This diploma thesis deals with comparison of experimental and simulated low energy ion scattering spectra. There is a theoretical description of basic principles of low energy ion scattering and description of the spectrometer, which is situated at Institute of physical engineering. It is shown, how to prepare samples using the colloidal gold solution. The deposition of gold nanoparticles is characterized. The usage and meaning of time and energy spectra of low energy ion scattering is explained. There is also shown the effect of channeling in Si substrate.

This thesis deals with metal nanostructures and their use in detection of biomolecules. A protocol for stabilizing solutions of gold nanoparticles was developed for better usage in biological samples or biochemical processes, where different pH or salt concentrations can be used. A model of optical properties of the nanoparticles was presented and supported by spectroscopic experiments. A possible utilization of plasmonic nanostructures on surfaces for detection of biomolecules was also demonstrated.

This diploma thesis is focused on characterization of semiconductive nanowires. Theoretical part of thesis deals with basic physical properties of TiO2 and a search of selected properties of titanium dioxide nanostructures is preseted. The experimental part describes several spectroscopic measurements carried out with complex of TiO2 nanowires. The influence of gold nanoparticles (deposited on the nanowire surface) on sample properties is also tested. The final part of thesis is devoted to methodology for measurement of electrical properties. These experiments are carried out only with one nanowire. Focused electron beam induced deposition (resp. Focused ion beam induced deposition) and electron lithography are utilized.

This thesis aims to prepare functional gold nanoparticles (AuNPs) and use them in conjunction with a surface plasmon resonance (SPR) biosensor for highly sensitive detection of carcinoembryonic antigen (CEA). In this work, preparation of colloidal AuNPs was investigated and a three-step synthesis was optimized to yield spherical nanoparticles with a diameter of about 100 nm and smooth surface. The synthesized AuNPs were functionalized by a self-assembled monolayer of carboxy-PEG alkanethiols and streptavidin and characterized by UV/VIS spectroscopy and -potential method. Finally, the functionalized AuNPs were employed in sandwich assay for the sensitive detection of CEA and it was demonstrated that they can enhance sensor response to CEA by a factor of 100 compared to the direct detection of CEA.

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>Magister Scientiae - MSc / Nanotechnology has emerged as an elementary division of modern science and stemmed directly from green chemistry twelve basic concepts, it receives global attention due to its unique character and ample applications. It also has great potential to mitigate the challenges they face in various fields, especially medical sector. Nanodrugs are increasingly considered as a potential candidate to carry therapeutic agents safely into a targeted compartment in an organ, particular tissue or cell. In this study, twenty (20) Libyan plants were selected and evaluated for their potential to synthesis gold and silver nanoparticles. The screening of the different plant extracts was performed using 96 well plate method at 25 °C and 70 °C. The NPs formation was confirmed and characterized using UV- Vis, DLS, HR-TEM and EDX. A well-defined NPs were obtained at high temperature (70 °C). The Au NPs had an average diameter of 92 nm at 25 °C and 66 nm at 70 °C. The zeta potential values were observed to be negative (-14 to -24) and indicate the stability of the Au NPs. The HR-TEM showed polydispersity, which decreased at higher temperature (70 °C). The stability of Au NPs in nutrient broth prior was conducted as well. All the Au NPs under study showed stability, only minimal changes in the UV-Vis spectra can be observed. Two plant extract viz Pistacia atlantica, Junipers phoenicea showed consistent results and forming stable and smaller NPs compared to others, both of the plant extracts and the corresponding NPs were tested against Streptococcus mutans and showed MIC value ~ 49 g/mL. In case of silver NPs, two plant extracts viz J. phoenicea, Rosmarinus officinalis, showed superior results than the others; both plants produced stable and small Ag NPs. The antibacterial activity against S. mutans demonstrated MIC valus ~ 50 g/mL. The synthesised NPs showed a promising bioactivity for developments of new antibacterial agents against S. mutans strains. Dose-dependent activity was observed for the tested NPs.

