Photonen-Aufkonversion in Nanokapseln

Die vorliegende Dissertation zeigt eine erfolgreiche Verknüpfung der Triplett-Triplett-Annihilations-Aufkonversion (TTA-UC) mit möglichen biologischen Anwendungen. Die Grundlage für solche Anwendungen ist ein Transfer der TTA-UC aus seinem üblicherweise verwendeten organischen Medium in eine wässrige Umgebung. Um diesen Transfer zu realisieren, wurden, unter Anwendung der Technik des Miniemulsionsprozesses, in Wasser dispergierte Nanokapseln herstellt. Der Kern dieser Nanokapseln besteht aus einem flüssigen hydrophoben Medium (meist Hexadekan oder Phenylheptadekan), in dem die zur TTA-UC notwendigen Farbstoffe gelöst sind. Dieser flüssige Kern ist vollständig von einer festen Polymerhülle umschlossen und somit isoliert von seiner wässrigen Umgebung. Es wurden insgesamt drei Generationen solcher Nanokapseln hergestellt, die sich hauptsächlich im Herstellungsprozess, aber auch beim Material von Kern und Hülle unterscheiden. Mittels dieser Variationen konnten die Nanokapseln in Bezug auf Effizienz, Anregungswellenlänge und Sauerstoffempfindlichkeit optimiert werden. Bei der ersten Generation wurde die radikalische Miniemulsionspolymerisation zur Kapselbildung verwendet. Die zweite Generation wurde durch die Kombination des Lösungsmittelverdampfungsprozesses mit dem Miniemulsionsprozess entwickelt und liefert somit eine alternative Möglichkeit der Kapselbildung unter milden Reaktionsbedingungen, was eine uneingeschränkte Auswahl der UC-Farbstoffpaare ermöglicht. Durch den Einsatz unterschiedlicher Sensitizer konnte die Anregungswellenlänge der TTA-UC in den roten und in den nahen Infrarot-Bereich des sichtbaren Spektrums verschoben werden. Diese Verschiebung ist im biologischen Anwendungsbereich von enormer Bedeutung, da dort eine Überlappung mit dem natürlichen optischen Fenster von menschlicher Haut und Gewebe stattfindet. Dies reduziert die Streuung der Anregungsquelle im zu untersuchende Medium und ermöglicht hohe Eindringtiefen. Mit den Kapseln der zweiten Generation wurde zum ersten Mal TTA-UC in lebenden HeLa-Zellen (Krebszellen) und MSCs (Mesenchymale Stammzellen) nachgewiesen. Die verzögerte Fluoreszenz aus den Zellen wurde mit biologischen Standardverfahren, sowohl mit der Durchflusszytometrie (FACS) als auch am cLSM nachgewiesen. Besondere Vorteile gegenüber direkter Fluoreszenz konnten bei der Bildgebung von Zellen erreicht werden. Die relativ energiearme Anregungswellenlänge und die dazu anti-Stokes verschobene, detektierte verzögerte UC-Fluoreszenz lieferte eine bessere Bildqualität und eine sehr geringe Phototoxizität der Zellen. Die Kapseln der dritten Generation zeichnen sich durch ihre anorganische, tetraedrisch verknüpfte SiO2-Hülle aus und wurden mittels einer Grenzflächenreaktion (Sol-Gel-Prozess) in Miniemulsion hergestellt. Diese Kapseln weisen im Vergleich zu den Polymernanokapseln eine bessere UC-Effizienz auf und sind zusätzlich stabiler und robuster.

