Currently, it is very challenging to accurately monitor the response of patients to radiation therapy over the course of treatment. The initial response to ionizing radiation occurs in the cells at a molecular level, and effects of the response are not typically noticeable on short time scales. Surface-enhanced Raman Spectroscopy, or SERS, has proven to be a useful technique in the analysis of tissues and cells at a molecular level. Specifically, the use of targeted SERS probes allows for the detection of specific proteins on the cell membrane. The work presented here looks to assess the feasibility of using targeted SERS probes and two-dimensional SERS microscopy to measure the response of tumour cells to ionizing radiation, by identifying changes in the distribution of membrane proteins following exposure to clinically relevant doses of ionizing radiation (≤ 60Gy). Two different types of targeted SERS probes were investigated, based on the work of Grubisha et al. ([1]; Type I) and Qian et al. ([2]; Type II), both containing a gold nanoparticle core. In a simplified cellular experiment, biotin on the surface of biotinylated OVCAR5 cells was targeted with streptavidin-SERS probes, and the Type-II SERS probes showed the most promising results. However, SERS maps still provided less characteristic spectral signal than expected, and challenges remain in the development of a reproducible cellular imaging technique. Despite difficulties in cellular imaging, the functionality of the Type-II SERS probes was verified separately, using gold slides with a biotin monolayer in place of cells. Following verification, the SERS intensities provided by differently sized clusters of the SERS probes were characterized. To begin, both SERS maps and scanning electron microscope (SEM) images of gold slides were acquired after incubation with Type-II SERS probes for multiple times (1hr, 2hr, 3hr, 12hr). Data analysis of the SEM images provided a measure of the physical distribution of the SERS probes on the surface of the slide, while analysis of the SERS maps provided information about the spectral distribution of the probes. By relating the information provided by the SEM images and SERS maps, a simple polynomial relationship between SERS intensity and the number of clustered SERS probes providing the enhancement was determined, providing a framework for quantifiable SERS imaging. Finally, an independent experiment was devised to ensure that exposure to clinically relevant doses of ionizing radiation would affect the ability of the targeted protein to bind to SERS probes, thus leading to measurable differences in SERS maps of irradiated and unirradiated cells. A series of experiments utilizing the enzyme-linked immunosorbant assay (ELISA) was performed to test the effect of ionizing radiation-induced damage on the ability of streptavidin to bind to biotin, and the results confirmed that a noticeable reduction in binding could be detected at doses as low as 10 Gy. The results of this work demonstrate that following the development of a suitable cell/SERS probe incubation technique, Type-II SERS probes would be appropriate for use in quantifiable SERS imaging. Also, it is suggested that a measurable change in protein function will be present when comparing SERS maps of control cells to those of cells irradiated to clinically relevant doses. / Graduate

This thesis addresses the issue of a potential future microelectronics technology, namely the possibility of utilising the optical properties of nanocrystalline silicon for optoelectronic circuits. The subject is subdivided into three chapters. Chapter 1 is an introduction. It formulates the oncoming problem for microelectronic development, explains the basics of Integrated Optoelectronics, introduces porous silicon as a new light-emitting material and gives a brief review of other competing light-emitting material systems currently under investigation. Examples of existing porous silicon devices are given. Chapter 2 reviews the basic physics relevant to the subject of this thesis and informs on the present situation in this field of research, including both experimental and theoretical knowledge gained up-to-date. The chapter provides the necessary background for correct interpretation of the results reported in Chapter 3 and for a realistic decision on the direction for future work. Chapter 3 describes my own experimental and computational results within the framework of the subject, obtained at De Montfort University. These include: onestep preparation of laterally structured porous silicon with photoluminescence and microscopy characterisation, Raman spectroscopy of porous silicon, a polarisation study of the photoluminescence from porous silicon, computer simulations of the conductivity of two-component media and of laser focused atomic deposition for nanostructure fabrication. Thus, this thesis makes a dual contribution to the chosen field: it summarises the present knowledge on the possibility of utilising optical properties of nanocrystalline silicon in silicon-based electronics, and it reports new results within the framework of the subject. The main conclusion is that due to its promising optoelectronic properties nanocrystalline silicon remains a prospective competitor for the cheapest and fastest microelectronics of the next century.

