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 - 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 - 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 - Dosche, Carsten
A1 - Löhmannsröben, Hans-Gerd
A1 - Bieser, A.
A1 - Dosa, P. I.
A1 - Han, S.
A1 - Iwamoto, M.
A1 - Schleifenbaum, A.
A1 - Vollhardt, K. Peter C.
T1 - Photophysical properties of [N]phenylenes
N2 - In the present study, photophysical properties of [N]phenylenes were studied by means of stationary and time-resolved absorption and fluorescence spectroscopy (in THF at room temperature). For biphenylene (1) and linear [3]phenylene (2a), internal conversion (IC) with quantum yields ΦIC > 0.99 is by far the dominant mechanism of S1 state deactivation. Angular [3]phenylene (3a), the zig-zag [4]- and [5]phenylenes (3b), (3c), and the triangular [4]phenylene (4) show fluorescence emission with fluorescence quantum yieds and lifetimes between ΦF = 0.07 for (3a) and 0.21 for (3c) and τF = 20 ns for (3a) and 81 ns for (4). Also, compounds (3) and (4) exhibit triplet formation upon photoexcitation with quantum yields as high as ΦISC = 0.45 for (3c). The strong differences in the fluorescence properties and in the triplet fromation efficiencies between (1) and (2a) on one hand and (3) and (4) on the other are related to the remarkable variation of the internal conversion (IC) rate constants kIC. A tentative classification of (1) and (2a) as “fast IC compounds”, with kIC > 109 s-1, and of (3) and (4) as “slow IC compounds”, with kIC ≈ 107 s-1, is suggested. This classification cannot simply be related to Hückel’s rule-type concepts of aromaticity, because the group of “fast IC compounds” consists of “antiaromatic” (1) and “aromatic” (2a), and the group of “slow IC compounds” consists of “antiaromatic” (3b), (4) and “aromatic” (3a), (3c). The IC in the [N]phenylenes is discussed within the framework of the so-called energy gap law established for non-radiative processes in benzenoid hydrocarbons.
T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 001
Y1 - 2002
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-11936
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 - 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 - 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 - 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 - 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 - 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 - 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 - 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 - Hildebrandt, Nico
A1 - Charbonnière, Loïc J.
A1 - Ziessel, Raymond F.
A1 - Löhmannsröben, Hans-Gerd
T1 - Quantum dots as resonance energy transfer acceptors for monitoring biological interactions
N2 - Quantum dots (QDs) are common as luminescing markers for imaging in biological applications because their optical properties seem to be inert against their surrounding solvent. This, together with broad and strong absorption bands and intense, sharp tuneable luminescence bands, makes them interesting candidates for methods utilizing Forster Resonance Energy Transfer (FRET), e. g. for sensitive homogeneous fluoroimmunoassays (FIA). In this work we demonstrate energy transfer from Eu3+-trisbipyridin (Eu-TBP) donors to CdSe-ZnS-QD acceptors in solutions with and without serum. The QDs are commercially available CdSe-ZnS core-shell particles emitting at 655 nm (QD655). The FRET system was achieved by the binding of the streptavidin conjugated donors with the biotin conjugated acceptors. After excitation of Eu-TBP and as result of the energy transfer, the luminescence of the QD655 acceptors also showed lengthened decay times like the donors. The energy transfer efficiency, as calculated from the decay times of the bound and the unbound components, amounted to 37%. The Forster-radius, estimated from the absorption and emission bands, was ca. 77Å. The effective binding ratio, which not only depends on the ratio of binding pairs but also on unspecific binding, was obtained from the donor emission dependent on the concentration. As serum promotes unspecific binding, the overall FRET efficiency of the assay was reduced. We conclude that QDs are good substitutes for acceptors in FRET if combined with slow decay donors like Europium. The investigation of the influence of the serum provides guidance towards improving binding properties of QD assays.
T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 012
Y1 - 2006
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-12213
ER -
TY - GEN
A1 - Hörner, Gerald
A1 - Lau, Steffen
A1 - Kantor, Zoltan
A1 - Löhmannsröben, Hans-Gerd
T1 - Isotope selective analysis of CO2 with tunable diode laser (TDL) spectroscopy in the NIR
N2 - The performance of a home-built tunable diode laser (TDL) spectrometer, aimed at multi-line detection of carbon dioxide, has been evaluated and optimized. In the regime of the (3001)III / (000) band of 12CO2 around 1.6 μm, the dominating isotope species 12CO2, 13CO2, and 12C18O16O were detected simultaneously without interference by water vapor. Detection limits in the range of few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. High sensitivity in conjunction with high precision —typically ±1‰ and ±6‰ for 3% and 0.7% of CO2, respectively— renders this experimental approach a promising analytical concept for isotope-ratio determination of carbon dioxide in soil and breath gas. For a moderate 12CO2 line, the pressure dependence of the line profile was characterized in detail, to account for pressure effects on sensitive measurements.
T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 020
KW - Isotopenverhältnis
KW - Kohlendioxid
KW - Diodenlaserspektroskopie
KW - Isotope ratio
KW - carbon monoxide
KW - diode laser spectroscopy
Y1 - 2004
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-10167
ER -
TY - GEN
A1 - Hörner, Gerald
A1 - Lau, Steffen
A1 - Löhmannsröben, Hans-Gerd
T1 - NIR-diode laser spectroscopy for isotope-selective sensing of soil-respired carbon dioxide
N2 - The performance of a home-built tunable diode laser (TDL) spectrometer has been optimized regarding multi-line detection of carbon dioxide in natural gases. In the regime of the (3001)III ← (000) band of 12CO2 around 1.6 μm, the dominating isotope species 12CO2, 13CO2, and 12C18O16O were detected simultaneously. In contrast to most established techniques, selective measurements are performed without any sample preparation. This is possible since the CO2 detection is free of interference from water, ubiquitous in natural gases. Detection limits in the range of a few ppmv were obtained for each species utilizing wavelength modulation (WM) spectroscopy with balanced detection in a long-path absorption cell set-up. Linear calibration plots cover a dynamic range of four orders of magnitude, allowing for quantitative CO2 detection in various samples, like soil and breath gas. High isotopic resolution enables the excellent selectivity, sensitivity, and stability of the chosen analytical concept. The obtained isotopic resolution of typically ± 1.0 ‰ and ± 1.5 ‰ (for 3 vol. % and 0.7 vol. % of CO2, respectively) offers a promising analytical tool for isotope-ratio determination of carbon dioxide in soil gas. Preliminary experiments on soil respiration for the first time combine the on-line quantification of the overall carbon dioxide content with an optode sensor and isotopic determination (TDL system) of natural gas species.
T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 021
KW - Kohlendioxid
KW - Isotopenverhältnis
KW - Bodengas
KW - Diodenlaserspektroskopie
KW - tunable diode laser (TDL)
KW - carbon dioxide
KW - isotope ratios
KW - soil gas
Y1 - 2004
U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-10148
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 - 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 - 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 - 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 - 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 -