Analyse der intrazellulären Freisetzung von Wirkstoffmodellen via konfokaler Laser-Raster-Mikroskopie

In der vorliegenden Arbeit wurde gezeigt, wie man das Potential nanopartikulärer Systeme, die vorwiegend via Miniemulsion hergestellt wurden, im Hinblick auf „Drug Delivery“ ausnutzen könnte, indem ein Wirkstoffmodell auf unterschiedliche Art und Weise intrazellulär freigesetzt wurde. Dies wurde hauptsächlich mittels konfokaler Laser-Raster-Mikrokopie (CLSM) in Kombination mit dem Bildbearbeitungsprogramm Volocity® analysiert.rnPBCA-Nanokapseln eigneten sich besonders, um hydrophile Substanzen wie etwa Oligonukleotide zu verkapseln und sie so auf ihrem Transportweg in die Zellen vor einem etwaigen Abbau zu schützen. Es konnte eine Freisetzung der Oligonukleotide in den Zellen aufgrund der elektrostatischen Anziehung des mitochondrialen Membranpotentials nachgewiesen werden. Dabei war die Kombination aus Oligonukleotid und angebundenem Cyanin-Farbstoff (Cy5) an der 5‘-Position der Oligonukleotid-Sequenz ausschlaggebend. Durch quantitative Analysen mittels Volocity® konnte die vollständige Kolokalisation der freigesetzten Oligonukleotide an Mitochondrien bewiesen werden, was anhand der Kolokalisationskoeffizienten „Manders‘ Coefficients“ M1 und M2 diskutiert wurde. Es konnte ebenfalls aufgrund von FRET-Studien doppelt markierter Oligos gezeigt werden, dass die Oligonukleotide weder beim Transport noch bei der Freisetzung abgebaut wurden. Außerdem wurde aufgeklärt, dass nur der Inhalt der Nanokapseln, d. h. die Oligonukleotide, an Mitochondrien akkumulierte, das Kapselmaterial selbst jedoch in anderen intrazellulären Bereichen aufzufinden war. Eine Kombination aus Cyanin-Farbstoffen wie Cy5 mit einer Nukleotidsequenz oder einem Wirkstoff könnte also die Basis für einen gezielten Wirkstofftransport zu Mitochondrien liefern bzw. die Grundlage schaffen, eine Freisetzung aus Kapseln ins Zytoplasma zu gewährleisten.rnDer vielseitige Einsatz der Miniemulsion gestattete es, nicht nur Kapseln sondern auch Nanopartikel herzustellen, in welchen hydrophobe Substanzen im Partikelkern eingeschlossen werden konnten. Diese auf hydrophobe Wechselwirkungen beruhende „Verkapselung“ eines Wirkstoffmodells, in diesem Fall PMI, wurde bei PDLLA- bzw. PS-Nanopartikeln ausgenutzt, welche durch ein HPMA-basiertes Block-Copolymer stabilisiert wurden. Dabei konnte gezeigt werden, dass das hydrophobe Wirkstoffmodell PMI innerhalb kürzester Zeit in die Zellen freigesetzt wurde und sich in sogenannte „Lipid Droplets“ einlagerte, ohne dass die Nanopartikel selbst aufgenommen werden mussten. Daneben war ein intrazelluläres Ablösen des stabilisierenden Block-Copolymers zu verzeichnen, welches rn8 h nach Partikelaufnahme erfolgte und ebenfalls durch Analysen mittels Volocity® untermauert wurde. Dies hatte jedoch keinen Einfluss auf die eigentliche Partikelaufnahme oder die Freisetzung des Wirkstoffmodells. Ein großer Vorteil in der Verwendung des HPMA-basierten Block-Copolymers liegt darin begründet, dass auf zeitaufwendige Waschschritte wie etwa Dialyse nach der Partikelherstellung verzichtet werden konnte, da P(HPMA) ein biokompatibles Polymer ist. Auf der anderen Seite hat man aufgrund der Syntheseroute dieses Block-Copolymers vielfältige Möglichkeiten, Funktionalitäten wie etwa Fluoreszenzmarker einzubringen. Eine kovalente Anbindung eines Wirkstoffs ist ebenfalls denkbar, welcher intrazellulär z. B. aufgrund von enzymatischen Abbauprozessen langsam freigesetzt werden könnte. Somit bietet sich die Möglichkeit mit Nanopartikeln, die durch HPMA-basierte Block-Copolymere stabilisiert wurden, gleichzeitig zwei unterschiedliche Wirkstoffe in die Zellen zu bringen, wobei der eine schnell und der zweite über einen längeren Zeitraum hinweg (kontrolliert) freigesetzt werden könnte.rnNeben Nanokapseln sowie –partikeln, die durch inverse bzw. direkte Miniemulsion dargestellt wurden, sind auch Nanohydrogelpartikel untersucht worden, die sich aufgrund von Selbstorganisation eines amphiphilen Bock-Copolymers bildeten. Diese Nanohydrogelpartikel dienten der Komplexierung von siRNA und wurden hinsichtlich ihrer Anreicherung in Lysosomen untersucht. Aufgrund der Knockdown-Studien von Lutz Nuhn konnte ein Unterschied in der Knockdown-Effizienz festgestellt werden, je nach dem, ob 100 nm oder 40 nm große Nanohydrogelpartikel verwendet wurden. Es sollte festgestellt werden, ob eine größenbedingte, unterschiedlich schnelle Anreicherung dieser beiden Partikel in Lysosomen erfolgte, was die unterschiedliche Knockdown-Effizienz erklären könnte. CLSM-Studien und quantitative Kolokalisationsstudien gaben einen ersten Hinweis auf diese Größenabhängigkeit. rnBei allen verwendeten nanopartikulären Systemen konnte eine Freisetzung ihres Inhalts gezeigt werden. Somit bieten sie ein großes Potential als Wirkstoffträger für biomedizinische Anwendungen.rn