The objective of this dissertation is to understand the structural and optoelectronic properties of group III-nitride materials grown by High-Pressure Metal Organic Chemical Vapor Deposition (HP-MOCVD) and Migration Enhanced Plasma Assisted MOCVD by FTIR reflectance spectroscopy, Raman spectroscopy, X-ray diffraction, and Atomic Force Microscopy. The influence of the substrates/templates (Sapphire, AlN, Ga-polar GaN, N-polar GaN, n-GaN, and p-GaN) on the free carrier concentration, carrier mobility, short-range crystalline ordering, and surface morphology of the InN layers grown on HP-MOCVD were investigated using those techniques. The lowest carrier concentration of 7.1×1018 cm-3 with mobility of 660 cm2V-1s-1 was found in the InN film on AlN template, by FTIR reflectance spectra analysis. Furthermore, in addition to the bulk layer, an intermediate InN layers with different optoelectronic properties were identified in these samples. The best local crystalline order was observed in the InN/AlN/Sapphire by the Raman E2 high analysis. The smoothest InN surface was observed on the InN film on p-GaN template. The influence of reactor pressures (2.5–18.5 bar) on the long-range crystalline order, in plane structural quality, local crystalline order, free carrier concentration, and carrier mobility of the InN epilayers deposited on GaN/sapphire by HP-MOCVD has also been studied using those methods. Within the studied process parameter space, the best material properties were achieved at a reactor pressure of 12.5 bar and a group-V/III ratio of 2500 with a free carrier concentration of 1.5x1018 cm-3, a mobility in the bulk InN layer of 270 cm2 V-1s-1 and the Raman (E2 high) FWHM of 10.3 cm-1. The crystalline properties, probed by XRD 2θ–ω scans have shown an improvement with the increasing reactor pressure. The effect of an AlN buffer layer on the free carrier concentration, carrier mobility, local crystalline order, and surface morphology of InN layers grown by Migration-Enhanced Plasma Assisted MOCVD were also investigated. Here, the AlN nucleation layer was varied to assess the physical properties of the InN layers. This study was focused on optimization of the AlN nucleation layer (e.g. temporal precursor exposure, nitrogen plasma exposure, and plasma power) and its effect on the InN layer properties.

In 2018 ESA and NASA plan to send the ExoMars rover to the Martian surface. This rover is planned to have a suite of analytical equipment that includes a Raman spectrometer. In this context, an evaluation of Raman spectroscopy as an analytical tool for interplanetary studies is investigated. The preparation techniques for appropriate inorganic and organic mixtures are interrogated. Methods are investigated to optimize the homogeneity of over 50 samples involving mineral phases; calcite, gypsum and goethite and selected organic biomolecular systems; anthracene, naphthalene and beta-carotene. From mixtures produced of these organic and inorganic materials differences between homogeneity of the samples is observed. Different mixing techniques are investigated to reduce this, however all the samples display variation on a micron scale. To resolve this issue a grid system of 9 points is implemented on solid samples and solutions are used to produce standards. The standards are devised using a range of instrument validation parameters for comparison between commercially available spectrometers and the prototype instrument. From these standards a prototype instrument is optimized for data acquisition and an evaluation procedure for instrument performance is established. The prototype Raman spectrometer is evaluated to match the specifications of the spectrometer on board ExoMars rover. A range of astrobiological relevant samples are interrogated; geological samples, biomarkers, cellular systems and bio-geological inclusions. From these samples detection of organics is observed to be only possible, with Raman spectroscopy where organics are localised in high concentrations, upon grinding and mixing geological inclusions Raman spectroscopy is unable to detect the organic components.