Mitochondria are an attractive target for the design of cancer therapy. One of the mechanisms by which chemotherapeutics destroy cancer cells is by inducing apoptosis through extrinsic or intrinsic apoptotic pathways. Extrinsic pathways target cell surface receptors whilst intrinsic pathways target mitochondria. Several studies have shown cancer cell destruction through the extrinsic pathways, which target cancer-specific overexpressed growth factor receptors on the cell membrane. Although the mitochondria dependent apoptotic process is well understood, its application in cancer therapy is still not well developed. Therefore, to design an effective cancer therapy targeting mitochondria, a good understanding in mitochondria dependent apoptotic process is required. Recent developments in nanotechnology have enabled live cell investigations and non-destructive methods to obtain cellular information. The availability of such information would assist to design methods of targeted apoptosis induction. In view of this, I report on studies towards development of cancer therapy where nanoparticles (NPs) were targeted to human cell mitochondria for two purposes: (a) development of cell-imaging tools to investigate the fundamental cell biological pathways inside cells and (b) induction of apoptosis by targeting nanoparticles to mitochondria. Current medical and biological fluorescent imaging methods are mainly based on dye markers, which are limited in light emission per molecule, as well as photostability. Consequently, NPs are gaining prominence for molecular imaging because of their strong and stable fluorescence. Additionally, in order to get insight of mitochondrial molecular information, I investigated the use of optical properties of gold nanoparticles (Au NPs) for surface enhanced Raman spectroscopy (SERS). In this study, two types of Au NPs - nanospheres (Au NS) and nanorods (Au NR) were investigated. Results from this study showed the enhancement effect of Au NPs in Raman spectra of mitochondria, especially in the region from 1500 to 1600 cm-1. In this region, normal Raman spectra of mitochondria showed the presence of some understated Raman peaks probably due to the excitation wavelength dependence. Au NRs showed a larger enhancement effect than Au NS with respect to the penetration depth of the plasmonic nearfield enhancement effect. Although, the details of the enhancement mechanism are beyond the current studies, Au NPs could be enhancing vibrations of aromatic residues in proteins. This study therefore showed that Au NPs could enhance Raman spectra of mitochondria and in addition the shape of the nanoparticles had a significant effect on SERS spectra. In living cells, I investigated some transfection methods and targeting of NPs to mitochondria or cytosolic actin subunits. I tested the performance of three transfection reagents to deliver nanodiamonds (NDs) into living cells. Antibody functionalized NDs were targeted to mitochondria or cytosolic actin subunits. Three transfection reagents were used: cationic liposomes PULSin™, the cell penetrating peptide protamine, and oligosaccharide modified polypropylene imine (PPI) dendrimers. Fluorescence imaging results revealed that dendrimers were the most efficient in delivering ND conjugates to targeted organelles. Protamine-mediated transfections appeared to target ND conjugates to intended organelles, although there was a tendency of unfunctionalized NDs to be directed to the nucleus. PULSin™-mediated transfection formed ND aggregates regardless of the functionalization moiety. This reflected the unsuitability of the cationic liposome to mediate ND transfections. Further, I investigated the potential use of Au NPs for cell imaging and photothermal lysis of mitochondria inside cells. Just as above, I also tested the performance of the three-transfection reagents mentioned above on transfection capacity of Au NPs into living cells. Using transmission electron microscopy (TEM), oligosaccharide modified dendrimers showed the best transfection of functionalized Au NPs. Further experiments explored the use of the nearfield enhancement effect of Au NPs in combination with low-level laser irradiation (LLLI) to induce apoptosis in living cells. Analysis of the apoptotic process using cytochrome c release showed that Au NPs induced apoptosis most probably through mechanical disruption of the outer mitochondrial membrane. However, apoptosis was significantly accelerated in cells with mitochondrially targeted Au NRs than in cells without Au NRs. This study showed successful targeting of Au NPs to mitochondria in living cells, and demonstrated the potential of using Au NPs in combination with laser irradiation to induce the mitochondria dependent apoptotic pathway. In conclusion, the potential use of Au NPs in SERS of mitochondria and the application of NDs for cell imaging of intracellular organelles were demonstrated. Lastly, Au NPs were targeted to mitochondria in living cells and could induce apoptosis due to mechanical disruption of the outer mitochondrial membrane. Consequently, application of low-level laser irradiation to Au NP transfected cells accelerated the apoptotic process.

