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 - THES A1 - Kröner, Dominik T1 - Analysis and control of light-induced processes in molecules: Electron and nuclear quantum dynamics for aspects of stereoisomerism and spectroscopy T1 - Analyse und Kontrolle lichtinduzierter Prozesse in Molekülen: Elektronen- und Kernquantendynamik für Aspekte der Stereoisomerie und Spektroskopie N2 - The habilitation thesis covers theoretical investigations on light-induced processes in molecules. The study is focussed on changes of the molecular electronic structure and geometry, caused either by photoexcitation in the event of a spectroscopic analysis, or by a selective control with shaped laser pulses. The applied and developed methods are predominantly based on quantum chemistry as well as on electron and nuclear quantum dynamics, and in parts on molecular dynamics. The studied scientific problems deal with stereoisomerism and the question of how to either switch or distinguish chiral molecules using laser pulses, and with the essentials for the simulation of the spectroscopic response of biochromophores, in order to unravel their photophysics. The accomplished findings not only explain experimental results and extend existing approaches, but also contribute significantly to the basic understanding of the investigated light-driven molecular processes. The main achievements can be divided in three parts: First, a quantum theory for an enantio- and diastereoselective or, in general, stereoselective laser pulse control was developed and successfully applied to influence the chirality of molecular switches. The proposed axially chiral molecules possess different numbers of "switchable" stable chiral conformations, with one particular switch featuring even a true achiral "off"-state which allows to enantioselectively "turn on" its chirality. Furthermore, surface mounted chiral molecular switches with several well-defined orientations were treated, where a newly devised highly flexible stochastic pulse optimization technique provides high stereoselectivity and efficiency at the same time, even for coupled chirality-changing degrees of freedom. Despite the model character of these studies, the proposed types of chiral molecular switches and, all the more, the developed basic concepts are generally applicable to design laser pulse controlled catalysts for asymmetric synthesis, or to achieve selective changes in the chirality of liquid crystals or in chiroptical nanodevices, implementable in information processing or as data storage. Second, laser-driven electron wavepacket dynamics based on ab initio calculations, namely time-dependent configuration interaction, was extended by the explicit inclusion of magnetic field-magnetic dipole interactions for the simulation of the qualitative and quantitative distinction of enantiomers in mass spectrometry by means of circularly polarized ultrashort laser pulses. The developed approach not only allows to explain the origin of the experimentally observed influence of the pulse duration on the detected circular dichroism in the ion yield, but also to predict laser pulse parameters for an optimal distinction of enantiomers by ultrashort shaped laser pulses. Moreover, these investigations in combination with the previous ones provide a fundamental understanding of the relevance of electric and magnetic interactions between linearly or non-linearly polarized laser pulses and (pro-)chiral molecules for either control by enantioselective excitation or distinction by enantiospecific excitation. Third, for selected light-sensitive biological systems of central importance, like e.g. antenna complexes of photosynthesis, simulations of processes which take place during and after photoexcitation of their chromophores were performed, in order to explain experimental (spectroscopic) findings as well as to understand the underlying photophysical and photochemical principles. In particular, aspects of normal mode mixing due to geometrical changes upon photoexcitation and their impact on (time-dependent) vibronic and resonance Raman spectra, as well as on intramolecular energy redistribution were addressed. In order to explain unresolved experimental findings, a simulation program for the calculation of vibronic and resonance Raman spectra, accounting for changes in both vibrational frequencies and normal modes, was created based on a time-dependent formalism. In addition, the influence of the biochemical environment on the electronic structure of the chromophores was studied by electrostatic interactions and mechanical embedding using hybrid quantum-classical methods. Environmental effects were found to be of importance, in particular, for the excitonic coupling of chromophores in light-harvesting complex II. Although the simulations for such highly complex systems are still restricted by various approximations, the improved approaches and obtained results have proven to be important contributions for a better understanding of light-induced processes in biosystems which also adds to efforts of their artificial reproduction. N2 - Die Habilitationsschrift behandelt theoretische Untersuchungen von durch Licht ausgelösten Prozessen in Molekülen. Der Schwerpunkt liegt dabei auf Veränderungen in der Elektronenstruktur und der Geometrie der Moleküle, die durch Bestrahlung mit Licht entweder bei einer spektroskopischen Untersuchung oder bei gezielter Kontrolle durch geformte Laserpulse herbeigeführt werden. Um die dabei auftretende Elektronen- und Kerndynamik zu simulieren, wurden vornehmlich quantentheoretische Methoden eingesetzt und weiterentwickelt. Die wissenschaftlichen Fragestellungen beschäftigen sich mit dem gezielten Verändern und dem Erkennen der räumlichen Struktur von Molekülen ohne Drehspiegelachse, der sog. molekularen Chiralität, sowie mit durch Licht eingeleiteten Prozessen in biologisch relevanten Pigmenten auf sehr kurzen Zeitskalen. Die entwickelten Ansätze und gewonnenen Erkenntnisse lassen sich drei Haupterfolge unterteilen: Erstens gelang die Entwicklung einer generellen Kontrolltheorie für das Ein- und Umschalten von molekularer Chiralität mit geformten Laserpulsen. Dabei wird die räumliche Struktur der vorgeschlagenen molekularen Schalter zwischen ihren stabilen sog. stereoisomeren Formen selektiv geändert, was sich auf ihre optischen und chemischen Eigenschaften auswirkt. Für komplexere Bedingungen, wie z.B. auf einer Oberfläche verankerten molekularen Schaltern verschiedener Orientierung, wurde eine neue Pulsoptimierungsmethode basierend auf Wahrscheinlichkeiten und Statistik entwickelt. Solche laserpulskontrollierten chiralen molekularen Schalter hofft man u.a. in der Nanotechnologie zum Einsatz zu bringen, wo sie z.B. als Informationsspeicher dienen könnten. Zweitens konnte geklärt werden, welche die wesentlichen Einflüsse sind, die das Erkennen von sog. Enantiomeren, das sind spiegelbildliche Moleküle von entgegengesetzter Chiralität, nach Ionisierung durch ultrakurze zirkular polarisierte Laserpulse ermöglichen. Diese Form des sog. Zirkulardichroismus in der Ionenausbeute erlaubt die quantitative und qualitative Unterscheidung von Enantiomeren in der Massenspektrometrie. Durch Simulation der Elektronendynamik während der Laseranregung konnte u.a. erstmals gezeigt werden, dass neben der Zirkularpolarisation der Laserpulse vor allem die schwachen magnetischen Wechselwirkungen für die Unterscheidung entscheidend sind. Drittens wurden die Spektren von in der Natur vorkommenden Pigmenten simuliert, welche u.a. an wichtigen biologischen Funktionen, wie dem Sammeln von Sonnenenergie für die Photosynthese, beteiligt sind. Die Lichtanregung führt dabei zu einer Veränderung der Elektronenstruktur und Geometrie der Pigmente, wobei letzteres wichtige Konsequenzen für die Verteilung der Energie auf die spektroskopisch beobachteten Molekülschwingungen mit sich bringen. Auch der wichtige Einfluss der biochemischen Umgebung auf die Elektronenstruktur der Pigmente bzw. den Energietransfer zwischen solchen wurde untersucht. Neben der Klärung experimenteller Ergebnisse ermöglichen die Untersuchungen neue Einblicke in die fundamentalen Prozesse kurz nach der Lichtanregung -- Erkenntnisse, die auch für die technische Nachahmung der biologischen Funktionen von Bedeutung sein können. KW - Elektronendynamik KW - chirale Schalter KW - chirale Erkennung KW - Biochromophore KW - Laserpulskontrolle KW - electron dynamics KW - chiral switches KW - chiral recognition KW - biochromophores KW - laser pulse control Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-70477 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 - THES A1 - Metzke, Sarah T1 - Synthesis and characterization of transition metal nitrides and carbides for catalysis and electrochemistry application N2 - It was the goal of this work to explore two different synthesis pathways using green chemistry. The first part of this thesis is focusing on the use of the urea-glass route towards single phase manganese nitride and manganese nitride/oxide nano-composites embedded in carbon, while the second part of the thesis is focusing on the use of the “saccharide route” (namely cellulose, sucrose, glucose and lignin) towards metal (Ni0), metal alloy (Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5, Cu0.5Ni0.5 and W0.15Ni0.85) and ternary carbide (Mn0.75Fe2.25C) nanoparticles embedded in carbon. In the interest of battery application, MnN0.43 nanoparticles surrounded by a graphitic shell and embedded in carbon with a high surface area (79 m^2/g) were synthesized, following a previously set route.The comparison of the material characteristics before and after the discharge showed no remarkable difference in terms of composition and just slight differences in the morphological point of view, meaning the particles are stable but agglomerate. The graphitic shell is contributing to the resistance of the material and leads to a fine cyclic stability over 140 cycles of 230 mAh/g after the first charge/discharge and coulombic efficiencies close to 100%. Due to the low voltage towards Li/Li+ and the low polarization, it might be an attractive anode