TY - THES A1 - Derese, Solomon A1 - Yenesew, Abiy A1 - Midiwo, Jacob O. A1 - Heydenreich, Matthias A1 - Peter, Martin G. T1 - A new isoflavone from stem bark of Millettia dura Y1 - 2003 SN - 1011-3924 ER - TY - THES A1 - Bahrke, Sven A1 - Einarsson, Jon M. A1 - Gislason, Johannes A1 - Haebel, Sophie A1 - Peter-Katalinic, Jasna A1 - Peter, Martin G. T1 - Characterization of chitooligosaccharides by mass spectrometry Y1 - 2003 SN - 82-47-15901-5 ER - TY - THES A1 - Taden, Andreas Jörg T1 - Kristalisationsphänomene in Minienmulsionssystemen : geordnete Strukturen und Anwendungen für die enzymatische Polymerisation Y1 - 2003 ER - TY - THES A1 - Wohlrab, Erdmann Sebastian T1 - Polymerinduzierte Morphogenese bei der Kristalisation von Aminosäuren Y1 - 2003 ER - TY - THES A1 - Lucas, Gordon T1 - Gradientenzentrifugation : neue Anwendungen eines klassischen Verfahrens Y1 - 2003 ER - TY - THES A1 - Ibarz-Ric, Gemma T1 - Controlling internal structure and permeability of polyelectrolyte multilayer microcapsules Y1 - 2003 ER - TY - THES A1 - Schöler, Björn T1 - Einfluss der Ladungsdichte aud den Aufbau von Polyelektrolyt Multischichten mit der Layer-by-Layer Technik Y1 - 2003 ER - TY - THES A1 - Schütz, Peter T1 - Dünne Kompostfilme aus Nanopartikeln und Polyelektrolyten Y1 - 2003 ER - TY - THES A1 - Thomas, Arne Christian T1 - Poröse Silikate durch Nanocasting : von chiralen Templaten zu neuer Chemie in Poren Y1 - 2003 ER - TY - THES A1 - Wang, Liying T1 - Lipid monolayers coupled to polyelectrolyte multilayers : stability, dynamics and interactions Y1 - 2003 ER - TY - THES A1 - Radtchenko, Igor Leonidovich T1 - Nanoengineered polymeric capsules as physico-chemical microreactors Y1 - 2003 ER - TY - THES A1 - Klod, Sabrina T1 - Elektronische, sterische und Anistorische-Effekte in Push-pull-Alkenen : NMR-spektroskopische und quantenchemische Untersuchungen Y1 - 2003 ER - TY - THES A1 - Antipov, Alexei T1 - Polyelectrolyte multilayer capsules as controlled permeability vehicles and catalyst carriers Y1 - 2003 ER - TY - THES A1 - Engelhard, Sonja T1 - Optische Verfahren zur Qualitätskontrolle von Bier und zur Zellzahlbestimung in S. cerevisiae Kultivierungen Y1 - 2003 ER - TY - THES A1 - Tzoneva-Velinova, Rumiana T1 - The wettability of biomaterials determines the protein adsorption and the cellular responses N2 - During the past several decades polymer materials become widely used as components of medical devices and implants such as hemodialysers, bioartificial organs as well as vascular and recombinant surgery. Most of the devices cannot avoid the blood contact in their use. When the polymer materials come in contact with blood they can cause different undesired host responses like thrombosis, inflammatory reactions and infections. Thus the materials must be hemocompatible in order to minimize these undesired body responses. The earliest and one of the main problems in the use of blood-contacting biomaterials is the surface induced thrombosis. The sequence of the thrombus formation on the artificial surfaces has been well established. The first event, which occurs, after exposure of biomaterials to blood, is the adsorption of blood proteins. Surface physicochemical properties of the materials as wettability greatly influence the amount and conformational changes of adsorbed proteins. In turn the type, amount and conformational state of the adsorbed protein layer determines whether platelets will adhere and become activated or not on the artificial surface and thus to complete the thrombus formation. The adsorption of fibrinogen (FNG), which is present in plasma, has been shown to be closely related to surface induced thrombosis by participating in all processes of the thrombus formation such as fibrin formation, platelet adhesion and aggregation. Therefore study the FNG adsorption to artificial surfaces could contribute to better understanding of the mechanisms of platelet adhesion and activation and thus to controlling the surface induced thrombosis. Endothelization of the polymer surfaces is one of the strategies for improving the materials hemocompatibility, which is believed to be the most ideal solution for making truly blood-compatible materials. Since at physiological conditions proteins such as FNG and fibronectin (FN) are the usual extracellular matrix (ECM) for endothelial cells (EC) adhesion, precoating of the materials with these proteins has been shown to improve EC adhesion and growth in vitro. ECM proteins play an essential role not only like a structural support for cell adhesion and spreading, but also they are important factor in transmitting signals for different cell functions. The ability of cells to remodel plasma proteins such as FNG and FN in matrix-like structures together with the classical cell parameters such as actin cytoskeleton and focal adhesion formation could be used as an criteria for proper cell functioning. The establishment and the maintaining of delicate balance between cell-cell and cell-substrate contacts is another important factor for better EC colonization of the implants. The functionality of newly established endothelium in order to produce antithromotic substances should be always considered when EC seeding is used for improving the hemocompatibility of the polymer materials. Controlling the polymer surface properties such as surface wettability represents a versatile approach to manipulate the above cellular responses and therefore can be used in biomaterial and tissue engineering applications for producing better hemocompatible materials. KW - wettability KW - hemocompatibility KW - extracellular matrix proteins KW - endothelization Y1 - 2003 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0001103 ER - TY - THES A1 - Sobal, Neli T1 - Kolloidale Nanosysteme aus magnetischen und metallischen Materialien : Synthese und Charakterisierung N2 - Ein Spezialgebiet der modernen Mikroelektronik ist die Miniaturisierung und Entwicklung von neuen nanostrukturierten und Komposit-Materialen aus 3d-Metallen. Durch geeignete Zusammensetzungen können diese sowohl mit einer hohen Sättigungsmagnetisierung und Koerzitivfeldstärke als mit besserer Oxidationsbeständigkeit im Vergleich zu den reinen Elementen erzielt werden. In der vorliegenden Arbeit werden neue Methoden für die Herstellung von bimetallischen kolloidalen Nanopartikeln vor allem mit einer Kern-Hülle-Struktur (Kern@Hülle) präsentiert. Bei der überwiegenden Zahl der vorgestellten Reaktionen handelt es sich um die thermische Zersetzung von metallorganischen Verbindungen wie Kobaltcarbonyl, Palladium- und Platinacetylacetonate oder die chemische Reduktion von Metallsalze mit langkettigem Alkohol in organischem Lösungsmittel. Daneben sind auch Kombinationen aus diesen beiden Verfahren beschrieben. Es wurden Kolloide aus einem reinen Edelmetall (Pt, Pd, Ag) in einem organischen Lösungsmittel synthetisiert und daraus neue, bisher in dieser Form nicht bekannte Ag@Co-, Pt@Co-, Pd@Co- und Pt@Pd@Co-Nanopartikel gewonnen. Der Kobaltgehalt der Ag@Co-, Teilchen konnte im Bereich von 5 bis 73 At. % beliebig eingestellt werden. Der mittlere Durchmesser der Ag@Co-Partikel wurde von 5 nm bis 15 nm variiert. Bei der Herstellung von Pt@Co-Teilchen wurde eine unterschiedlich dicke Kobalt-Hülle von ca. 1,0 bis 2,5 nm erzielt. Im Fall des Palladiums wurden sowohl monodispere als auch polydisperse Pd-Nanopartikel mit einer maximal 1,7-2,0nm dicken Kobalthülle synthetisiert. Ein großer Teil dieser Arbeit befasst sich mit den magnetischen Eigenschaften der kolloidalen Teilchen, wobei die SQUID-Magnetometrie und Röntgenzirkulardichroismus (XMCD) dafür eingesetzt wurden. Weil magnetische Messungen alleine nur indirekte Schlüsse über die untersuchten Systeme erlauben, wurde dabei besonderer Wert auf die möglichst genaue strukturelle Charakterisierung der Proben mittels moderner Untersuchungsmethoden gelegt. Röntgendiffraktometrie (XRD), Röntgenabsorptionsfeinstruktur- (EXAFS) und UV-Vis-Spektroskopie sowie Transmissionselektronenmikroskopie (TEM) in Kombination mit Elektronen Energieverlustspektroskopie (EELS) und energiedispersive Röntgenfluoreszensanalyse (EDX) wurden verwendet. N2 - Magnetic colloidal particles are attractive because of their possible application to ultra-high-density magnetic data storage media, sensors, electronic devices and medical diagnostics. The properties of small particles depend on their composition, shape, and method of preparation. The combination of 3d-metals (Fe, Co, Ni) with noble metals improves the stability of the colloids and leads to new properties of the magnetic systems, often distinct from those of the corresponding monometallic particles. Core-shell