The suitability of biodegradable poly(dl-lactide-co-glycolide)75:25 microspheres for the sustained release of antibiotics

Post-operative infections resulting from total hip arthroplasty are caused by bacteria such as Staphylococcus aureus and Pseudomonas aeruginosa entering the wound perioperatively or by haemetogenous spread from distant loci of infection. They can endanger patient health and require expensive surgical revision procedures. Gentamicin impregnated poly (methyl methacrylate) bone cement is traditionally used for treatment but is often removed due to harbouring bacterial growth, while bacterial resistance to gentamicin is increasing. The aim of this work was to encapsulate the antibiotics vancomycin, ciprofloxacin and rifampicin within sustained release microspheres composed of the biodegradable polymer poly (dl-lactide-co-glycolide) [PLCG] 75:25. Topical administration to the wound in hydroxypropylmethylcellulose gel should achieve high local antibiotic concentrations while the two week in vivo half life of PLCG 75:25 removes the need for expensive surgical retrieval operations. Unloaded and 20% w/w antibiotic loaded PLCG 75:25 microspheres were fabricated using a Water in Oil emulsification with solvent evaporation technique. Microspheres were spherical in shape with a honeycomb-like internal matrix and showed reproducible physical properties. The kinetics of in vitro antibiotic release into newborn calf serum (NCS) and Hank's balanced salt solution (HBSS) at 37°C were measured using a radial diffusion assay. Generally, the day to day concentration of each antibiotic released into NCS over a 30 day period was in excess of that required to kill St. aureus and Ps. auruginosa. Only limited microsphere biodegradation had occurred after 30 days of in vitro incubation in NCS and HBSS at 37°C. The moderate in vitro cytotoxicity of 20% w/w antibiotic loaded microspheres to cultured 3T3-L1 cells was antibiotic induced. In conclusion, generated data indicate the potential for 20% w/w antibiotic loaded microspheres to improve the present treatment regimens for infections occurring after total hip arthroplasty such that future work should focus on gaining industrial collaboration for commercial exploitation.