Magister Philosophiae - MPhil / The fascinating optical properties of metallic nanostructures, dominated by collective oscillations of free electrons known as plasmons, open new opportunities for the development of devices fabrication based on noble metal nanoparticle composite materials. This thesis demonstrates a low-cost and versatile technique to produce stimuli-responsive ultrafast plasmonic nanostructures with reversible tunable optical properties. Albeit challenging, further control using thermal external stimuli to tune the local environment of gold nanoparticles embedded in V02 host matrix would be ideal for the design of responsive functional nanocomposites. We prepared Au-V02 nanocomposite thin films by the inverted cylindrical reactive magnetron sputtering (ICMS) known as hollow cathode magnetron sputtering for the first time and report the reversible tuning of surface plasmon resonance of Au nanoparticles by only adjusting the external temperature stimuli. The structural, morphological, interfacial analysis and optical properties of the optimized nanostructures have been studied. ICMS has been attracting much attention for its enclosed geometry and its ability to deposit on large area, uniform coating of smart nanocomposites at high deposition rate. Before achieving the aforementioned goals, a systematic study and optimization process of V02 host matrix has been done by studying the influence of deposition parameters on the structural, morphological and optical switching properties of V02 thin films. A reversible thermal tunability of the optical/dielectric constants of V02 thin films by spectroscopic ellipsometry has been intensively also studied in order to bring more insights about the shift of the plasmon of gold nanoparticles imbedded in V02 host matrix.

Contrast agents are often crucial in medical imaging for disease diagnosis. Novel contrast agents, such as gold nanoparticles (AuNPs) and lanthanides, are being ex- plored for a variety of clinical applications. Preclinical testing of these contrast agents is necessary before being approved for use in humans, which requires the use of small animal imaging techniques. Small animal imaging demands the detection of these contrast agents in trace amounts at acceptable imaging time and radiation dose. Two such imaging techniques include x-ray fluorescence computed tomography (XFCT) and photon-counting CT (PCCT). XFCT combines the principles of CT with x-ray fluorescence by detecting fluorescent x-rays from contrast agents at various projections to reconstruct contrast agent maps. XFCT can image trace amounts of AuNPs but is limited to small animal imaging due to fluorescent x-ray attenuation and scatter. PCCT uses photon-counting detectors that separate the CT data into energy bins. This enables contrast agent detection by recognizing the energy dependence of x-ray attenuation in different materials, independent of AuNP depth, and can provide anatomical information that XFCT cannot. To achieve the best of both worlds, we modeled and built a table-top x-ray imaging system capable of simultaneous XFCT and PCCT imaging. We used Monte Carlo simulation software for the following work in XFCT imaging of AuNPs. We simulated XFCT induced by x-ray, electron, and proton beams scanning a small animal-sized object (phantom) containing AuNPs with Monte Carlo techniques. XFCT induced by x-rays resulted in the best image quality of AuNPs, however high-energy electron and medium-energy proton XFCT may be feasible for on-board x-ray fluorescence techniques during radiation therapy. We then simulated a scan of a phantom containing AuNPs on a table-top system to optimize the detector arrangement, size, and data acquisition strategy based on the resulting XFCT image quality and available detector equipment. To enable faster XFCT data acquisition, we separately simulated another AuNP phantom and determined the best collimator geometry for Au fluorescent x-ray detection. We also performed experiments on our table-top x-ray imaging system in the lab. Phantoms containing multiples of three lanthanide contrast agents were scanned on our tabletop x-ray imaging system using a photon-counting detector capable of sustaining high x-ray fluxes that enabled PCCT. We used a novel subtraction algorithm for reconstructing separate contrast agent maps; all lanthanides were distinct at low concentrations including gadolinium and holmium that are close in atomic number. Finally, we performed the first simultaneous XFCT and PCCT scan of a phantom and mice containing both gadolinium and gold based on the optimized parameters from our simulations. This dissertation outlines the development of our tabletop x-ray imaging system and the optimization of the complex parameters necessary to obtain XFCT and PCCT images of multiple contrast agents at biologically-relevant concentrations. / Graduate

