TY - GEN A1 - Schäfer-Bung, Boris A1 - Nest, Mathias T1 - Correlated dynamics of electrons with reduced two-electron density matrices N2 - We present an approach to the correlated dynamics of many-electron systems. We show, that the twoelectron reduced density matrix (2RDM) can provide a suitable description of the real time evolution of a system. To achieve this, the hierarchy of equations of motion must be truncated in a practical way. Also, the computational effort, given that the 2RDM is represented by products of two-electron determinants, is discussed, and numerical model calculations are presented. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 100 Y1 - 2008 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-41774 SN - 1866-8372 ER - TY - THES A1 - Sütterlin, Martin T1 - New inverse hydogel opals as protein responsive sensors T1 - Neue inverse Hydrogelopale als proteinresponsive Sensoren N2 - In this work, the development of temperature- and protein-responsive sensor materials based on biocompatible, inverse hydrogel opals (IHOs) is presented. With these materials, large biomolecules can be specifically recognised and the binding event visualised. The preparation of the IHOs was performed with a template process, for which monodisperse silica particles were vertically deposited onto glass slides as the first step. The obtained colloidal crystals with a thickness of 5 μm displayed opalescent reflections because of the uniform alignment of the colloids. As a second step, the template was embedded in a matrix consisting of biocompatible, thermoresponsive hydrogels. The comonomers were selected from the family of oligo(ethylene glycol)methacrylates. The monomer solution was injected into a polymerisation mould, which contained the colloidal crystals as a template. The space in-between the template particles was filled with the monomer solution and the hydrogel was cured via UV-polymerisation. The particles were chemically etched, which resulted in a porous inner structure. The uniform alignment of the pores and therefore the opalescent reflection were maintained, so these system were denoted as inverse hydrogel opals. A pore diameter of several hundred nanometres as well as interconnections between the pores should facilitate a diffusion of bigger (bio)molecules, which was always a challenge in the presented systems until now. The copolymer composition was chosen to result in a hydrogel collapse over 35 °C. All hydrogels showed pronounced swelling in water below the critical temperature. The incorporation of a reactive monomer with hydroxyl groups ensured a potential coupling group for the introduction of recognition units for analytes, e.g. proteins. As a test system, biotin as a recognition unit for avidin was coupled to the IHO via polymer-analogous Steglich esterification. The amount of accessible biotin was quantified with a colorimetric binding assay. When avidin was added to the biotinylated IHO, the wavelength of the opalescent reflection was significantly shifted and therefore the binding event was visualised. This effect is based on the change in swelling behaviour of the hydrogel after binding of the hydrophilic avidin, which is amplified by the thermoresponsive nature of the hydrogel. A swelling or shrinking of the pores induces a change in distance of the crystal planes, which are responsible for the colour of the reflection. With these findings, the possibility of creating sensor materials or additional biomolecules in the size range of avidin is given. N2 - In dieser Arbeit wird die Entwicklung von temperatur- und proteinresponsiven Sensormaterialien auf Basis von biokompatiblen, inversen Hydrogelopalen (IHO) vorgestellt, mit welchen die spezifische Erkennung größerer Biomoleküle visuell ausgelesen werden kann. Die Darstellung der IHOs erfolgte mittels Templatverfahren, bei dem im ersten Schritt monodisperse Silicapartikel vertikal auf Objektträger abgeschieden wurden. Die so erhaltenen Kolloidkristalle mit einer Dicke von 5 μm zeigten opaleszente Reflexionen aufgrund der gleichförmigen Anordnung der Partikel. Im zweiten Schritt wurde das Templat in eine Matrix aus biokompatiblen, thermoresponsiven Hydrogelen eingebettet. Die Comonomere wurden aus der Familie der Oligo(ethylenglykol)methacrylate ausgewählt. Zur Synthese des Hydrogels wurde die Monomerlösung in eine Polymerisationsform injiziert, welche die Kolloidkristalle als Templat beinhaltete. Die Zwischenräume der Templatpartikel wurden mit der Monomerlösung gefüllt und das Hydrogelnetzwerk per UV-Polymerisation erhalten. Die Templatpartikel wurden anschließend nasschemisch heraus gelöst, so dass eine poröse innere Struktur erhalten wurde. Die regelmäßige Anordnung der Poren und damit die opaleszenten Reflexionen wurden dabei beibehalten, so dass diese Systeme als inverse Hydorgelopale bezeichnet werden. Ein Porendurchmesser von mehreren hundert Nanometer, sowie durchgängige Verbindungskanäle zwischen den einzelnen Poren sollten eine Diffusion von großen (Bio)molekülen erleichtern, was bei bisherigen Systemen ein Problem darstellte. Die Copolymerzusammensetzung wurde dabei so gewählt, dass ein Kollaps des Hydrogels über 35 °C stattfand. Alle Hydrogele zeigten ausgeprägte Quellung in Wasser unterhalb der kritischen Temperatur. Der Einbau von reaktiven Comonomeren mit Hydroxylgruppen gewährleistete dabei die