particles, where dia- or paramagnetic noble metal-cores are surrounded by a ferromagnetic Co-shell, are an interesting system to study surface and interfacial magnetism such as an induced polarization or a giant magnetoresistance effect. In this work, new synthetic routes for the preparation of monometallic (Pt, Pd, Ag) and bimetallic magnetic nanocrystals (Ag@Co, Pt@Co, Pd@Co) with core-shell structure are presented. Stable colloids with a narrow particle size distribution were obtained in organic solvents using methods of wet chemistry. The method of preparation of Ag@Co is based on the thermal decomposition of dicobalt octycarbonyl in combination with a transmetalation reaction with water free AgClO4. The cobalt amount in the Ag@Co system could be tuned from 5 to 73 at. %. The average diameter of the particles was varied from 5 to 15 nm. The reduction of platinum and palladium salts in organic solution using long chained alcohol as the reductant leads to stable metal nanostructures. Monodisperse Pd and Pt particles with average sizes of 1.7 to 7.0 nm were synthesized via thermal decomposition of metal-surfactant complexes too. Alkylamines and alkylphosphines were used in this procedure. The thickness of the Co-shell was controlled by a simple high-temperature thermolysis of dicobalt octacarbonyl at the presence of Pd and Pt seeds and was tunable from 0.5 to 2.5 nm. The crystalline structure of the samples was characterized by transmission electron microscopy (TEM), energy dispersive x-ray spectroscopy (EDX), UV-VIS and electron-energy loss spectroscopy (EELS). SQUID magnetometry, x-ray magnetic circular dichroism (XMCD) and extended x-ray absorption fine structure (EXAFS) measurements gave information about the magnetic properties of the bimetallic systems and revealed their dependency on the particle size and the chemical composition. A high spin to orbital moments ratio µL/µS of 0.26±0.06 for Ag@Co and 0.22±0.05 for Pt@Co nanocrystals was observed at XMCD measurements due to the lowered dimensionality the investigated systems. KW - Kolloid KW - AgCo KW - PtCo KW - PdCo KW - TEM KW - EDX KW - EELS KW - XMCD KW - Kern-Hülle KW - Herstellung KW - Nanopartikel KW - Kobaltcarbonyl KW - Acetylacetonat KW - Colloid KW - AgCo KW - PtCo KW - PdCo KW - TEM KW - EDX KW - EELS KW - XMCD KW - core-shell KW - synthesis KW - nanoparticles KW - organic solvent KW - decomposition KW - reduction KW - cobalt dicarbonyl KW - a Y1 - 2003 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0001071 ER - TY - THES A1 - Krasia, Theodora T1 - Synthese und kolloidale Eigenschaften neuartiger Blockcopolymere mit beta-Dicarbonyl Einheiten = Synthesis and colloidal properties of a novel type of block copolymers bearing beta-dicarbonyl residues T1 - Synthese und kolloidale Eigenschaften neuartiger Blockcopolymere mit beta-Dicarbonyl Einheiten N2 - The present work is dealing with the first synthesis and characterisation of amphiphilic diblock copolymers bearing b-dicarbonyl (acetoacetoxy) chelating residues. Polymers were obtained by Group Transfer Polymerisation (GTP)/acetoacetylation and controlled radical polymerisation techniques (RAFT).Different micellar morphologies of poly(n-butyl methacrylate)-block-poly[2-(acetoacetoxy)ethyl methacrylate] (pBuMA-b-pAEMA) were observed in cyclohexane as a selective solvent. Depending on the block length ratio, either spherical, elliptical, or cylindrical micelles were formed. The density of the polymer chains at the core/corona interface is considerably higher as compared to any other strongly segregating system reported in the literature. It is demonstrated that there are H-bond interactions existing between acetoacetoxy groups, which increase the incompatibility between block segments. In addition, such interactions lead to the formation of secondary structures (such as b-sheets or globular structures) and larger superstructures in the micrometer length scale.Block copolymers were also used to solubilise metal ion salts of different geometries and oxidation states in organic media, in which are otherwise insoluble. Sterically stabilised colloidal hybrid materials are formed, i.e. monodisperse micelles having the metal ion salt incorporated in their core upon complexation with the ligating pAEMA block, whereas pBuMA forms the solvating corona responsible for