L'objectif principal de cette thèse a été d'expérimenter de nouvelles voies d'exfoliation des feuillets de graphène dans des matrices polysaccharides telles que la cellulose et le chitosane dopé avec des nanoparticules d'or (Au). Notre stratégie a été d'explorer de nouvelles voies de greffage de molécules et de macromolécules sur des feuillets d'oxyde de graphène (GO). Dans un premier temps, nous avons donc oxydé un graphite commercial par la méthode de Hummers qui est apriori la méthode la plus simple à mettre en oeuvre pour produire une suspension stable de feuillets d'oxyde de graphène totalement exfoliés dans l'eau. L'intérêt de cette oxydation est l'obtention de fonctions acide carboxylique et époxyde susceptibles d'être fonctionnalisées en deux étapes par l'éthylénediamine puis par un polysaccharide tel que la cellulose. En effet, afin d'améliorer la compatibilité du graphite oxydé avec des matrices organiques telle que la cellulose, l'idée est de lui greffer des chaînes polysaccharides. Ces résultats ont permis de mettre en évidence l'exfoliation partielle des feuillets de graphène après fonctionnalisation et l'obtention d'un taux de greffage massique d'environ 35% pour la cellulose. La conductivité électrique des nano-composites correspondants a aussi été étudiée par des mesures diélectriques à des températures variées. L'augmentation de la conductivité électrique après la fonctionnalisation du graphite oxydé a mis en évidence une solvo-thermoréduction simultanément à la fonctionnalisation. Enfin, le dopage de ce matériau par des particules d'or a permis d'obtenir une conductivité électrique de 1.60 10-4 S m-1. En ce qui concerne le matériau composite à base de chitosane, la démarche scientifique a été la même que pour l'analogue cellulose, le taux de greffage massique a été d'environ 68% et nous avons en plus testé son activité catalytique vis-à-vis de la conversion du 4-Nitrophénol en 4-Aminophénol et les résultats obtenus ont été très satisfaisants / The main objective of this thesis has been to experiment a new ways of exfoliation of graphene sheets in polysaccharide matrices such as cellulose and chitosan doped with gold nanoparticles (Au). Our strategy was to explore new routes for the grafting of molecules and macromolecules onto graphene oxide (GO). First, we have oxidized commercial graphite by the method of Hummers which is a priori the simplest method to implement to produce a stable suspension of graphene oxide sheets totally exfoliated in water. The advantage of this oxidation is the formation of carboxylic acid and epoxy functional groups onto the graphite surface that can be functionalized in two stages by ethylenediamine and then by a polysaccharide such as cellulose. Indeed, in order to improve the compatibility of graphite oxide with organic matrix such as cellulose, the idea is to graft it onto polysaccharide chains. These results made it possible to demonstrate the partial exfoliation of the graphene sheets after functionalization and to obtain a percentage of grafting of about 35wt% for cellulose. The electrical conductivity of the corresponding nanocomposites has also been studied by dielectric measurements at various temperatures. The increase of the electrical conductivity after the functionalization of graphite oxide showed a solvo-thermo reduction simultaneously with the functionalization. Finally, the doping of this material by gold particles made it possible to obtain an electrical conductivity of 1.60 10-4 S m-1. Concerning chitosan-based composite materials, the scientific approach was the same as cellulose substrate and we obtained a percentage of grafting of 68wt%. In addition, its catalytic activity for the conversion of 4-Nitrophenol to 4-Aminophenol was of high efficiency