The technique of Raman spectroscopy was applied in order to identify and characterize the number of minerals in the mineralogical collection at the Department of Earth Sciences. The collection was broadened with five rare carbonates borrowed from the collection of the Swedish Museum of Natural History in Stockholm. In total, 66 specimens were examined.The characteristics of interest included possible presence and nature of defects and impurities, degree of crystallinity, residual stresses, possible treatment by natural heat sources (e.g. radionuclides) or chemicals (e.g. polishing agents), and fluorescence.Raman spectroscopy was chosen as examination method because of its distinctive advantage over traditional techniques – a non-destructive probing of pristine materials and minimum or no preparation. Besides, Raman spectroscopy performs very well in collecting the needed characteristics, in terms of its sensitivity, as well ability to probe miniature grains in a matrix with a high spatial resolution.A portable system was used to identify the presence of impurities and the fingerprint of the host rock in the majority of the examined carbonates. The rare carbonate burbankite showed distinct fluorescence bands, which likely can be explained by its complicated chemical composition.The Raman system was used for gemmological purposes and helped to identify the purity of the gems. Diamond and two rubies showed to be free from impurities, but red corundum showed a broad peak, which may represent traces of natural heat treatment, which in turn could be caused by regional metamorphism or even by a radiation source. Furthermore, the correlation between the signal intensity of the fluorites’ bands and the chemical composition of the minerals were studied. The experiment showed that blue fluorite fully misses the peak T2g while purple and grey fluorites showed a well-developed and easily recognizable peak at this location. Thus, it was discovered that the presence and intensity of this peak is directly dependent on the fluorite’s colour, i.e. on the host species, which are incorporated in the crystal structure, such as metals, rare earth elements (REE) or even organic substances. Moreover, residual tensile stress was identified in colourless quartz. The tensile stress was estimated to be in the interval between 0.23 and 1.0 GPa.The Raman system was used to identify different end-members of the garnet family. Raman spectroscopy showed to have high analytical power and helped to estimate the ratio between the end-members in eight garnet samples. In one case, fluorescence was linked to the presence of REEs in the structure of almandine. One sample of calcite showed to be incorrectly placed in the collection. This work will now form a solid foundation for the mineral characteristics handbook. / Ramanspektroskopitekniken applicerades för att identifiera och karakterisera antalet mineraler i den mineralogiska samlingen vid Institutionen för geovetenskaper. Samlingen breddades med fem sällsynta karbonater som lånades från Naturhistoriska riksmuseets samling i Stockholm. Sammanlagt analyserades 66 prover. Egenskaperna av intresse inkluderade eventuell förekomst av och karaktären hos defekter och föroreningar, graden av kristallinitet, restspänningar, eventuella spår av naturlig värmebehandling (till exempel radionuklider) eller kemisk behandling (till exempel polermedel), och fluorescens. Ramanspektroskopi valdes som undersökningsmetod på grund av dess tydliga fördel över traditionella metoder – en icke-förstörande undersökning av rena material och minimal eller ingen förberedelse. Därutöver fungerar Ramanspektroskopi väldigt bra för undersökning av de efterfrågade egenskaperna, vad gäller dess känslighet och kapacitet vid sondering av miniatyrkorn i matriser med hög spatial upplösning. Ett portabelt system användes för att identifiera föroreningar och fingeravtryck av den omslutande bergarten i de flesta undersökta karbonatprov. Den sällsynta karbonaten burbankit visade på distinkta fluorescensband, som sannolikt kan tillskrivas dess komplicerade kemiska sammansättning. Ramansystemet användes i gemmologiskt syfte och kunde identifiera ädelstenarnas renhet. Diamant och två rubiner visade sig sakna föroreningar, men den röda korunden visade en bred topp, som kan indikera på spår av naturlig värmebehandling, som i sin tur kan ha orsakats av regional metamorfos eller till och med en strålningskälla. Därutöver studerades sambandet mellan signalstyrkan hos fluoriters band och mineralers kemiska sammansättning. Experimentet visade att blå fluorit fullständigt saknar toppen från T2g, medan de lila och grå fluoriterna hade välutvecklade och lättigenkännliga toppar vid denna position. Således upptäcktes att denna topps närvaro och intensitet är direkt beroende av fluroritens färg, det vill säga av elementen som är inkorporerade i kristallstrukturen, så som metaller, sällsynta jordartsmetaller eller till och med organiska substanser. Därutöver identifierades restdragspänning i den färglösa kvartsen. Spänningen uppskattades ligga i intervallet 0.23 – 1.0 GPa. Ramansystemet användes för att identifiera olika ändelement i granatfamiljen. Ramanspektroskopin hade hög analytisk förmåga och hjälpte till att estimera förhållandet mellan ändelementen i åtta granatprover. I ett fall kunde fluorescens bindas till förekomsten av sällsynta jordartsmetaller i almandinets struktur. Ett kalcitprov visade sig vara felaktigt placerat i samlingen. Detta arbete kommer nu utgöra en god grund för den mineralogiska samlingens handbok.