stabilisation in solution. Systematic studies show that the aggregation behaviour is dependent on different factors, such as the tautomeric form of the beta-dicarbonyl ligand (keto/enol) as well as the nature and amount of added metal ion salt. T2 - Synthesis and colloidal properties of a novel type of block copolymers bearing beta-dicarbonyl residues KW - amphiphilic block copolymers KW - chelates KW - Group Transfer polymerisation KW - reversible addition-fragmentation chain transfer KW - micelles KW - organic-inorganic c Y1 - 2003 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0000787 ER - TY - THES A1 - Montenegro, Rivelino V. D. T1 - Crystallization, biomimetics and semiconducting polymers in confined systems T1 - Kristallisation, Biomimetik und halbleitende Polymere in räumlich begrenzten Systemen N2 - populärwissenschaftlicher Abstract: Kristallisation, Biomimetik und halbleitende Polymere in räumlich begrenzten Systemen: Öl und Wasser mischen sich nicht, man kann aber aus beiden Flüssigkeiten Emulsionen herstellen, bei denen Tröpfchen der einen Flüssigkeit in der anderen Flüssigkeit vorliegen. Das heißt, es können entweder Öltröpfchen in Wasser oder Wassertröpfchen in Öl erzeugt werden. Aus täglichen Erfahrungen, z.B. beim Kochen weiß man jedoch, dass sich eine Emulsion durch Schütteln oder Rühren herstellen lässt, diese jedoch nicht besonders stabil ist. Mit Hilfe von hohen Scherenergien kann man nun sehr kleine, in ihrer Größe sehr einheitliche und außerdem sehr stabile Tröpfchen von 1/10000 mm erhalten. Eine solche Emulsion wird Miniemulsion genannt. In der Dissertation wurden nun z.B. Miniemulsionen untersucht, die aus kleinen Wassertröpfchen in einem Öl bestehen. Es konnte gezeigt werden, dass das Wasser in diesen Tröpfchen, also in den räumlich begrenzten Systemen, nicht bei 0 °C, sondern bei -22 °C kristallisierte. Wie lässt sich das erklären? Wenn man einen Eimer Wasser hat, dann bildet sich normalerweise bei 0 °C Eis, da nämlich in dem Wasser einige (manchmal ganz wenige) Keime (z.B. Schutzteilchen, ein Fussel etc.) vorhanden sind, an denen sich die ersten Kristalle bilden. Wenn sich dann einmal ein Kristall gebildet hat, kann das Wasser im gesamten Eimer schnell zu Eis werden. Ultrareines Wasser würde bei -22 °C kristallisieren. Wenn man jetzt die Menge Wasser aus dem Eimer in kleine Tröpfchen bringt, dann hat man eine sehr, sehr große Zahl, nämlich 1017 Tröpfchen, in einem Liter Emulsion vorliegen. Die wenigen Schmutzpartikel verteilen auf sehr wenige Tröpfchen, die anderen Tröpfchen sind ultrarein. Daher kristallisieren sie erst bei -22 °C. Im Rahmen der Arbeit konnte auch gezeigt werden, dass die Miniemulsionen genutzt werden können, um kleine Gelatine-Partikel, also Nanogummibärchen, herzustellen. Diese Nanogummibärchen quellen bei Erhöhung der Temperatur auf ca. 38 °C an. Das kann ausgenutzt werden, um zum Beispiel Medikamente zunächst in den Partikeln im menschlichen Körper zu transportieren, die Medikamente werden dann an einer gewünschten Stelle freigelassen. In der Arbeit wurde auch gezeigt, dass die Gelatine-Partikel genutzt werden können, um die Natur nachzuahnen (Biomimetik). Innerhalb der Partikel kann nämlich gezielt Knochenmaterial aufgebaut werden kann. Die Gelatine-Knochen-Partikel können dazu genutzt werden, um schwer heilende oder komplizierte Knochenbrüche zu beheben. Gelatine wird nämlich nach einigen Tagen abgebaut, das Knochenmaterial kann in den Knochen eingebaut werden. LEDs werden heute bereits vielfältig verwendet. LEDs bestehen aus Halbleitern, wie z.B. Silizium. Neuerdings werden dazu auch halbleitende Polymere eingesetzt. Das große Problem bei diesen Materialien ist, dass sie aus Lösungsmitteln aufgebracht werden. Im Rahmen der Doktorarbeit wurde gezeigt, dass der Prozess der Miniemulsionen genutzt werden kann, um umweltfreundlich diese LEDs herzustellen. Man stellt dazu nun wässrige Dispersionen mit den Polymerpartikeln her. Damit hat man nicht nur das Lösungsmittel vermieden, das hat nun noch einen weiteren Vorteil: man kann nämlich diese Dispersion auf sehr einfache Art verdrucken, im einfachsten Fall verwendet man einfach einen handelsüblichen Tintenstrahldrucker. N2 - The colloidal systems are present everywhere in many varieties such as emulsions (liquid droplets dispersed in liquid), aerosols (liquid dispersed in