Funktionalisierbarkeit des Hydrogels mit Erkennungsgruppen für entsprechende Analytmoleküle, wie z.B. Proteine. Als Testsystem wurde Biotin als Erkennungseinheit für Avidin in das Hydrogel mittels polymeranaloger Steglich Veresterung eingebaut. Die Menge an zugänglichem Biotin wurde dabei per colorimetrischem Bindungsassay quantifiziert. Dabei zeigte sich, dass sich die Wellenlänge der Reflexion nach Zugabe von Avidin zum biotinylierten inversen Hydrogelopal signifikant verschob und damit das Bindungsereignis visuell auslesbar ist. Dieser Effekt beruht auf dem veränderten Quellungsverhalten des Hydrogels nach Bindung des hydrophilen Proteins Avidin in Wasser, welches durch den thermosresponsiven Charakter des Hydrogels verstärkt ist. Ein Aufweiten oder Schrumpfen der Poren ändert die Abstände der gleichmäßig angeordneten Poren, welche für die Farbe des inversen Opals verantwortlich sind. Auf Basis dieser Erkenntnisse lassen sich möglicherweise Sensormaterialen für die Erkennung weiterer Biomoleküle in der Größenordnung von Avidin erstellen. KW - hydrogel KW - opal KW - protein KW - responsive KW - sensor Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-70179 ER - TY - GEN A1 - Tremblay, Jean Christophe A1 - Blanco-Rey, Maria T1 - Manipulating interfacial hydrogens at palladium via STM N2 - In this contribution, we provide a detailed dynamical analysis of the interfacial hydrogen migration mediated by scanning tunneling microscopy (STM). Contributions from the STM-current and from the non-adiabatic couplings are taken into account using only first principle models. The slight asymmetry of the tunnelling rates with respect to the potential bias sign inferred from experimental observations is reproduced by weighting the contributions of the metal acceptor–donor states for the propagation of the impinging electrons. The quasi-thermal inelastic collision mechanism is treated perturbatively. The influence of hydrogen pre-coverage is also investigated using new potential energy surfaces obtained from periodic density functional theory calculations. Fully quantum dynamical simulations of the system evolution are performed by solving the Pauli master equation, providing insight into the reaction mechanism of STM manipulation of subsurface hydrogens. It is observed that the hydrogen impurity favors resurfacing over occupation of the bulk and subsurface sites whenever possible. The present simulations give strong indication that the experimentally observed protuberances after STM-excitation are due to hydrogen accumulating in the vicinity of the surface. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 291 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-99511 ER - TY - GEN A1 - Tsukamoto, Junko A1 - Heabel, Sophie A1 - Valenca, Gustavo P. A1 - Peter, Martin A1 - Franco, Telma T1 - Enzymatic direct synthesis of acrylic acid esters of mono- and disaccharides N2 - BACKGROUND: There is an increased need to replace materials derived from fossil sources by renewables. Sugar-cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the preparation of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous preparation of protected sugar derivatives, such as glycosides, or activated acrylates, such as vinyl acrylate. RESULTS: Lipase catalyzed esterification of three mono- and two disaccharides with acrylic acid, in the presence or absence of molecular sieves was investigated. The reactions were monitored by high-performance liquid chromatography (HPLC) and the products were analyzed by matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry. The main products are mono- and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was observed for the D-glucose and D-fructose, followed by D-xylose and D-maltose. Molecular sieves had no pronounced effect on the conversion CONCLUSIONS: A feasible method is described to produce and to characterize sugar acrylates, including those containing more than two acrylate groups. The process for production of these higher esters could potentially be optimized further to produce molecules for cross-linking in acrylate polymerization and other applications. The direct enzymatic esterification of free carbohydrates with acrylic acid is unprecedented. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 106 KW - carbohydrate esters KW - enzymatic esterification KW - acrylic acid esters KW - MALDI-TOF mass spectrometry Y1 - 2008 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-42652 ER - TY - GEN A1 - Tsukruk, Vladimir A1 - Mischenko, Nikolay A1 - Köberle, Peter A1 - Laschewsky, André T1 - The structural order of some novel ionic polymers; 2. : Models of molecular packing N2 - The molecular packing and spatial correlations of two isomeric zwitterionic polymethacrylates and one polyacrylate analog are studied by means of X-ray analysis and conformational calculations. The analysis of the correlation functions and density distribution profiles suggest a double-layered molecular packing which is discussed for the three polymers investigated, with respect to their different chemical structures. Whereas the zwitterionic polymethacrylates studied exhibit liquid-like short-range order, the polyacrylate analog exhibits an ordered double-layered superstructure. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 096 Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17256 ER -