Based upon experimental evidence from the 1970’s we proposed that a reduced form of hydroxocobalamin should be capable of producing carbon dioxide (CO2) from carbon monoxide (CO) in blood, and that this conversion should be detectable. Using resonance raman spectroscopy we demonstrated that a mixture of hydroxocobalamin and ascorbic acid could create the reduced form of hydroxocobalamin. We used a closed-loop circulation system with a hollow-fiber membrane oxygenator to produce carboxyhemoglobin. Using sensitive gas monitoring equipment to the gas-out port of the oxygenator we analyzed the CO and CO2 concentrations coming from the oxygenator. The mixture of hydroxocobalamin and ascorbic acid caused a 5-fold increase in the CO2 concentration of the gas-out flow, in comparison to baseline and negative controls. These findings offer initial support for the potential use of a mixture of hydroxocobalamin and ascorbic acid as an injectable antidote for carbon monoxide poisoning.

The main objective of this thesis is to efficiently disperse and align SWNTs in two different polymer matrices to obtain an orthotropic composite whose strength, stiffness and electrical properties depend on the orientation of the SWNTs. The SWNTs are successfully dispersed and aligned in a polyimide matrix and a polymer blend of UDMA/HDDMA. In-situ polymerization under sonication is used to disperse the SWNTs in polyimide matrix and sonication is used to disperse SWNTs in the UDMA/HDDMA matrix. In both cases, an electric field is used to align the SWNTs in the polymer matrices. In the polyimide, the SWNTs are aligned by electrospinning technique, and in (UDMA/HDDMA) the SWNTs are aligned by applying an AC electric field, while the composite is cured.The electrical and mechanical properties of randomly dispersed SWNT polyimide composites and SWNT/UDMA/HDDMA composite are measured. The dielectric constant and storage modulus of SWNT polyimide composite increased with SWNT concentration. Low percolation (0.06 wt%) and an increase of 113% in storage modulus with 0.2 wt% SWNTs, both indicate good dispersion of SWNTs in the polyimide matrix. The dielectric constants, conductivity for the unaligned SWNT/UDMA/HDDMA composite are isotropic. The electrical and mechanical properties of the randomly dispersed SWNT polyimide composite and SWNT/UDMA/HDDMA composite are used as references when analyzing the aligned counter parts. Different characterization methods are used to assess the alignment of the SWNTs in the polyimide and (UDMA/HDDMA) matrices. A variety of characterization techniques, i.e. microscopy, Raman spectroscopy, electrical conductivity, dynamic dielectric spectroscopy and dynamic mechanical analysis, indicate preferential alignment of SWNTs in two types of polymers: Polyimide and (UDMA/HDDMA). Optical microscope images showed alignment of the SWNTs in the UDMA/HDDMA composite. Inspection of the Raman spectra on aligned SWNT polyimide composite fibers and aligned SWNT/UDMA/HDDMA composite indicates a decrease in the intensity of the tangential peak of the SWNT with increase in the polarizer angle. The difference in the perpendicular and parallel Raman peaks indicate preferential alignment of SWNTs in both the polymer matrices. In the aligned polyimide composite, percolation transition is at 0.2 wt% SWNT concentrations when dielectric constant is measured parallel to the aligned SWNTs. But percolation transition is at 0.65 wt% SWNT concentrations when dielectric constant is measured perpendicular to the aligned SWNTs. Electrical measurements on aligned SWNT polyimide and UDMA/HDDMA composite are highly anisotropic. In both cases, the dielectric constant values parallel to the direction of SWNT alignment are higher than the values perpendicular to the direction of SWNT alignment. To analyze the resulting anisotropy in the dielectric constant, Bruggeman's effective medium approach is used. The effective medium theory predicts the effective dielectric constant of a composite with aligned anisotropic inclusions. The effective dielectric constant, perpendicular to the aligned inclusions and parallel to the aligned inclusions is estimated. The dielectric constant values of aligned SWNT polyimide and aligned SWNT/UDMA/HDDMA composites are compared to the experimental results. Both the values from the theory and experiment show anisotropy in dielectric constant. The theory indicated that the dielectric constant parallel to the aligned inclusions is highly influenced by the dielectric constant of the inclusion and the dielectric constant perpendicular to the aligned inclusions is highly influenced by the dielectric constant of the polymer matrix. Results from the different characterizing techniques indicate that SWNTs are successfully aligned in the polyimide matrix and (UDMA/HDDMA) matrix by electrospinning technique and by an AC electric field respectively.

