to electron plasma oscillation of metals at a metal-dielectric interface. At optical frequencies, these modes are of great interest because of their high confinement to a metal-dielectric interface. Due to the field enhancement at the interface, they have been used in different applications such as sensors, second harmonic generation and enhanced Raman scattering. Surface plasmon resonance based sensors are being used for detection of molecular adsorption such as DNA and proteins. These sensors are known to be highly sensitive and have successfully become commercialized. Terahertz (THz) frequency band of electromagnetic spectrum has attracted researchers in the last few years mostly because of sensing and imaging applications. Many important chemical and biological molecules have their vibrational and rotational resonance frequencies in the THz range that makes the THz sensing one of the most important applications of THz technology. Considering above mentioned facts, extending the concept of surface plasmon sensors to THz frequencies can result in sensitive sensors. In this work the possibility of this extension has been investigated. After reviewing optical surface plasmon polariton waves and a basic sensor configuration, surface plasmon polariton waves propagating on at metallic and doped semiconductor surfaces have been examined for this purpose. It has been shown that these waves on metallic surfaces are loosely confined to the metal-dielectric interface and doped semiconductors are also too lossy and cannot meet the requirements for sensing applications. Afterwards, it is shown that periodically patterned metallic surfaces can guide surface waves that resemble surface plasmon polariton waves. A periodically patterned metallic surface is used to guide THz surface plasmon polariton-like surface waves and a highly sensitive sensor is proposed based on that. The quasi-optical continuous wave (CW) THz radiation is coupled to this structure using the Otto's attenuated total reflection (ATR) configuration and the sensitivity of the device is discussed. A general scattering parameter based model for prism coupling has been proposed and verified. It is shown that a critical coupling condition can happen by changing the gap size between the prim and periodic surface. Details of fabrication of the periodic structure and experimental setup have also been presented.

As the critical dimensions of many devices, especially electronics, continue to become smaller, the ability to accurately analyze the properties at ever smaller scales becomes necessary. Optical techniques, such as confocal microscopy and various spectroscopies, have produced a wealth of information on larger length scales, above the diffraction limit. Scanning probe techniques, such as scanning tunneling microscopy and atomic force microscopy, provide information with an extremely fine resolution, often on the order of nanometers or angstroms. In this document, plasmon coupling is used to generate large signal increases, with clear future applications toward scanning probe optical spectroscopies. A variation on scanning tunneling microscopy is also used to study the surface structure of environmentally interesting nanoparticles. Traditional Raman spectroscopy is used to examine doped graphene, which is becoming a hot material for future electronic applications.