Simulação da destilação molecular de filme descendente para o petróleo

The heavy part of the oil can be used for numerous purposes, e.g. to obtain lubricating oils. In this context, many researchers have been studying alternatives such separation of crude oil components, among which may be mentioned molecular distillation. Molecular distillation is a forced evaporation technique different from other conventional processes in the literature. This process can be classified as a special distillation case under high vacuum with pressures that reach extremely low ranges of the order of 0.1 Pascal. The evaporation and condensation surfaces must have a distance from each other of the magnitude order of mean free path of the evaporated molecules, that is, molecules evaporated easily reach the condenser, because they find a route without obstacles, what is desirable. Thus, the main contribution of this work is the simulation of the falling-film molecular distillation for crude oil mixtures. The crude oil was characterized using UniSim® Design and R430 Aspen HYSYS® V8.5. The results of this characterization were performed in spreadsheets of Microsoft® Excel®, calculations of the physicochemical properties of the waste of an oil sample, i.e., thermodynamic and transport. Based on this estimated properties and boundary conditions suggested by the literature, equations of temperature and concentration profiles were resolved through the implicit finite difference method using the programming language Visual Basic® (VBA) for Excel®. The result of the temperature profile showed consistent with the reproduced by literature, having in their initial values a slight distortion as a result of the nature of the studied oil is lighter than the literature, since the results of the concentration profiles were effective allowing realize that the concentration of the more volatile decreases and of the less volatile increases due to the length of the evaporator. According to the transport phenomena present in the process, the velocity profile tends to increase to a peak and then decreases, and the film thickness decreases, both as a function of the evaporator length. It is concluded that the simulation code in Visual Basic® language (VBA) is a final product of the work that allows application to molecular distillation of petroleum and other similar mixtures.

In-situ carbon control in the preparation of precursors to boron carbide by a non-aqueous solution technique

Synthesis of high quality boron carbide (B4C) powders is achieved by carbothermal reduction of boron oxide (B2O3) from a condensed boric acid (H3BO3)/polyvinyl acetate (PVAc) product. Precursor solutions are prepared via free radical polymerisation of vinyl acetate (VA) monomer in methanol in the presence of dissolved H3BO3. A condensed product is then formed by flash evaporation under vacuum. As excess VA monomer is removed at the evaporation step, the polymerisation time is used to manage availability of carbon for reaction. This control of carbon facilitates dispersion of H3BO3 in solution due to the presence of residual VA monomer. B4C powders with very low residual carbon are formed at temperatures as low as 1,250 °C with a 4 hour residence time.

Optical, Field-Emission, and Antimicrobial Properties of ZnO Nanostructured Films Deposited at Room Temperature by Activated Reactive Evaporation

ZnO nanostructures were deposited on flexible polymer sheet and cotton fabrics at room temperature by activated reactive evaporation. Room-temperature photoluminescence spectrum of ZnO nanostructured film exhibited a week intrinsic UV emission and a strong broad yellow-orange visible emission. TEM and HRTEM studies show that the grown nanostructures are crystalline in nature and their growth direction was indentified to be along [002]. ZnO nanostructures grown on the copper-coated flexible polymer sheets exhibited stable field-emissio characteristics with a threshold voltage of 2.74 V/mu m (250 mu A) and a very large field enhancement factor (beta) of 23,213. Cotton fabric coated with ZnO nanostructures show an excellent antimicrobial activity against Staphylococcus aureus bacteria (Gram positive), and similar to 73% reduction in the bacterial population is achieved compared to uncoated fabrics after 4 h in viability. Using a shadow mask technique, we also selectively deposited the nanostructures at room temperature on polymer substrates.

Growth of rutile TiO2 nanorods on TiO2 seed layer deposited by electron beam evaporation

Dense rutile TiO2 nanorods were grown on anatase TiO2 seed layer coated glass substrate by solution technique. The crystalline nature of nanorods has confirmed by transmission electron microscopy. The band gap of the TiO2 seed layer and nanorods were calculated using the UV-vis absorption spectrum and the band gap value of the anatase seed layer and rutile nanorods were 3.39 eV and 3.09 eV respectively. Water contact angle measurements were also made and showed that the contact angle of rutile nanorods was (134 degrees) larger than the seed layer contact angle (93 degrees). The RMS surface roughness of the TiO2 seed layer (0.384 nm) and nanorods film (18.5 nm) were measured by an atomic force microscope and correlated with their contact angle values. (C) 2011 Elsevier B.V. All rights reserved.