Parts of human telomere sequences containing at least 4 guanine subsequences show the ability to form intrastrand quadruplexes of remarkable conformational diversity. Former studies using conventional Raman spectroscopy have revealed that the sequence G3(TTAG3)3 at milimolar concentrations in phosphate buffer solution doped with Na+ ions (ionic strength 150 mM) adopts antiparallel conformation regardless of the length of standing at room temperature or annealing, whereas K+ ions cause gradual transition to "3+1" or even parallel conformation. On the other hand, measurements carried out upon sequence AG3(TTAG3)3 at similar concentrations using Photonic Crystal Fibre-enhanced Raman Spectroscopy (PCFRS) suggest that in the respective presence of both Na+ and K+ (ionic strength 100 mM), a parallel structure is adopted. The hereby presented work employs conventional Raman spectroscopy and Drop Coating Deposition Raman spectroscopy to examine the sequence AG3(TTAG3)3 at concentrations ranging from units to hundreds of milimoles in strands. It concludes that the structure adopted in the presence of Na+, resp. K+ ions is antiparallel, resp. "3+1", and doesn't change over time despite both long standing and annealing. Two hypotheses about the cause of the differences between the results obtained by PCFRS and...

L'objectif principal de ce travail est l'étude fondamentale de nanostructures à base de carbone individuelles dans le but d'améliorer la compréhension de leurs propriétés vibrationnelles et optiques intrinsèques ainsi que d'estimer et de quantifier les effets d'environnement. Dans ce but, nous avons synthétisé des nanotubes de carbone mono- et multi-feuillets par décomposition catalytique en phase vapeur sur des substrats dédiés. L'aspect principal du travail est basé sur l'utilisation combinée de plusieurs sondes expérimentales sur la même nanostructure carbonée individuelle. Nous avons effectué une analyse structurale complète par diffraction électronique et microscopie électronique haute résolution et mesuré les spectres Raman de ces nanostructures individuelles. Plusieurs effets environnementaux importants ont été mis en évidence pour la première fois, comme par exemple l'effet d'un couplage mécanique (due à l'interaction de van-der-Waals) entre les parois des nanotubes bi-feuillets conduisant à une modification des modes Raman de basse fréquence et des conditions de résonances optiques. De plus, le comportement des modes de haute fréquence des nanotubes bi-feuillets a été analysé. Suite à ce travail plusieurs critères expérimentaux permettant un diagnostic de la structure des nanotubes multi-feuillets ont été proposés. / The main objective of this work is the fundamental physical study of individual isolated carbon nanostructures in order to address their intrinsic vibrational and optical properties and also to estimate and quantify the environmental effects. For these purposes, we synthesized individual single- and multi-walled carbon nanotubes by chemical vapour deposition method on dedicated substrates. The main aspect of the work involves the combined use of different experimental probes on the same individual nanostructures. We performed a complete structure analysis by electron diffraction and high-resolution electron microscopy and the measurement of the Raman spectra on these individual nanostructures. Several important environmental effects were evidenced for the first time, e.g. the effect of mechanical coupling (van-der-Waals interaction) between the layers of double-walled carbon nanotubes leading to the change in the low-frequency Raman modes and the optical resonance conditions. Moreover the behaviour of high-frequency modes of double-walled tubes was also analysed and described. As a result of this work several experimental criteria for structure diagnostics of multi-walled carbon nanotubes were proposed.

Call number: LD2668 .T4 1986 Y36 / Master of Science / Physics