material for lithium ion batteries. However, the capacity is still noticeably lower than the theoretical value for MnN0.43. A mixture of MnN0.43 and MnO nanoparticles embedded in carbon (surface area 93 m^2/g) was able to improve the cyclic stability to over 160 cycles giving a capacity of 811 mAh/g, which is considerably higher than the capacity of the conventional material graphite (372 mAh/g). This nano-composite seems to agglomerate less during the process of discharge. Interestingly, although the capacity is much higher than of the single phase manganese nitride, the nano-composite seems to only contain MnN0.43 nanoparticles after the process of discharge with no oxide phase to be found. Concerning catalysis application, different metal, metal alloy, and metal carbide nanoparticles were synthesized using the saccharide route. At first, systems that were already investigated before, being Pd0.9Ni0.1, Pd0.5Ni0.5, Fe0.5Ni0.5 and Mn0.75Fe2.25C using cellulose as the carbon source were prepared and tested in an alkylation reaction of toluene with benzylchloride. Unexpectedly, the metal alloys did not show any catalytic activity, but the ternary carbide Mn0.75Fe2.25C showed fine catalytic activity of 98% conversion after 9 hour reaction time (110 °C). In a second step, the saccharide route was modified towards other carbon sources and carbon to metal ratios in order to improve the homogeneity of the samples and accessibility of the particle surfaces. The used carbon sources sucrose and glucose are similar in their basic structure of carbohydrates, but reducing the (polymeric) chain length. Indeed, the cellulose could be successfully replaced by sucrose and glucose. A lower carbon to metal ratio was found to influence the size, homogeneity and accessibility (as evidenced by TEM) of the samples. Since sucrose is an aliment, glucose is the better choice as a carbon source. Using glucose, the synthesis of Cu0.5Ni0.5 and W0.15Ni0.85 nano-composites was also possible, although the later was never obtained as pure phase. These alloy nano-composites were tested, along with nickel0 nanoparticles also prepared with glucose and on their catalytic activity towards the reduction of phenylacetylene. The results obtained let believe that any (poly) saccharide, including lignin, could be used as carbon source. The nickel0 nano-composites prepared with lignin as a carbon source were tested along with those prepared with cellulose and sucrose for their catalytic activity in the transfer hydrogenation of nitrobenzene (results compared with exposed nickel nanoparticles and nickel supported on carbon) leading to very promising results. Based on the urea-glass route and the saccharide route, simple equipment and transition metals, it was possible to have a one-pot synthesize with scale-up possibilities towards new material that can be applied in catalysis and battery systems. N2 - Im Rahmen dieser Arbeit wird sowohl die Synthese von Mangannitrid- und -oxid-Nanopartikeln, als auch die Synthese verschiedener Metall- und Legierungsnanopartikel untersucht. Einen Schwerpunkt stellt dabei die Optimierung der Synthese unter den Gesichtspunkten der Nachhaltigkeit dar, was sich insbesondere in der Verwendung diverser nachwachsender Rohstoffe als Kohlenstoffquelle äußert. Für eine mögliche Anwendung in Akkumulatoren werden mit Graphit ummantelte MnN0.43-Nanopartikel mit einer großen Oberfläche (79 m^2/g) synthetisiert. Diese werden exemplarischen Ladezyklen unterzogen, wobei eine strukturelle und auch elektrochemische Stabilität festgestellt werden kann. Eine Mischung der Mangannitride mit Manganoxiden führt zu einer weiteren Verbesserung der Ladekapazität und einer weiteren Oberflächenvergrößerung (93 m^2/g). Die Langlebigkeit der Strukturen wird durch die Einbettung der Nanopartikel in Kohlenstoff unterstützt und kann zu einer Anwendung als Anodenmaterial in den heutzutage vielfach verwendeten Lithiumionen-Akkus führen. Im Sinne der Nachhaltigkeit ist auch die Entwicklung von Katalysatoren. Dabei soll insbesondere die Verwendung von Lignin, was als Bestandteil vieler Pflanzen zwar leicht verfügbar, aber unglücklicherweise bisher chemisch unverwertbar ist, fokussiert werden. Um sich diesem Ziel zu nähern und entsprechende Mechanismen zur Reduktion des Lignins zu entwickeln, werden in dieser Arbeit zunächst verschiedene Kohlenstoffquellen (wie Cellulose, Sucrose und Glucose) zur Synthese von reduktiven Katalysatoren untersucht. Der Kohlenstoff dient dabei sowohl als preiswertes Reduktionsmittel für Metallsalze zur Gewinnung von Metallnanopartikel als auch zur Stabilisierung ebendieser. Es werden vielfältige Legierungen mit Nickel (z.B. Pd0.9Ni0.1, Pd0.5.Ni0.5, Fe0.5.Ni0.5, und Cu0.5.Ni0.5) aber auch ternäre Carbide (z.B. Mn0.75Fe2.25C) erhalten, die schon in ersten Alkylierungs- und Hydrierungsreaktionen ein großes Potential als Katalysatoren zeigen. Um die erhaltenen Nanopartikel in zukünftigen Anwendungen nutzbar zu machen, ist eine ausführliche Charakterisierung unabdingbar. Auch die Ergebnisse der zahlreichen durchgeführten Analysen werden in dieser Arbeit zusammengestellt und bilden gemeinsam mit den optimierten Syntheserouten einen tiefgreifenden Überblick über dieses Forschungsfeld. KW - Nanopartikel KW - Katalyse KW - Übergangsmetall KW - grüne Chemie KW - carbothermisch KW - nanoparticles KW - catalysis KW - transition metal KW - green chemistry KW - carbothermal Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-69835 ER - TY - THES A1 - Mondal, Suvendu Sekhar T1 - Design of isostructural metal-imidazolate frameworks : application for gas storage T1 - Synthese isostruktureller Metall-Imidazolat Frameworks : Anwendung für Gasspeicherung N2 - The sharply rising level of atmospheric carbon dioxide resulting from anthropogenic emissions is one of the greatest environmental concerns facing our civilization today. Metal-organic frameworks (MOFs) are a new class of materials that constructed by metal-containing nodes bonded to organic bridging ligands. MOFs could serve as an ideal platform for the development of next generation CO2 capture materials owing to their large capacity for the adsorption of gases and their structural and chemical tunability. The ability to rationally select the framework components is expected to allow the affinity of the internal pore surface toward CO2 to be precisely controlled, facilitating materials properties that are optimized for the specific type of CO2 capture to be performed (post-combustion capture, precombustion capture, or oxy-fuel combustion) and potentially even for the specific power plant in which the capture system is to be installed. For this reason, significant effort has been made in recent years in improving the gas separation performance of MOFs and some studies evaluating the prospects of deploying these materials in real-world CO2 capture systems have begun to emerge. We have developed six new MOFs, denoted as IFPs (IFP-5, -6, -7, -8, -9, -10, IFP = Imidazolate Framework Potsdam) and two hydrogen-bonded molecular building block (MBB, named as 1 and 2 for Zn and Co based, respectively) have been synthesized, characterized and applied for gas storage. The structure of IFP possesses 1D hexagonal channels. Metal centre and the substituent groups of C2 position of the linker protrude into the open channels and determine their accessible diameter. Interestingly, the channel diameters (range : 0.3 to 5.2 Å) for IFP structures are tuned by the metal centre (Zn, Co and Cd) and substituent of C2 position of the imidazolate linker. Moreover hydrogen bonded MBB of 1 and 2 is formed an in situ functionalization of a ligand under solvothermal condition. Two different types of channels are observed for 1 and 2. Materials contain solvent accessible void space. Solvent could be easily removed by under high vacuum. The porous framework has maintained the crystalline integrity even without solvent molecules. N2, H2, CO2 and CH4 gas sorption isotherms were performed. Gas uptake capacities are comparable with other frameworks. Gas uptake capacity is reduced when the channel diameter is narrow. For example, the channel diameter of IFP-5 (channel diameter: 3.8 Å) is slightly lower than that of IFP-1 (channel diameter: 4.2 Å); hence, the gas uptake capacity and Brunauer-Emmett-Teller (BET) surface area are slightly lower than IFP-1. The selectivity does not depend only on the size of the gas components (kinetic diameter: CO2 3.3 Å, N2 3.6 Å and CH4 3.8 ) but also on the polarizability of the surface and of the gas components. IFP-5 and-6 have the potential applications for the separation of CO2 and CH4 from N2-containing gas mixtures and CO2 and CH4 containing gas mixtures. Gas sorption isotherms of IFP-7, -8, -9, -10 exhibited hysteretic behavior due to flexible alkoxy (e.g., methoxy and ethoxy) substituents. Such phenomenon is a kind of gate effects which is rarely observed in microporous MOFs. IFP-7 (Zn-centred) has a flexible methoxy substituent. This is the first example where a flexible methoxy substituent shows the gate opening behavior in a MOF. Presence of methoxy functional group at the hexagonal channels, IFP-7 acted as molecular gate for N2 gas. Due to polar methoxy group and channel walls, wide hysteretic isotherm was observed during gas uptake. The N2 The estimated BET surface area for 1 is 471 m2 g-1 and the Langmuir surface area is 570 m2 g-1. However, such surface area is slightly higher than azolate-based hydrogen-bonded supramolecular assemblies and also comparable and higher than some hydrogen-bonded porous organic molecules. N2 - Metallorganische Gerüstverbindungen (MOFs) sind eine neue Klasse von porösen Koordinationspolymeren, die aus Metall-Knoten und verbrückenden Liganden bestehen. MOFs können Gasgemische trennen und Gase speichern. Aufgrund ihres modularen Aufbaus können die MOF-Eigenschaften systematisch variiert werden. Ein wichtiges Ziel für das Design von MOFs ist die Synthese von Materialien, die eine hohe selektive Aufnahmefähigkeit und -kapazität für Kohlenstoffdioxid besitzen. Im Rahmen der Arbeit ist es gelungen sechs neue MOFs (IFP-5, -6, -7, -8, -9 und -10) zu