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Infektionen medizinscher Titanoberflächen stellen ein aktuelles Problem in der rekonstruktiven Medizin dar. Dabei wird oft versucht, diesem Problem mit systemischer Antibiotikaanwendung zu begegnen, die jedoch Resistenzentstehung begünstigt und am Ort der Infektion nur einen oft unzureichenden Wirkspiegel ermöglicht. Eine mögliche Verbesserung wir hierbei in lokaler Wirkstofffreisetzung gesehen. Gegenstand dieser Arbeit war die Modifikation medizinischer Titanoberflächen mittels Anodisierung in fluoridhaltigen Elektrolyten und die Abschätzung ihres Potentials hinsichtlich der Einlagerung und der Freisetzung ausgewählter antibakteriell wirksamer Substanzen. Durch die Anodisierung der Titanoberflächen konnten Titannanotubes aus Titanoxiden mit Röhrenlängen von bis zu 6,54 m und Röhrendurchmessern von bis zu 160 nm erzeugt werden. Als Modellwirkstoffe wurden das noch heute als Reserveantibiotikum gegen manche Problemkeime geltende Chemotherapeutikum Vancomycin, sowie Silber als Element mit breiter antibakterieller Wirkung, verwendet. Es konnte gezeigt werden, dass durch die Oberflächenvergrößerung, die sich aus der Entstehung von nanotubeförmigem Titanoxid ergab, im Vergleich zu nicht anodisierten Referenzproben um bis zu 447 % mehr Wirkstoff eingelagert werden konnte. In der Freisetzungskinetik von Vancomycin zeigten sich oberflächenabhängig deutliche Unterschiede. Dabei setzten Titanoberflächen, die in einem Elektrolyten auf Wasserbasis anodisiert worden waren, den adsorbierten Wirkstoff schneller frei als die Referenzproben, während das Vancomycin auf Oberflächen, die in einem Elektrolyten auf Ethylenglycolbasis modifiziert worden waren, deutlich retardiert über einen Zeitraum von circa 305 Tagen freigesetzt wurde. Des weiteren wurde Silber in Proben eingelagert, die in einem Elektrolyten auf Wasserbasis anodisiert worden waren. Auch für Silber resultierte eine deutliche Steigerung der Gesamtmenge des adsorbierten Wirkstoffs um bis zu 229 %. Dabei war seine Freisetzung, verglichen mit der Referenzprobe, deutlich verzögert. Durch die Anodisierung der Titanproben in fluoridhaltigen Elektrolyten konnten Oberflächen erzeugt werden, die entsprechend ihrer Morphologie verschiedene Wirkstoffbeladungen und Freisetzungskinetiken ermöglichen. Hinsichtlich der unterschiedlichen Anforderungen in der klinischen Medizin nach Abgabemenge und Abgabekinetik antibakteriell wirksamer Substanzen zur postoperativen Infektionsprävention offerieren diese Oberflächenmodifikationen ein hohes Potential für die Erzeugung schnell verfügbarer und kostengünstiger Drug-Release-Systeme.
Nanoelectronics is an essential technology for down-scaling beyond the limit of silicon-based electronics. Single-Wall Carbon Nanotubes (SWNT) are semiconducting components that exhibit a large variety of properties that make them usable for sensing, telecommunication, or computational tasks. Due to their high surface to volume ratio, carbon nanotubes are strongly affected by molecular adsorptions, and almost all properties depend on surface adsorption. SWNT with smaller diameters (0.7-0.9nm) show a stronger sensitivity to surface effects. An optimized synthesis route was developed to produce these nanotubes directly. They were produced with a clean surface, high quality, and large lengths of 2 μ m. The results complement previous studies on larger diameters (0.9-1.4nm). They allow performing statistically significant assumptions for a perfect nanotube, which is selected from a subset of nanotubes with good emission intensity, and high mechanical durability. The adsorption of molecules on the surface of carbon nanotubes influences the motion and binding strength of chargeseparated states in this system. To gain insight into the adsorption processes on the surface with a minimum of concurrent overlapping effects, a microscopic setup, and a measurement technique were developed. The system was estimated to exhibit excellent properties like long exciton diffusion lengths (>350nm), and big exciton sizes (8.5(5)nm), which was substantiated by a simulation. We studied the adsorption processes at the surface of Single-Wall Carbon Nanotubes for molecules in the gas phase, solvent molecules, and surfactant molecules. The experiments were all carried out on suspended individualized carbon nanotubes on a silicon wafer substrate. The experiments in the gas-phase showed that the excitonic emission energy and intensity experiences a rapid blue shift during observation. This shift was associated with the spontaneous desorption of large clusters of gaseous molecules caused by laser heat up. The measurement of this desorption was essential for creating a reference to an initially clean surface and allows us to perform a comparison with previous measurements on this topic. Furthermore, the adsorption of hydrogen on the nanotube surface at high temperatures was investigated. It was found that a new emission mode arises slightly red-shifted to the excitonic emission in these systems. The new signal is almost