Growth of Germanium Nanowires by electron beam evaporation

Growth of high density germanium nanowires on Si substrates by electron beam evaporation (EBE) has been demonstrated using gold as catalyst. The germanium atoms are provided by evaporating germanium by electron beam evaporation (EBE) technique. Effect of substrate (growth) temperature and deposition time on the growth of nanowires has studied. The morphology of the nanowires was investigated by field emission scanning electron microscope (FESEM). It has been observed that a narrow temperature window from 380 degrees C to 480 degrees C is good for the nanowires growth as well as restriction on the maximum length of nanowires. It is also observed that high substrate temperature leading to the completely absence of nanowire growth.

Suspended multiwalled carbon nanotubes as self-aligned evaporation masks

We describe the nanofabrication study of self-aligned electrodes on suspended multiwalled carbon nanotube structures. When metal is deposited on a suspended multiwalled carbon nanotube structure, the nanotube acts as an evaporation mask, resulting in the formation of discontinuous electrodes. The metal deposits on the nanotubes are removed with lift-off. Using Al sacrificial layers, it was possible to fabricate self-aligned contact electrodes and control electrodes nanometers from the suspended carbon nanotubes with a single lithography step. It was also shown that the fabrication technique may also be used to form nano-gapped contact electrodes. The technique should prove useful for the fabrication of nano-electromechanical systems.

I. The effect of droplet solidification upon two-phase flow in a rocket nozzle. II. A kinetic theory investigation of some condensation-evaporation phenomena by a moment method

Part I:

The perturbation technique developed by Rannie and Marble is used to study the effect of droplet solidification upon two-phase flow in a rocket nozzle. It is shown that under certain conditions an equilibrium flow exists, where the gas and particle phases have the same velocity and temperature at each section of the nozzle. The flow is divided into three regions: the first region, where the particles are all in the form of liquid droplets; a second region, over which the droplets solidify at constant freezing temperature; and a third region, where the particles are all solid. By a perturbation about the equilibrium flow, a solution is obtained for small particle slip velocities using the Stokes drag law and the corresponding approximation for heat transfer between the particle and gas phases. Singular perturbation procedure is required to handle the problem at points where solidification first starts and where it is complete. The effects of solidification are noticeable.

Part II:

When a liquid surface, in contact with only its pure vapor, is not in the thermodynamic equilibrium with it, a net condensation or evaporation of fluid occurs. This phenomenon is studied from a kinetic theory viewpoint by means of moment method developed by Lees. The evaporation-condensation rate is calculated for a spherical droplet and for a liquid sheet, when the temperatures and pressures are not too far removed from their equilibrium values. The solutions are valid for the whole range of Knudsen numbers from the free molecule to the continuum limit. In the continuum limit, the mass flux rate is proportional to the pressure difference alone.

Laser-induced damage threshold of ZrO2 thin films prepared at different oxygen partial pressures by electron-beam evaporation

ZrO2, films were deposited by electron-beam evaporation with the oxygen partial pressure varying from 3 X 10(-3) Pa to I I X 10(-3) Pa. The phase structure of the samples was characterized by x-ray diffraction (XRD). The thermal absorption of the films was measured by the surface thermal lensing technique. A spectrophotometer was employed to measure the refractive indices of the samples. The laser-induced damage threshold (LIDT) was assessed using a 1064, nm Nd: yttritium-aluminium-garnet pulsed laser at pulse width of 12 ns. The influence of oxygen partial pressure on the microstructure and LIDT of ZrO2 films was investigated. XRD data revealed that the films changed from polycrystalline to amorphous as the oxygen partial pressure increased. The variation of refractive index at 550 nm wavelength indicated that the packing density of the films decreased gradually with increasing oxygen partial pressure. The absorptance of the samples decreased monotonically from 125.2 to 84.5 ppm with increasing oxygen partial pressure. The damage threshold, values increased from 18.5 to 26.7 J/cm(2) for oxygen partial pressures varying from 3 X 10(-3) Pa to 9 X 10(-3) Pa, but decreased to 17.3 J/cm(2) in the case of I I X 10(-3) Pa. (C) 2005 American Vacuum Society.