gas), foam (gas in liquid), etc. Among several new methods for the preparation of colloids, the so-called miniemulsion technique has been shown to be one of the most promising. Miniemulsions are defined as stable emulsions consisting of droplets with a size of 50-500 nm by shearing a system containing oil, water, a surfactant, and a highly water insoluble compound, the so-called hydrophobe 1. In the first part of this work, dynamic crystallization and melting experiments are described which were performed in small, stable and narrowly distributed nanodroplets (confined systems) of miniemulsions. Both regular and inverse systems were examined, characterizing, first, the crystallization of hexadecane, secondly, the crystallization of ice. It was shown for both cases that the temperature of crystallization in such droplets is significantly decreased (or the required undercooling is increased) as compared to the bulk material. This was attributed to a very effective suppression of heterogeneous nucleation. It was also found that the required undercooling depends on the nanodroplet size: with decreasing droplet size the undercooling increases. 2. It is shown that the temperature of crystallization of other n-alkanes in nanodroplets is also significantly decreased as compared to the bulk material due to a very effective suppression of heterogeneous nucleation. A very different behavior was detected between odd and even alkanes. In even alkanes, the confinement in small droplets changes the crystal structure from a triclinic (as seen in bulk) to an orthorhombic structure, which is attributed to finite size effects inside the droplets. An intermediate metastable rotator phase is of less relevance for the miniemulsion droplets than in the bulk. For odd alkanes, only a strong temperature shift compared to the bulk system is observed, but no structure change. A triclinic structure is formed both in bulk and in miniemulsion droplets. 3. In the next part of the thesis it is shown how miniemulsions could be successfully applied in the development of materials with potential application in pharmaceutical and medical fields. The production of cross-linked gelatin nanoparticles is feasible. Starting from an inverse miniemulsion, the softness of the particles can be controlled by varying the initial concentration, amount of cross-link agent, time of cross-linking, among other parameters. Such particles show a thermo-reversible effect, e.g. the particles swell in water above 37 °C and shrink below this temperature. Above 37 °C the chains loose the physical cross-linking, however the particles do not loose their integrity, because of the chemical cross-linking. Those particles have potential use as drug carriers, since gelatin is a natural polymer derived from collagen. 4. The cross-linked gelatin nanoparticles have been used for the biomineralization of hydroxyapatite (HAP), a biomineral, which is the major constituent of our bones. The biomineralization of HAP crystals within the gelatin nanoparticles results in a hybrid material, which has potential use as a bone repair material. 5. In the last part of this work we have shown that layers of conjugated semiconducting polymers can be deposited from aqueous dispersion prepared by the miniemulsion process. Dispersions of particles of different conjugated semiconducting polymers such as a ladder-type poly(para-phenylene) and several soluble derivatives of polyfluorene could be prepared with well-controlled particle sizes ranging between 70 - 250 nm. Layers of polymer blends were prepared with controlled lateral dimensions of phase separation on sub-micrometer scales, utilizing either a mixture of single component nanoparticles or nanoparticles containing two polymers. From the results of energy transfer it is demonstrated that blending two polymers in the same particle leads to a higher efficiency due to the better contact between the polymers. Such an effect is of great interest for the fabrication of opto-electronic devices such as light emitting diodes with nanometer size emitting points and solar cells comprising of blends of electron donating and electron accepting polymers. KW - Confinement KW - miniemulsion KW - crystallization KW - biomimetics and semiconducting polymers Y1 - 2003 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-0000726 ER -