synthetisieren. Diese MOFs tragen die Kurzbezeichnung IFP. IFP steht als Abkürzung für Imidazolat-Framework-Potsdam (Imidazolat-basierte Gerüstverbindung Potsdam). In diesen IFPs wurde der Metallknoten (Zink, Cobalt, Cadmium) und der Brückenligand, ein 2-substituiertes Imidazolat-amid-imidat, in der Position variiert, um gute und selektive Sorptionseigenschaften für Kohlenstoffdioxid zu erzielen. Von den synthetisierten Verbindungen hat das IFP-5 die besten Sorptionseigenschaften für Kohlenstoffdioxid. Es konnte weiter gezeigt werden, dass sich die IFP-Struktur bei der Wahl von geeigneten Substituenten 2, wie z.B. Methoxy und Ethoxy auch für das Design von gate-opening (Tür-öffnenden) Effekten eignet. Diese Effekte können wiederum genutzt werden, um selektiv Gasmischungen zu trennen. Wenn man das 4,5-Dicyano-2-methoxy-imidazol in Gegenwart von Zink- und Cobalt-Salzen unter solvothermalen Bedingungen zur Reaktion bringt, erhält man beispiellose supramolekulare Wasserstoffbrückenbindungen zu einem dreidimensionalen Netzwerk, die mit Kanälen verknüpft sind. Diese Kanäle können von Lösungsmittelmolekülen (Wasser und Dimethylformamid) befreit werden und Gase aufnehmen. Insgesamt besteht nun die neue MOF-Klasse der Imidazolat-basierten IFPs aus Vertretern. Das Potential der 2-substituierten 4,5-Dicyanoimidazole ist nicht nur auf die Bildung von porösen Koordinationspolymeren beschränkt, sondern kann auch für die Synthese von bisher unbekannten supramolekularen Strukturen genutzt werden. KW - Metal-organic framework KW - Gas Sorption KW - Cobalt KW - Zinc KW - Ionic Liquid KW - metal-organic framework KW - gas sorption KW - cobalt KW - zinc KW - ionic liquid Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-69692 ER - TY - THES A1 - Glatzel, Stefan T1 - Cellulose based transition metal nano-composites : structuring and development T1 - Zellulose-basierte Übergangsmetall Nano-Komposite : Strukturierung und Entwicklung N2 - Cellulose is the most abundant biopolymer on earth. In this work it has been used, in various forms ranging from wood to fully processed laboratory grade microcrystalline cellulose, to synthesise a variety of metal and metal carbide nanoparticles and to establish structuring and patterning methodologies that produce highly functional nano-hybrids. To achieve this, the mechanisms governing the catalytic processes that bring about graphitised carbons in the presence of iron have been investigated. It was found that, when infusing cellulose with an aqueous iron salt solution and heating this mixture under inert atmosphere to 640 °C and above, a liquid eutectic mixture of iron and carbon with an atom ratio of approximately 1:1 forms. The eutectic droplets were monitored with in-situ TEM at the reaction temperature where they could be seen dissolving amorphous carbon and leaving behind a trail of graphitised carbon sheets and subsequently iron carbide nanoparticles. These transformations turned ordinary cellulose into a conductive and porous matrix that is well suited for catalytic applications. Despite these significant changes on the nanometre scale the shape of the matrix as a whole was retained with remarkable precision. This was exemplified by folding a sheet of cellulose paper into origami cranes and converting them via the temperature treatment in to magnetic facsimiles of those cranes. The study showed that the catalytic mechanisms derived from controlled systems and described in the literature can be transferred to synthetic concepts beyond the lab without loss of generality. Once the processes determining the transformation of cellulose into functional materials were understood, the concept could be extended to other metals and metal-combinations. Firstly, the procedure was utilised to produce different ternary iron carbides in the form of MxFeyC (M = W, Mn). None of those ternary carbides have thus far been produced in a nanoparticle form. The next part of this work encompassed combinations of iron with cobalt, nickel, palladium and copper. All of those metals were also probed alone in combination with cellulose. This produced elemental metal and metal alloy particles of low polydispersity and high stability. Both features are something that is typically not associated with high temperature syntheses and enables to connect the good size control with a scalable process. Each of the probed reactions resulted in phase pure, single crystalline, stable materials. After showing that cellulose is a good stabilising and separating agent for all the investigated types of nanoparticles, the focus of the work at hand is shifted towards probing the limits of the structuring and pattering capabilities of cellulose. Moreover possible post-processing techniques to further broaden the applicability of the materials are evaluated. This showed that, by choosing an appropriate paper, products ranging from stiff, self-sustaining monoliths to ultra-thin and very flexible cloths can be obtained after high temperature treatment. Furthermore cellulose has been demonstrated to be a very good substrate for many structuring and patterning techniques from origami folding to ink-jet printing. The thereby resulting products have been employed as electrodes, which was exemplified by electrodepositing copper onto them. Via ink-jet printing they have additionally been patterned and the resulting electrodes have also been post functionalised by electro-deposition of copper onto the graphitised (printed) parts of the samples. Lastly in a preliminary test the possibility of printing several metals simultaneously and thereby producing finely tuneable gradients from one metal to another have successfully been made. Starting from these concepts future experiments were outlined. The last chapter of this thesis concerned itself with alternative synthesis methods of the iron-carbon composite, thereby testing the robustness of the devolved reactions. By performing the synthesis with partly dissolved scrap metal and pieces of raw, dry wood, some progress for further use of the general synthesis technique were made. For example by using wood instead of processed cellulose all the established shaping techniques available for wooden objects, such as CNC milling or 3D prototyping, become accessible for the synthesis path. Also by using wood its intrinsic well defined porosity and the fact that large monoliths are obtained help expanding the prospect of using the composite. It was also demonstrated in this chapter that the resulting material can be applied for the environmentally important issue of waste water cleansing. Additionally to being made from renewable resources and by a cheap and easy one-pot synthesis, the material is recyclable, since the pollutants can be recovered by washing with ethanol. Most importantly this chapter covered experiments where the reaction was performed in a crude, home-built glass vessel, fuelled – with the help of a Fresnel lens – only by direct concentrated sunlight irradiation. This concept carries the thus far presented synthetic procedures from being common laboratory syntheses to a real world application. Based on cellulose, transition metals and simple equipment, this work enabled the easy one-pot synthesis of nano-ceramic and metal nanoparticle composites otherwise not readily accessible. Furthermore were structuring and patterning techniques and synthesis routes involving only renewable resources and environmentally benign procedures established here. Thereby it has laid the foundation for a multitude of applications and pointed towards several future projects reaching from fundamental research, to application focussed research and even and industry relevant engineering project was envisioned. N2 - Die vorliegende Arbeit beschäftigt sich mit der Synthese und Strukturierung von Nanokompositen, d.h. mit ausgedehnten Strukturen, welche Nanopartikel enthalten. Im Zuge der Arbeit wurde der Mechanismus der katalytischen Graphitisierung, ein Prozess, bei dem ungeordneter Kohlenstoff durch metallische Nanopartikel in geordneten (graphitischen) Kohlenstoff überführt wird, aufgeklärt. Dies wurde exemplarisch am Beispiel von Zellulose und Eisen durchgeführt. Die untersuchte Synthese erfolgte durch das Lösen eines Eisensalzes in Wasser und die anschließende Zugabe von so viel Zellulose, dass das die gesamte Eisensalzlösung aufgenommen wurde. Die so erhaltene Mischung wurde anschließend unter Schutzgas innerhalb kürzester Zeit auf 800 °C erhitzt. Hierbei zeigte sich, dass zu Beginn der Reaktion Eisenoxidnanopartikel (Rost) auf der Oberfläche der Zellulose entstehen. Beim weiteren Erhöhen der Temperatur werden diese Partikel zu Eisenpartikeln umgewandelt. Diese lösen dann kleine Bereiche der Zellulose auf, wandeln sich in Eisenkarbid um und scheiden graphitischen Kohlenstoff ab. Nach der Reaktion sind die Zellulosefasern porös, jedoch bleibt ihre Faserstruktur vollkommen erhalten. Dies konnte am Beispiel eines Origamikranichs gezeigt werden, welcher nach dem Erhitzen zwar seine Farbe von Weiß zu Schwarz verändert hatte, ansonsten aber seine Form vollkommen beibehält. Aufgrund der eingebetteten Eisenkarbid Nanopartikel war der Kranich außerdem hochgradig magnetisch. Basierend auf dieser Technik wurden außerdem winzige metallische Nanopartikel aus Nickel, Nickel-Palladium, Nickel-Eisen, Kobalt, Kobalt-Eisen und Kupfer, sowie Partikel aus den Verbundkarbiden Eisen-Mangan-Karbid und Eisen-Wolfram-Karbid, jeweils in verschiedenen Mischungsverhältnissen, hergestellt und analysiert. Da die Vorstufe der Reaktion flüssig ist, konnte diese mit Hilfe eines einfachen kommerziellen Tintenstrahldruckers strukturiert auf Zellulosepapier aufgebracht werden. Dies ermöglicht gezielt Leiterbahnen, bestehend aus graphitisiertem Kohlenstoff, in ansonsten ungeordnetem (amorphen) Kohlenstoff zu erzeugen. Diese Methode wurde anschließend auf Systeme mit mehreren Metallen übertragen. Hierbei wurde die Tatsache, dass moderne Drucker vier Tintenpatronen beherbergen, ausgenutzt um Nanopartikel mit beliebigen Mischungsverhältnisse von Metallen zu erzeugen. Dieser Ansatz hat potentiell weitreichende Auswirkungen im Feld der Katalyse, da hiermit