Laser-induced damage threshold of ZrO2 thin films prepared at different oxygen partial pressures by electron-beam evaporation

ZrO2, films were deposited by electron-beam evaporation with the oxygen partial pressure varying from 3 X 10(-3) Pa to I I X 10(-3) Pa. The phase structure of the samples was characterized by x-ray diffraction (XRD). The thermal absorption of the films was measured by the surface thermal lensing technique. A spectrophotometer was employed to measure the refractive indices of the samples. The laser-induced damage threshold (LIDT) was assessed using a 1064, nm Nd: yttritium-aluminium-garnet pulsed laser at pulse width of 12 ns. The influence of oxygen partial pressure on the microstructure and LIDT of ZrO2 films was investigated. XRD data revealed that the films changed from polycrystalline to amorphous as the oxygen partial pressure increased. The variation of refractive index at 550 nm wavelength indicated that the packing density of the films decreased gradually with increasing oxygen partial pressure. The absorptance of the samples decreased monotonically from 125.2 to 84.5 ppm with increasing oxygen partial pressure. The damage threshold, values increased from 18.5 to 26.7 J/cm(2) for oxygen partial pressures varying from 3 X 10(-3) Pa to 9 X 10(-3) Pa, but decreased to 17.3 J/cm(2) in the case of I I X 10(-3) Pa. (C) 2005 American Vacuum Society.

Influences of oxygen partial pressure on structure and related properties of ZrO2 thin films prepared by electron beam evaporation deposition

ZrO2 thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on structure and related properties of ZrO2 thin films were studied. Transmittance, thermal absorption, structure and residual stress of ZrO2 thin films were measured by spectrophotometer, surface thermal lensing technique (STL), X-ray diffraction and optical interferometer, respectively. The results showed that the structure and related properties varied progressively with the increase of oxygen partial pressure. The refractive indices and the packing densities of the thin films decreased when the oxygen partial pressure increased. The tetragonal phase fraction in the thin films decreased gradually as oxygen partial pressure increased. The residual stress of film deposited at base pressure was high compressive stress, the value decreased with the increase of oxygen partial pressure, and the residual stress became tensile with the further increase of oxygen pressure, which was corresponding to the evolution of packing densities and variation of interplanar distances. (c) 2007 Elsevier B.V. All rights reserved.

Influence of oxygen post-treatment on laser-induced damage of antireflection coatings prepared by electron-beam evaporation and ion beam assisted deposition

Antireflection coatings at the center wavelength of 1053 nm were prepared on BK7 glasses by electron-beam evaporation deposition (EBD) and ion beam assisted deposition (IBAD). Parts of the two kinds of samples were post-treated with oxygen plasma at the environment temperature after deposition. Absorption at 1064 nm was characterized based on surface thermal lensing (STL) technique. The laser-induced damage threshold (LIDT) was measured by a 1064-nm Nd:YAG laser with a pulse width of 38 ps. Leica-DMRXE Microscope was applied to gain damage morphologies of samples. The results revealed that oxygen post-treatment could lower the absorption and increase the damage thresholds for both kinds of as-grown samples. However, the improving effects are not the same. (c) 2008 Elsevier B.V. All rights reserved.

Synthesis of GaN nanowires and nano-pyramids in a two-hot-boat chemical vapor deposition system via an in-doping technique

A two-hot-boat chemical vapor deposition system was modified from a thermal evaporation equipment. This system has the advantage of high vacuum, rapid heating rate and temperature separately controlled boats for the source and samples. These are in favor of synthesizing compound semiconducting nano-materials. By the system, we have synthesized high-quality wurtzite single crystal GaN nanowires and nanotip triangle pyramids via an in-situ doping indium surfactant technique on Si and 3C-SiC epilayer/Si substrates. The products were analyzed by x-ray diffraction, field emission scanning electron microscopy, highresolution transmission electron microscopy, energy- dispersive x-ray spectroscopy, and photoluminescence measurements. The GaN nanotip triangle pyramids, synthesized with this novel method, have potential application in electronic/ photonic devices for field-emission and laser.