equally strong as the main excitonic peak and was associated with the brightening of dark excitons at sp3-defects through a K-phonon assisted pathway. The finding is useful for the direct synthesis of spintronic devices as these systems are known to act as single-photon emitters. The suspended nanotubes were further studied to estimate the effect of solvent adsorption on the excitonic states during nanotube dispersion for each nanotube individually. A significant quantum yield loss is observable for hexane and acetonitrile, while the emission intensity was found to be the strongest in toluene. The reference to a clean surface allowed us to estimate the exact influence of the dielectric environment of adsorbing solvents on the excitonic emission energy. Solvent adsorption was found to lead to an energy shift that is almost twice as high as suggested in previous studies. The amount of this energy shift, however, was comparably similar for all solvents, which suggests that the influence of the distinct dielectric constant in the outer environment less significantly influences the energy shift than previously thought. An interesting phenomenon was found when using acetonitrile as a solvent, which leads to greatly enhanced emission properties. The emission is more than twice as high as in the same air-suspended nanotubes, which suggests a process that depends on the laser intensity. In this study, it was reasonably explained how an energy down-conversion is possible through the coupling of the excitonic states with solvent vibrations. The strength of this coupling, however, also suggests adsorptions to the inside of the tubular nanotube structure leading to a coupled vibration of linear acetonitrile molecules that are adsorbed to the inner surface. The findings are important for the field of nanofluidics and provide an excellent system for efficient energy down-conversion in the transmission window of biological tissue. Having separated the pure effect of solvent adsorption allowed us to study the undisturbed molecular adsorption of polymers in these systems. The addition of polyfluorene polymer leads to a slow but stepwise intensity increase. The intensity increase is overlapping with a concurrent process that leads to an intensity decrease. Unfortunately, observing the stepwise process has a low spacial resolution of only 100-250nm, which is in the range of the exciton diffusion length in these systems and hinders detailed analysis. The two competing and overlapping processes processes are considered to originate from slow π-stacking and fast side-chain binding. Insights into this process are essential for selecting suitably formed polymers. However, the findings also emphasize the importance of solvent selection during nanotube dispersion since solvent effects were proven to be far more critical on the quantum yield in these systems. These measurements can shed light on the ongoing debate on polymers adsorption during nanotube individualization and allow us to direct the discussion more towards the selection of suitable solvents. This work provides fundamental insights into the adsorption of various molecules on the surface of individually observed suspended Single-Wall Carbon Nanotubes. It allows observing the adsorption of individual molecules below the optical limit in the solid, liquid, and gas phases. Nanotubes are able to act as sensing material for detecting changes in their direct surrounding. These fundamental findings are also crucial for increasing the quantum yield of solvent-dispersed nanotubes. They can provide better light-harvesting systems for microscopy in biological tissue and set the base for a more efficient telecommunication infrastructure with nano-scale spintronics devices and lasing components. The newly discovered solvent alignment in the nanotube surrounding can potentially also be used for supercapacitors that are needed for caching the calculation results in computational devices that use polymer wrapped nanotubes as transistors. Although fundamental, these studies develop a strategy to enlighten this room that is barely only visible at the bottom of the nano-scale.
A donor-acceptor-donor (D-A-D) type naphthalene-diimide (NDI-H) chromophore exhibits highly cooperative J-aggregation leading to nanotubular self-assembly and gelation in n-decane, as demonstrated by UV/Vis, FT-IR, photoluminescence and microscopy studies. Analysis of temperature-dependent UV/Vis spectra using the nucleation-elongation model and FT-IR data reveals the molecular origin of the cooperative nature of the self-assembly. The supramolecular polymerization is initiated by H-bonding up to a degree of polymerization similar to 20-25, which in a subsequent elongation step promotes J-aggregation in orthogonal direction leading to possibly a sheet-like structure that eventually produces nanotubes. Time-resolved fluorescence and absorption measurements demonstrate that such a tubular assembly enables very effective delocalization of excited states resulting in a remarkably prolonged excited state lifetime.