hunderte oder gar tausende Mischungen simultan erzeugt und getestet werden können. Daraus würden sich große Zeiteinsparungen (Tage anstelle von Monaten) bei der Entwicklung neuer Katalysatoren ergeben. Der letzte Teil der Arbeit beschäftigt sich mit der umweltfreundlichen Synthese der obengenannten Komposite. Hierbei wurden erfolgreich Altmetall und Holzstücke als Ausgangstoffe verwandt. Zusätzlich wurde gezeigt, dass die gesamte Synthese ohne Verwendung von hochentwickeltem Equipment durchgeführt werden kann. Dazu wurde eine sogenannte Fresnel-Linse genutzt um Sonnenlicht zu bündeln und damit direkt die Reaktionsmischung auf die benötigten 800 °C zu erhitzen. Weiterhin wurde ein selbst gebauter Glasreaktor eingesetzt und gezeigt, wie das entstehende Produkt als Abwasserfilter genutzt werden kann. Die Kombination dieser Ergebnisse bedeutet, dass dieses System sich beispielsweise zum Einsatz in Katastrophenregionen eignen würde, um ohne Strom und besondere Ausrüstung vor Ort Wasserfilter herzustellen. KW - Zellulose KW - Übergangsmetalle KW - Carbide KW - Nanopartikel KW - Komposite KW - Cellulose KW - Transitionmetals KW - Carbides KW - Nanoparticles KW - Composites Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-64678 ER - TY - GEN A1 - Jeličić, Aleksandra A1 - Friedrich, Alwin A1 - Jeremić, Katarina A1 - Siekmeyer, Gerd A1 - Taubert, Andreas T1 - Polymer hydrogel/polybutadiene/iron oxide nanoparticle hybrid actuators for the characterization of NiTi implants N2 - One of the main issues with the use of nickel titanium alloy (NiTi) implants in cardiovascular implants (stents) is that these devices must be of very high quality in order to avoid subsequent operations due to failing stents. For small stents with diameters below ca. 2 mm, however, stent characterization is not straightforward. One of the main problems is that there are virtually no methods to characterize the interior of the NiTi tubes used for fabrication of these tiny stents. The current paper reports on a robust hybrid actuator for the characterization of NiTi tubes prior to stent fabrication. The method is based on a polymer/hydrogel/magnetic nanoparticle hybrid material and allows for the determination of the inner diameter at virtually all places in the raw NiTi tubes. Knowledge of the inner structure of the raw NiTi tubes is crucial to avoid regions that are not hollow or regions that are likely to fail due to defects inside the raw tube. The actuator enables close contact of a magnetic polymer film with the inner NiTi tube surface. The magnetic signal can be detected from outside and be used for a direct mapping of the tube interior. As a result, it is possible to detect critical regions prior to expensive and slow stent fabrication processes. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 161 KW - NiTi KW - inner surface KW - hydrogel KW - polybutadiene KW - magnetic nanoparticles Y1 - 2009 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-48589 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 - Oliveira Jr, E. N. A1 - Gueddari, Nour E. El A1 - Moerschbacher, Bruno M. A1 - Peter, Martin A1 - Franco, Telma T1 - Growth of phytopathogenic fungi in the presence of partially acetylated chitooligosaccharides N2 - Four phytopathogenic fungi were cultivated up to six days in media containing chitooligosaccharide mixtures differing in average DP and FA. The three different mixtures were named Q3 (which contained oligosaccharides ofDP2–DP10, withDP2–DP7 asmain components), Q2 (which contained oligosaccharides of DP2–DP12, with DP2–DP10 as main components) and Q1 (which derived from Q2 and contained oligomers of DP5–DP8 with hexamer and a heptamer as the main components). The novel aspect of this work is the description of the effect of mixtures of oligosaccharides with different and known composition on fungal growth rates. The growth rate of Alternaria alternata and Rhizopus stolonifer was initially inhibited by Q3 and Q2 at higher concentrations. Q1 had a growth stimulating effect on these two fungi. Growth of Botrytis cinerea was inhibited by Q3 and Q2, while Q1 had no effect on the growth of this fungus. Growth of Penicillium expansum was only slightly inhibited by higher concentrations of sample Q3, while Q2 and Q1 had no effect. The inhibition of growth rates or their resistance toward chitooligosaccharides correlated with the absence or presence of chitinolytic enzymes in the culture media, respectively. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 105 KW - Chitosan KW - Chitinase KW - Fungi KW - Oligosaccharides KW - Phytopathogens Y1 - 2008 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-42646 ER - TY - GEN A1 - Bringmann, Gerhard A1 - Mutanyatta-Comar, Joan A1 - Maksimenka, Katja A1 - Wanjohi, John M. A1 - Heydenreich, Matthias A1 - Brun, Reto A1 - Müller, Werner E. G. A1 - Peter, Martin A1 - Midiwo, Jacob O. A1 - Yenesew, Abiy T1 - Joziknipholones A and B : the First Dimeric Phenylanthraquinones, from the Roots of Bulbine frutescens N2 - From the roots of the African plant Bulbine frutescens (Asphodelaceae), two unprecedented novel dimeric phenylanthraquinones, named joziknipholones A and B, possessing axial and centrochirality, were isolated, together with six known compounds. Structural elucidation of the new metabolites was achieved by spectroscopic and chiroptical methods, by reductive cleavage of the central bond between the monomeric phenylanthraquinone and -anthrone portions with sodium dithionite, and by quantum chemical CD calculations. Based on the recently revised absolute axial configuration of the parent phenylanthraquinones, knipholone and knipholone anthrone, the new dimers were attributed to possess the P-configuration (i.e., with the acetyl portions below the anthraquinone plane) at both axes in the case of joziknipholone A, whereas in joziknipholone B, the knipholone part was found to be M-configured. Joziknipholones A and B are active against the chloroquine resistant strain K1 of the malaria pathogen, Plasmodium falciparum, and show moderate activity against murine leukemic lymphoma L5178y cells. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 104 KW - antimalarial activity KW - chirality KW - joziknipholones KW - natural products KW - structure elucidation Y1 - 2008 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-42638 ER - 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 - GEN A1 - Biddle, M. B. A1 - Rickert, S. E. A1 - Lando, J. B. A1 - Laschewsky, André T1 - The use of the Langmuir-Blodgett technique to obtain ultra-thin polar films N2 - The piezoelectric and pyroelectric properties of oriented films possessing dipole moments are increasingly being used in pressure, acoustic, thermal and optical devices. The performance of these devices in many applications may be enhanced by thin-film technology.The developing Langmuir-Blodgett thin-film deposition technique offers the opportunity to obtain highly oriented and uniform organic-based films in the 10–5000 nm thickness range. Special techniques must be used, however, to assemble these molecules in such a way as to result in polar multilayer films. Several possible deposition techniques are investigated, with one resulting in a polar and pyroelectric film about 50 nm thick. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 098 Y1 - 1989 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17185 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 - TY - GEN A1 - Elbert, R. A1 - Laschewsky, André A1 - Ringsdorf, H. T1 - Hydrophilic spacer groups in polymerizable lipids: formation of biomembrane models from bulk polymerized lipids N2 - A variety of polymerizable lipids containing a hydrophilic spacer group between the reactive group and the main amphiphilic structure have been synthesized. They were investigated in monolayers, liposomes, and multilayers. When the spacer concept was used, efficient decoupling of the motions of the polymeric chain and the amphiphilic side groups is achieved. Thus, the often found loss of the important fluid phases by polymerization is avoided. Polymeric monolayers of the spacer lipid, prepared either by polymerization in the monolayer or by spreading of prepolymerized lipid, exhibit nearly identical surface pressure-area diagrams. Most distinctly, the successful decoupling of the motions of the polymer main chain and the membrane forming amphiphilic side groups is demonstrated by the self-organization of bulk polymerized spacer lipids to polymeric liposomes. In addition, spacer lipids are able to build polymeric Langmuir-Blodgett multilayers. The decoupling of the polymer main chain and the membrane-forming amphiphilic side groups enables the deposition of already polymeric monolayers onto supports to form defined multilayers. If, alternatively, monomeric monolayers are deposited and polymerized on the support, defects in the layers due to structural changes during the polymerization are avoided by the flexible spacer group. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 095 Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17361 ER - TY - GEN A1 - Lupo, Donald A1 - Prass, Werner A1 - Scheunemann, Ude A1 - Laschewsky, André A1 - Ringsdorf, Helmut A1 - Ledoux, Isabelle T1 - Second-harmonic generation in Langmuir-Blodgett monolayers of stilbazium salt and phenylhydrazone dyes N2 - Contents: 1. INTRODUCTION 2. SYNTHESIS OF THE COMPOUNDS 3. PREPARATION AND CHARACTERIZATION OF MONOLAYERS A. Monolayer Isotherms B. Langmuir-Blodgett Monolayer Films 4. EXPERIMENTAL SETUP FOR NONLINEAR MEASUREMENTS 5. NONLINEAR OPTICAL PROPERTIES 6. DISCUSSION 7. CONCLUSION T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 094 Y1 - 1988 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17401 ER - TY - GEN A1 - Rozanski, Stanislaw A. A1 - Kremer, Friedrich A1 - Köberle, Peter A1 - Laschewsky, André T1 - Relaxation and charge transport in mixtures of zwitterionic polymers and inorganic salts N2 - Dielectric spectroscopy is employed to analyze the molecular dynamics and the charge transport in mixtures of zwitterionic polymers of the type poly{3 [N(-methacryloyloxyalkyl)] N, [N-dimethylammonio propanesulfonate] with sodium iodide in the frequency range of 10²Hz-10(up)7 Hz and in the temperature range of 110 K-400 K. The amount of inorganic salt added varies from 0-200 mol-% relative to the number of zwitterionic groups present in the polymer, contributing strongly to the conductivity. One relaxation process is observed whose relaxation rate depends strongly on the length of the aliphatic spacer between the polymethacrylate main chain and the zwitterionic group. Exhibiting an Arrhenius-like temperature depence with activation energy EA = 47 KJ/mol, this relaxation process is assigned to fluctuation of the quaternary ammonium groups in the side chains. At higher temperatures, the dielectric properties and the conductivity are primarily dominated by the mobile inorganic ions: conductivity strongly depends on the salt concentration, showing a pronounced electrode polarization effect. The frequency and salt concentration, dependences of the conductivity can be quantitatively described as hopping of charge carriers being subject to spatially randomly varying energy barriers. For the low-frequency regime and for the critical frequency marking the onset of the conductivity's dispersion, the Barton-Nakajima-Namikawa (BNN) relationship is fulfilled. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 093 Y1 - 1995 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17438 ER - TY - GEN A1 - Laschewsky, André A1 - Schulz-Hanke, Wolfgang T1 - Ring-opening metathesis polymerization of amphiphilic norbornenes functionalized with non-linear optical (NLO) chromophores N2 - Contents: Potential of amphiphilic NLO polymers Ring-opening metathesis polymerization (ROMP) Properties of the polymers Monolayer properties Experimental part - Methods - Materials - Analytical data - General polymerization procedure Conclusions T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 092 Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-26917 ER - TY - GEN A1 - Anton, Peter A1 - Laschewsky, André T1 - Zwitterionic polysoaps with reduced density of surfactant side groups N2 - Several zwitterionic polymers were prepared by radical homopolymerization of surfactant monomers which bear diallyl, diene or vinylcyclopropane moieties. These polymer systems were complemented by alternating copolymers of appropriate zwitterionic vinyl compounds. Thus, polymers with reduced (as compared with simple vinylic homopolymers, or statistical copolymers) and well defined density of surfactant side groups are obtained. The solubilities found for these polymers are dominated by polymer geometry rather than by the balance of hydrophilic and hydrophobic fragments, thus corroborating a main-chain spacer model proposed recently. All water-soluble polymers exhibit characteristic features of classical polysoaps, as shown by surface tension measurements and by solubilization of hydrophobic dyes. In contrast, the water-insoluble copolymers are capable to form stable monolayers at the air-water interface. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 091 Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17301 ER - TY - GEN A1 - Anton, Peter A1 - Köberle, Peter A1 - Laschewsky, André T1 - Recent developments in the field of micellar polymers N2 - This article describes recent achievements in the field of micellar polymers, or polysoaps. Taking advantage of zwitterionic model polymers, systematic variations of the molecular architecture have provided an improved understanding of the relationship between the molecular structure of the polymers and their key properties such as surface activity and solubilization capacity. Useful rules are established, which take into account much of the previous data in the literature. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 090 Y1 - 1993 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17263 ER - TY - GEN A1 - Köberle, Peter A1 - Laschewsky, André A1 - Tsukruk, Vladimir T1 - The structural order of some novel ionic polymers : 1. X-ray scattering studies N2 - A set of novel zwitterionic side-chain polyacrylates and polymethacrylates is studied by X-ray scattering. The structural order both in the short-range and long-range scale is investigated. The influence of the polymer backbone, of different locations of the ionic groups in isomeric polymers, of bound water and of added inorganic salts on the bulk structures is studied, and the observed rearrangements are analysed. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 089 Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17247 ER - TY - GEN A1 - Anton, Peter A1 - Laschewsky, André T1 - Polysoaps via alternating olefin/SO2 copolymers N2 - Contents: Introduction Results and discussion - Monomers studied - Monomer properties - Polymerization, copolymer composition and general properties - Polymer properties in aqueous solution Conclusion Experimental part - Materials - Copolymerization with S02 (typical procedure) - Methods T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 088 Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17216 ER - TY - GEN A1 - Laschewsky, André T1 - Molecular concepts, self-organisation and properties of polysoaps N2 - The article reviews water-soluble polymers characterized by surfactant side chains, and related amphiphilic polymers. Various synthetic approaches are presented, and rules for useful molecular architectures are given. Models for the self-organization of such polymers in water are presented comparing them with the micellization of low molecular weight surfactants. Highlighting key properties of aqueous polysoap solutions such as viscosity, surface tension and solubilization power, some structure-property relationships are established. Further, the formation of mesophases and of superstructures in bulk is addressed. Finally, the functionalization of polysoaps, and potential applications are discussed. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 087 Y1 - 1995 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-26895 ER - TY - GEN A1 - Köberle, Peter A1 - Laschewsky, André T1 - Hybrid materials from organic polymers and inorganic salts N2 - The prepaparation of amorphous, homogeneous blends of zwitterionic polymers and transition metal salts was investigated. Homogeneous miscibility was achieved in many cases up to equimolar amounts of salt, depending on the anion and cation chosen. Various analytical techniques point to a solid state solution of the inorganic ions in the polymer matrix. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 086 Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-26884 ER - TY - GEN A1 - Cochin, Didier A1 - Hendlinger, P. A1 - Laschewsky, André T1 - Polysoaps with fluorocarbon hydrophobic chains N2 - A series of amphiphilic copolymers is prepared by copolymerization of choline methacrylate with 1,1,2,2-tetrahydroperfluorooctyl methacrylate in varying amounts. The copolymers bearing fluorocarbon chains are studied concerning their effects on viscosity, solubilization and surface activity in aqueous solution, exhibiting a general behavior characteristic for polysoaps. The results are compared with the ones obtained for an analogous series of amphiphilic copolymers bearing hydrocarbon chains. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 085 KW - Amphiphilic polymers KW - fluorocarbon polymers KW - associating polymers KW - polysoaps Y1 - 1995 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17347 ER - TY - GEN A1 - Anton, Peter A1 - Laschewsky, André A1 - Ward, M. D. T1 - Solubilization control by redox-switching of polysoaps N2 - Reversible changes in the self-organization of polysoaps may be induced by controlling their charge numbers via covalently bound redox moieties. This is illustrated with two viologen polysoaps, which in response to an electrochemical stimulus, change their solubility and aggregation in water, leading from homogeneously dissolved and aggregated molecules to collapsed ones and vice verse. Using the electrochemical quartz crystal microbalance (EQCM), it could be shown that the reversibility of this process is better than 95% in 16 cycles. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 084 KW - Quartz Crystal KW - microbalance KW - films KW - Electrochemistry KW - viologen Y1 - 1995 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17336 ER - TY - GEN A1 - Anton, Peter A1 - Laschewsky, André T1 - Solubilization by polysoaps N2 - The aqueous solubilization power of several series of micellar homopolymers and copolymers (polysoaps) is investigated. Using five insoluble or poorly water-soluble dyes, comparisons of the capacities are made with respect ot the influence of structural variables such as the polymer backbone, the polymer geometry, the comonomer content, and the charge of the hydrophilic group. Some guidelines for polysoap structures suited for efficient solubilization are established. Noteworthy is that the solubilization capacities of the polysoaps are neither linked to the ability to reduce the surface tension of water, nor to the polarity of the solubilization sites deduced from spectroscopic probes. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 083 KW - Micellar polymers KW - polysoaps KW - solubilization Y1 - 1994 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17327 ER - TY - GEN A1 - Bubeck, Christoph A1 - Laschewsky, André A1 - Lupo, Donald A1 - Neher, Dieter A1 - Ottenbreit, Petra A1 - Paulus, Wolfgang A1 - Prass, Werner A1 - Ringsdorf, Helmut A1 - Wegner, Gerhard T1 - Amphiphilic dyes for nonlinear optics: Dependence of second harmonic generation on functional group substitution T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 082 Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17201 ER - TY - GEN A1 - Embs, Frank A1 - Funhoff, Dirk A1 - Laschewsky, André A1 - Licht, Ulrike A1 - Ohst, Holger A1 - Prass, Werner A1 - Ringsdorf, Helmut A1 - Wegner, Gerhard A1 - Wehrmann, Rolf T1 - Preformed polymers for Langmuir-Blodgett films- molecular concepts N2 - The use of preformed polymers for the preparation of Langmuir-Blodgett (LB) multilayers is reviewed. Principles for polymer self-organization are outlined and the appropriate molecular designs are discussed. Recent developments in the different classes of polymers for LB multilayers are presented, and their outstanding properties highlighted. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 081 KW - Amphiphilic Polymers KW - Rod-like Polymers KW - LCPs KW - Stability of LB Films Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17196 ER - TY - GEN A1 - Erdelen, C. A1 - Laschewsky, André A1 - Ringsdorf, H. A1 - Schneider, J. A1 - Schuster, A. T1 - Thermal behaviour of polymeric Langmuir-Blodgett multilayers N2 - Langmuir-Blodgett multilayers of hydrocarbon and fluorocarbon polymers with hydrophilic spacer, lipid-polyelectrolyte complexes and mesogenic polymers have been prepared. The thermal behaviour of the multilayers was studied by small angle X-ray scattering, IR and UV—visible spectroscopy. Good thermal stabilities were found for the various classes of polymers. In addition, for both complexed multilayers and mesogenic polymer films, reorientation processes were observed. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 080 Y1 - 1989 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17378 ER - TY - GEN A1 - Albrecht, O. A1 - Cumming, W. A1 - Kreuder, W. A1 - Laschewsky, André A1 - Ringsdorf, Helmut T1 - Monolayers of rod-shaped and disc-shaped liquid crystalline compounds at the air-water interface N2 - Calamitic (rod-shaped) and discotic (disc-shaped) thermotropic liquid crystalline (LC) compounds were spread at the air-water interface, and their ability to form monolayers was studied. The calamitic LCs investigated were found to form monolayers which behave analogously to conventional amphiphiles such as fatty acids. The spreading of the discotic LCs produced monolayers as well, but with a behaviour different from classical amphiphiles. The areas occupied per molecule are too small to allow the contact of all hydrophilic groups with the water surface and the packing of all hydrophobic chains. Various molecular arrangements of the discotics at the water surface to fit the spreading data are discussed. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 079 KW - Monolayers KW - liquid crystals KW - discotics Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17124 ER - TY - GEN A1 - Koch, Horst A1 - Laschewsky, André A1 - Ringsdorf, Helmut A1 - Teng, Kang T1 - Photodimerization and photopolymerization of amphiphilic cinnamic acid derivatives in oriented monolayers, vesicles and solution N2 - Cinnamic acid moieties were incorporated into amphiphilic compounds containing one and two alkyl chains. These lipid-like compounds with photoreactive units undergo self-organization to form monolayers at the gas-water interface and bilayer structures (vesicles) in aqueous solutions. The photoreaction of the cinnamic acid moiety induced by 254 nm UV light was investigated in the crystalline state, in monolayers, in vesicles and in solution in organic solvents. The single-chain amphiphiles undergo dimerization to yield photoproducts with twice the molecular weight of the corresponding monomers in organized systems. The photoreaction of amphiphiles containing two cinnamic acid groups occurs via two mechanisms: The intramolecular dimerization produces bicycles, with retention of the molecular weight of the corresponding monomer. The intermolecular reaction leads to oligomeric and polymeric photoproducts. In contrast to the single-chain amphiphiles, photodimerization processes of lipoids containing two cinnamic acid moieties also occur in solution in organic solvents. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 078 Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17111 ER - TY - GEN A1 - Ferenz, Hans-Jürgen A1 - Peter, Martin G. A1 - Berg, Dieter T1 - Inhibition of farnesoic acid methyltransferase by sinefungin N2 - Sinefungin inhibited the S-adenosylmethionine-dependent farnesoic acid methyltransferase in a cell-free system containing a homogenate of corpora allata from female locusts, Locusta migratoria. The enzyme catalyzed the penultimate step of juvenile hormone biosynthesis in the insects. Culturing corpora allata in the presence of sinefungin greatly suppressed juvenile hormone production. The following in vivo effects were visible after injection of the inhibitor: increase in mortality and reduction of total haemolymph protein liter and ovary fresh weight, as well as length of terminal oocytes. Attempts to reverse these effects by topical application of the juvenile hormone analog ZR-515 (methoprene) were only partly successful. Therefore, the in vivo effects may be due to a general inhibition of methyltransferase enzymes in the insect. Sinefungin appeared to be of potential interest as the first representative of a new class of insect growth regulators. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 077 KW - Juvenile hormone analogue KW - Orthoptera KW - Juvenile hormone KW - Biosynthesis KW - Enzyme KW - Corpora allata KW - In vitro KW - Biological activity KW - Enzyme inhibitor Y1 - 1983 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17016 ER - TY - GEN A1 - Ferenz, Hans-Jörg A1 - Peter, Martin G. T1 - The inhibitory effect of sinefungin on juvenile hormone biosynthesis and development in locusts N2 - The antibiotic fungal metabolite sinefungin is a potent inhibitor of S-adenosylmethionine-acceptor methyltransferases. Its effect on insect metabolism and especially on corpora allata farnesoic acid methyltransferase, which catalyzes the penultimate step of juvenile hormone biosynthesis, was investigated in Locusta migratoria. Injection of sinefungin results in a delay of imaginal molt and in suppression of ovary development. Isolated corpora allata are unable to synthesize juvenile hormone III in the presence of more than 1.0 mM sinefungin. In a cell-free system containing the S-adenosylmethionine-dependent farnesoic acid methyltransferase from corpora allata sinefungin is a competitive inhibitor of the synthesis of methylfarnesoate with Ki of 1 μM. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 076 KW - Locust KW - sinefungin KW - O-methyltransferase KW - juvenile hormone biosynthesis Y1 - 1987 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-16811 ER - TY - GEN A1 - Andersen, Svend Olav A1 - Perter, Martin G. A1 - Roepstorff, Peter T1 - Cuticle-catalyzed coupling between N-acetylhistidine and N-acetyldopamine N2 - Several types of insect cuticle contain enzymes catalyzing the formation ofof adducts between N-acetyldopamine (NADA) and N-acetylhistidine (NAH). Two such adducts, NAH-NADA-I and NAH NADA-II, have been isolated and their structures determined. In one of the adducts the link connecting the two residues occurs between the I-position (ß-position) in the NADA side chain and the 1-N atom (τ-N) in the imidazole ring of histidine. Diphenoloxidase activity alone is not sufficient for formation of this adduct, whereas extracts containing both diphenoloxidase and o-quinone-p-quinone methide isomerase activities catalyze the coupling reaction. The adduct consists of a mixture of two diastereomers and they are presumably formed by spontaneous reaction between enzymatically produced NADA-p-quinone methide and N-acetylhistidine. The other adduct has been identified as a ring addition product of N-acetylhistidine and NADA. In contrast to the former adduct it can be formed by incubation of the two substrates with mushroom tyrosinase alone. An adduct between N-acetylhistidine and the benzodioxan-type NADA-dimer is produced in vitro, when the N-acetylhistidine-NADA adduct is incubated with NADA and locust cuticle containing a 1,2-dehydro-NADA generating enzyme system. Trimeric NADA-polymerization products of the substituted benzodioxan-type have been obtained from in vivo sclerotized locust cuticle, confirming the ability of cuticle to produce NADA-oligomers. The results indicate that some insect cuticles contain enzymes promoting linkage of oxidized NADA to histidine residues. It is suggested that histidine residues in the cuticular proteins can serve as acceptors for oxidized NADA and that further addition of NADA-residues to the phenolic groups of bound NADA can occur, resulting in formation of protein-linked NADA-oligomers. The coupling reactions identified may be an important step in natural cuticular sclerotization. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 072 KW - sclerotization KW - quinone KW - quinone methide KW - o-quinone isomerase KW - Hyalophora cecropia KW - Locusta migratoria Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-16762 ER - TY - GEN A1 - Kort, C. A. D. de A1 - Peter, Martin G. A1 - Koopmanschap, A. B. T1 - Binding and degradation of juvenile hormone III by haemolymph proteins of the Colorado potato beetle: a re-examination N2 - The haemolymph of the adult Colorado potato beetle, Lepinotarsa decemlineata Say, contains a high molecular weight (MW > 200,000) JH-III specific binding protein. The Kd value of the protein for racemic JH-III is 1.3 ± 0.2 × 10−7 M. It has a lower affinity for racemic JH-I and it does not bind JH-III-diol or JH-III-acid. The binding protein does discriminate between the enantiomers of synthetic, racemic JH-III as was determined by stereochemical anaysis of the bound and the free JH-III. Incubation of racemic JH-III with crude haemolymph results in preferential formation of (10S)-JH-III-acid, the unnatural configuration. The JH-esterase present in L. decemlineata haemolymph is not enantioselective. It is concluded that the most important function of the binding protein is that of a specific carrier, protecting the natural hormone against degradation by esterases. The carrier does not protect JH-I as efficiently as the lower homologue. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 068 KW - Juvenile hormone KW - Leptinotarsa decemlineata KW - JH-III-specific carrier protein KW - enantioselectivity Y1 - 1983 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-16777 ER - TY - GEN A1 - Peter, Martin G. A1 - Andersen, Svend Olav A1 - Hartmann, Rudolf A1 - Miessner, Merle A1 - Roepstorff, Peter T1 - Catecholamine-protein conjugates : isolation of 4-phenylphenoxazin-2-ones from oxidative coupling of N-acetyldopamine with alipathic amino acids N2 - 4-Phenylphenoxazinones were isolated after biomimetic oxidation, using diphenoloxidases of insect cuticle, mushroom tyrosinase, or after autoxidation of N-acetyldopamine (Image ) in the presence of β-alanine, β-alanine methyl ester or N-acetyl-L-lysine. They are formed presumably by addition of 2-aminoalkyl-5-alkylphenols to the o-quinone of biphenyltetrol which, in turn, arises from oxidative coupling of. The structures of present the first examples for the assembly of reasonably stable intermediates in the rather complex process of chemical modifications of aliphatic amino acid residues by o-quinones. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 062 Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17571 ER - TY - GEN A1 - Laschewsky, André T1 - Monolayers and Langmuir-Blodgett multilayers of discotic liquid crystals? N2 - Contents: 1. Discotic Liquid Crystals 2. Monolayers and Langmuir-Blodgett Multilayers 3. Theoretical Considerations on the Molecular Packing of Discotic LCs in Monolayers and Multilayers 4. Spreading Experiments with Discotic LCs 5. LB-Multilayers of Discotic LCs 6. Polymeric Discotic LCs 7. Summary T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 061 Y1 - 1989 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17396 ER - TY - GEN A1 - Laschewsky, André A1 - Paulus, Wolfgang A1 - Ringsdorf, Helmut A1 - Schuster, A. A1 - Frick, G. A1 - Mathy, A. T1 - Mixed polymeric monolayers and Langmuir-Blodgett multilayers with functional low molecular weight guest compounds N2 - Mixed monolayers and Langmuir-Blodgett multilayers of functional low molecular weight guest compounds, especially nonlinear optical (NLO) dyes, within the matrix of an amphotropic spacer polymer have been prepared. The polymer matrix enabled the transfer of guest compounds not capable of self-organizing at the air-water interface by themselves. The structure of the LB multilayers and the transfer process were studied by small angle X-ray scattering and UV-visible spectroscopy. Good NLO coefficients were found in the mixed films. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 060 Y1 - 1992 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17233 ER - TY - GEN A1 - Laschewsky, André T1 - Oligoethyleneoxide spacer groups in polymerizable surfactants N2 - Cationic and zwitterionic polymerizable surfactants bearing tri- and tetraethyleneglycol spacer groups between the polymerizable moiety and the surfactant structure were prepared and polymerized. Monomers and polymers were investigated with respect to their aggregation behavior in aqueous systems and compared to analogous monomers and polymers lacking spacer groups. In the case of the monomeric surfactants, the spacer groups depress both the Kraffttemperature and the critical micelle concentration. the area occupied per molecule at the air-water interface is substantially enlarged by the spacers, whereas the depression of surface tension is nearly constant. Although the monomers with and without spacers are true surfactants, all the polymers are water-insoluble, but form monomolecular layers at the air-water interface. In analogy to the monomer behavior, the incorporation of the spacer groups increases the area occupied per repeat unit at the air-water interface substantially, but hardly affects the surface activity. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 059 KW - Polymerizable surfactant KW - polysoap KW - sulfobetain KW - spacer KW - micelle KW - monolayer Y1 - 1991 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17221 ER - TY - GEN A1 - Laschewsky, André A1 - Ringsdorf, H. T1 - Polymerization of amphiphilic dienes in Langmuir-Blodgett multilayers N2 - Amphiphilic derivatives of octadiene and docosadiene were investigated in monolayers and Langmuir-Blodgett multilayers, with respect to their self-organization and their polymerization behavior. All amphiphiles investigated form monolayers. However, only acid and alcohol derivatives were able to build up multilayers. Those multilayers are rapidly photopolymerized in the layers via a two-step process: Irradiation with long-wavelength UV light yields soluble polymers, whereas additional irradiation with sfiort-wavelength UV light produces insoluble and presumably cross-linked polymers. The reaction meclianism is discussed according to the polymer characterization by UV spectroscopy, small-angle X-ray scattering, NMR spectroscopy, and gel permeation chromatography. All multilayers undergo structural changes during the polymerization; substantial changes result in defects in the polymerized layers as observed by scanning electron microscopy. In contrast to the acids and alcohols, the deposition of monolayers of the aldehyde derivatives did not yield well-ordered multilayers, but rather amorphous films. In this different film structure, the photopolymerization process differs from the one observed in multilayers. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 058 Y1 - 1988 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17176 ER - TY - GEN A1 - Laschewsky, André A1 - Ringsdorf, H. A1 - Schmidt, G. A1 - Schneider, J. T1 - Self-organization of polymeric lipids with hydrophilic spacers in side groups and main chain : investigation in monolayers and multilayers N2 - Several polymerizable lipids were synthesized and polymerized to amphiphilic homopolymers and to copolymers with the help of hydrophilic comonomers. The self-organization of these polymeric lipids was investigated in monolayers and Langmuir-Blodgett multilayers. The self-organization of these polymers in model membranes is due to hydrophilic spacer groups in the amphiphilic side groups as well as to hydrophilic spacer groups in the polymer backbone. Thus, highly ordered monolayers and LB-multilayers are easily obtained. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 057 Y1 - 1987 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17147 ER - TY - GEN A1 - Laschewsky, André A1 - Ringsdorf, H. A1 - Schneider, J. T1 - Oriented supramolecular systems-polymeric monolayers and multilayers from prepolymerized amphiphiles N2 - Oriented polymeric membranes were originally prepared by polymerization or polycondensation of preoriented monomers. The introduction of hydrophilic spacer groups into the polymeric amphiphiles allowed the formation of highly ordered systems (monolayers, liposomes, multilayers) from prepolymerized amphiphiles: due to the partial decoupling of the different mobilities and orientation tendencies of the polymer chain and the amphiphilic side groups, these polymers are able to self-organize. In monolayer experiments the high order of these membranes could be demonstrated by their surface pressure area-diagrams. In addition the combination of order and mobility of these spacer groups containing polymeric amphiphiles allowed the formation of Langmuir-Blodgett-multilyers with a high layer correlation. Thus, disturbancies in highly oriented layers can be avoided normally taking place during the polymerization reaction (e.g. contractions) or oriented monomeric layers. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 056 Y1 - 1986 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17131 ER - TY - GEN A1 - Laschewsky, André A1 - Ringsdorf, H. A1 - Schmidt, G. T1 - Polymerization of hydrocarbon and fluorocarbon amphiphiles in Langmuir-Blodgett multilayers N2 - Langmuir-Blodgett multilayers of polymerizable carboxylic acids with hydrocarbon or fluorocarbon chains were prepared. The multilayers were polymerized by UV light and the reactions were studied by UV/visible spectroscopy. The polyreactions strongly influence the multilayer structures which were investigated by X-ray small-angle scattering and scanning electron microscopy. The spreading behaviour of the monomers, the preparation of multilayers, their reactivities in multilayers and structural effects caused by the polyreactions are discussed with regard to the hydrophilic head groups, the polymerizable groups and the hydrophobic chains. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 055 Y1 - 1985 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17096 ER - TY - GEN A1 - Peter, Martin G. A1 - Förster, Hans T1 - On the structure of Eumelanins : identification of constitutional patterns by solid-state NMR spectroscopy N2 - Aus dem Inhalt: Melanins are complex polyphenolic polymers. They are usually formed in nature by enzyme-catalyzed oxidative polymerization of o-diphenols. The deep black eumelanins, derived from Dopa 1 or dopamine 3, are distinguished from the yellow to brown phaeomelanins obtained from Dopa in the presence of cysteine. Characteristic of eumelanins are the indole units, which are formed from catecholamines by intramolecular addition of the amino groups to the oxidatively generated o-quinones. [...] T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 053 Y1 - 1989 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-17027 ER - TY - GEN A1 - Peter, Martin G. T1 - Products of in vitro oxidation of N-acetyldopamine as possible components in the sclerotization of insect cuticle N2 - [1-14C]-N-Acetyldopamine (NADA) was oxidized in the presence of methyl [3-3H]-β-alanate with mushroom tyrosinase. The complex mixture of reaction products was partly resolved by chromatographic procedures and analyzed by spectroscopic methods. Methyl-β-alanate is incorporated to only a small extent into oxidation products of NADA which inter alia are presumed to be oligomeric hydroxyquinones. After oxidation of [1-14C, 2-3H]-NADA with preparations from tanning Manduca sexta pupal cuticle, N-acetylnoradrenalin was identified as one of the products. Binding of radioactivity to melanin-like material was also observed. These results suggest that oxidation products different from those formulated usually for the crosslinkages between protein amino groups and N-acetyldopaquinone are deposited in darkly brown coloured insect cuticles during sclerotization. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 041 KW - N-acetyldopamine KW - sclerotization KW - tyrosinase; o-quinones KW - tanning agents Y1 - 1980 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-16759 ER - TY - THES A1 - Frankovitch, Christine Marie T1 - Optical methods for monitoring biological parameters of phototropic microorganisms during cultivation T1 - Optische Verfahren zur Beobachtung biologischer Parameter während der Kultivierung phototropischer Mikroorganismen N2 - Phototropic microalgae have a large potential for producing valuable substances for the feed, food, cosmetics, pigment, bioremediation, and pharmacy industries as well as for biotechnological processes. Today it is estimated that the microalgal aquaculture worldwide production is 5000 tons of dry matter per year (not taking into account processed products) making it an approximately $1.25 billion U.S. per year industry. In this work, several spectroscopic techniques were utilized for the investigation of microalgae cells. Specifically, photondensity wave spectroscopy was applied as a technique for the on-line observation of the culture. For effective evaluation of the photosynthetic growth processes, fast and non-invasive sensor systems that analyze the relevant biological and technical process parameters are preferred. Traditionally, the biomass in a photobioreactor is quantified with the help of turbidimetry measurements, which require extensive calibration. Another problem frequently encountered when using spectral analysis for investigating solutions is that samples of interest are often undiluted and highly scattering and do not adhere to Beer-Lambert's law. Due to the fluorescence properties of chlorophyll, fluorescence spectroscopy techniques including fluorescence lifetime imaging and single photon counting could be applied to provide images of the cells as well as determine the effects of excitation intensity on the fluorescence lifetime, which is an indicator of the condition of the cell. A photon density wave is a sinusoidally intensity-modulated optical wave stemming from a point-source of light, which propagates through diffuse medium and exhibits amplitude and phase variations. Light propagation though strongly scattering media can be described by the P1 approximation to the Boltzmann transport equation. Photon density wave spectroscopy enables the ability to differentiate between scattered and absorbed light, which is desired so that an independent determination of the reduced scattering and absorption coefficients can be made. The absorption coefficient is related to the pigment content in the cells, and the reduced scattering coefficient can be used to characterize physical and morphological properties of the medium and was here applied for the determination of the average cell size. N2 - Phototropische Mikroalgen besitzen ein großes Potential für die Herstellung von wertvollen Substanzen sowohl für die Futtermittel-, Lebensmittel-, kosmetische und pharmazeutische Industrie, als auch für die Farbstoffsynthese. Heutzutage werden schätzungsweise 5000 Tonnen Mikroalgen Trockensubstanz pro Jahr mit einem Jahresumsatz von 1,25 Mrd. US-Dollar produziert. In dieser Arbeit wurden diverse spektroskopische Untersuchungsmethoden für die Betrachtung der Zellen verwendet. Die Photonendichtewellenspektroskopie (PDW) fand dabei insbesondere bei der on-line Beobachtung der Zellen Anwendung. Voraussetzungen für die effektive Beobachtung von photosynthetischen Wachstumsprozessen sind schnell und nicht-invasiv arbeitende Sensoren. Normalerweise wird die dabei zu untersuchende Biomasse in einem Photobioreaktor mittels Trübungsmessungen quantifiziert. Dies setzt jedoch eine sehr aufwendige Kalibration voraus. Da diese Proben zusätzlich meist in unverdünnter Form vorliegen, streuen sie stark und folgen daher nicht dem Lambert-Beer'schen Gesetz. Aufgrund der Fluoreszenzeigenschaften des Chlorophylls können fluoreszenzspektroskopische Methoden wie fluorescence lifetime imaging microscopy (FLIM) und time correlated single photon counting (TCSPC) angwendet werden. Diese Methoden werden dabei für die visuelle Darstellung der Zellen und für die Messung der Fluoreszenzlebenszeit genutzt. Eine Photondichtewelle ist eine sinusförmig intensitätsmodulierte optische Welle, die sich, ausgehend von einer punktförmigen Lichtquelle, durch das untersuchte Medium ausbreitet, wobei sich Phase und Amplitude der Welle verändern. Die Ausbreitung der Welle wird von der P1-Näherung der Boltzmann-Transport-Gleichung beschrieben. Mittels PDW kann zwischen streuenden und absorbierenden Eigenschaften von trüben Probe unterschieden werden. Dies erlaubt die Absolutbestimmung des Absorptions- und reduzierten Streukoeffizienten, die für die Qualifizierung der Probe, insbesondere der Teilchengrößenbestimmung, herangezogen werden. KW - Photonendichtewellen KW - Mikroalgen KW - Photon density waves KW - Microalgae KW - On.Line Monitoring Y1 - 2007 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-15403 ER - TY - GEN A1 - Kaafarani, Bilal R. A1 - Wex, Brigitte A1 - Strehmel, Bernd A1 - Neckers, Douglas C. T1 - Structural concept for fluorinated Y-enynes with solvatochromic properties N2 - An approach to the development of fluorescent probes to follow polymerizations in situ using fluorinated cross-conjugated enediynes (Y-enynes) is reported. Different substitution patterns in the Y-enynes result in distinct solvatochromic behavior. β,β-Bis(phenylethynyl)pentafluorostyrene 7, which bears no donor substituents and only fluorine at the styrene moiety, shows no solvatochromism. Donor substituted β,β-bis(3,4,5-trimethoxyphenylethynyl) pentafluorostyrene 8 and β,β-bis(4-butyl-2,3,5,6-tetrafluorophenylethynyl)-3,4,5-trimethoxystyrene 9 exhibit solvatochromism upon change of solvent polarity. Y-enyne 8 showed the largest solvatochromic shift (94 nm bathochromic shift) upon changing solvent from cyclohexane to acetonitrile. A smaller solvatochromic response (44 nm bathochromic shift) was observed for 9. Lippert–Mataga treatment of 8 and 9 yields slopes of -10,800 and -6,400 cm -1, respectively. This corresponds to a change in dipole moment of 9.6 and 6.9 D, respectively. The solvatochromic behavior in 8 and 9 supports the formation of an intramolecular charge transfer (ICT) state. The low fluorescence quantum yields are caused by competitive double bond rotation. The fluorescence decay time of 9 decreases in methyltetrahydrofuran from 2.1 ns at 77 K to 0.11 ns at 200 K. Efficient single bond rotation in 9 was frozen at -50 °C in a configuration in which the trimethoxyphenyl ring is perpendicular to the fluorinated rings. 7–9 are photostable compounds. The X-ray structure of 7 shows it is not planar and that its conjugation is distorted. Y-enyne 7 stacks in the solid state showing coulombic, actetylene–arene, and fluorine–π interactions. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 027 Y1 - 2002 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-13168 ER - TY - GEN A1 - Reich, Oliver A1 - Löhmannsröben, Hans-Gerd A1 - Schael, Frank T1 - Optical sensing with photon density waves: investigation of model media N2 - Investigations with frequency domain photon density waves allow elucidation of absorption and scattering properties of turbid media. The temporal and spatial propagation of intensity modulated light with frequencies up to more than 1 GHz can be described by the P1 approximation to the Boltzmann transport equation. In this study, we establish requirements for the appropriate choice of turbid model media and characterize mixtures of isosulfan blue as absorber and polystyrene beads as scatterer. For these model media, the independent determination of absorption and reduced scattering coefficients over large absorber and scatterer concentration ranges is demonstrated with a frequency domain photon density wave spectrometer employing intensity and phase measurements at various modulation frequencies. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 026 Y1 - 2003 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-13147 ER - TY - GEN A1 - Engelhard, Sonja A1 - Kumke, Michael Uwe A1 - Löhmannsröben, Hans-Gerd T1 - OPQS – optical process and quality sensing : exemplary applications in the beerbrewing and polyurethane foaming processes N2 - Optical methods play an important role in process analytical technologies (PAT). Four examples of optical process and quality sensing (OPQS) are presented, which are based on three important experimental techniques: near-infrared absorption, luminescence quenching, and a novel method, photon density wave (PDW) spectroscopy. These are used to evaluate four process and quality parameters related to beer brewing and polyurethane (PU) foaming processes: the ethanol content and the oxygen (O2) content in beer, the biomass in a bioreactor, and the cellular structures of PU foam produced in a pilot production plant. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 004 KW - process analytical technology KW - beer KW - biomass KW - foam analysis KW - NIR spectroscopy KW - fluorescence quenching KW - photon density wave spectroscopy Y1 - 2006 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12191 ER - TY - GEN A1 - Schmälzlin, Elmar A1 - Walz, Bernd A1 - Klimant, Ingo A1 - Schewe, Bettina A1 - Löhmannsröben, Hans-Gerd T1 - Monitoring hormone-induced oxygen consumption in the salivary glands of the blowfly, Calliphora vicina, by use of luminescent microbeads N2 - The salivary glands of the blowfly were injected with luminescent oxygen-sensitive microbeads. The changes in oxygen content within individual gland tubules during hormone-induced secretory activity were quantified. The measurements are based on an upgraded phase-modulation technique, where the phase shift of the sensor phosphorescence is determined independently from concentration and background signals. We show that the combination of a lock-in amplifier with a fluorescence microscope results in a convenient setup to measure oxygen concentrations within living animal tissues at the cellular level. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 006 Y1 - 2006 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12206 ER -