TY - GEN A1 - Mondal, Suvendu Sekhar A1 - Behrens, Karsten A1 - Matthes, Philipp R. A1 - Schönfeld, Fabian A1 - Nitsch, Jörn A1 - Steffen, Andreas A1 - Primus, Philipp-Alexander A1 - Kumke, Michael Uwe A1 - Müller-Buschbaum, Klaus A1 - Holdt, Hans-Jürgen T1 - White light emission of IFP-1 by in situ co-doping of the MOF pore system with Eu3+ and Tb3+ N2 - Co-doping of the MOF 3∞[Zn(2-methylimidazolate-4-amide-5-imidate)] (IFP-1 = Imidazolate Framework Potsdam-1) with luminescent Eu3+ and Tb3+ ions presents an approach to utilize the porosity of the MOF for the intercalation of luminescence centers and for tuning of the chromaticity to the emission of white light of the quality of a three color emitter. Organic based fluorescence processes of the MOF backbone as well as metal based luminescence of the dopants are combined to one homogenous single source emitter while retaining the MOF's porosity. The lanthanide ions Eu3+ and Tb3+ were doped in situ into IFP-1 upon formation of the MOF by intercalation into the micropores of the growing framework without a structure directing effect. Furthermore, the color point is temperature sensitive, so that a cold white light with a higher blue content is observed at 77 K and a warmer white light at room temperature (RT) due to the reduction of the organic emission at higher temperatures. The study further illustrates the dependence of the amount of luminescent ions on porosity and sorption properties of the MOF and proves the intercalation of luminescence centers into the pore system by low-temperature site selective photoluminescence spectroscopy, SEM and EDX. It also covers an investigation of the border of homogenous uptake within the MOF pores and the formation of secondary phases of lanthanide formates on the surface of the MOF. Crossing the border from a homogenous co-doping to a two-phase composite system can be beneficially used to adjust the character and warmth of the white light. This study also describes two-color emitters of the formula Ln@IFP-1a–d (Ln: Eu, Tb) by doping with just one lanthanide Eu3+ or Tb3+. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 190 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-79953 SP - 4623 EP - 4631 ER - TY - GEN A1 - Mondal, Suvendu Sekhar A1 - Bhunia, Asamanjoy A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Janiak, Christoph A1 - Holdt, Hans-Jürgen T1 - A supramolecular Co(II)₁₄-metal–organic cube in a hydrogen-bonded network and a Co(II)–organic framework with a flexible methoxy substituent N2 - The reaction of 4,5-dicyano-2-methoxyimidazole (L1) with Co(NO3)2·6H2O under solvothermal conditions in DMF, a MOF, IFP-8 and a hydrogen-bonded network consisting of tetradecanuclear Co(II)14-metal organic cube (1) are achieved. 1 shows the bcu net with 14 cobalt atoms. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 169 KW - zinc Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-74098 IS - 169 SP - 5441 EP - 5443 ER - TY - GEN A1 - Xie, Zai-Lai A1 - Huang, Xing A1 - Titirici, Maria-Magdalena A1 - Taubert, Andreas T1 - Mesoporous graphite nanoflakes via ionothermal carbonization of fructose and their use in dye removal N2 - The large-scale green synthesis of graphene-type two-dimensional materials is still challenging. Herein, we describe the ionothermal synthesis of carbon-based composites from fructose in the iron-containing ionic liquid 1-butyl-3-methylimidazolium tetrachloridoferrate(III), [Bmim][FeCl4] serving as solvent, catalyst, and template for product formation. The resulting composites consist of oligo-layer graphite nanoflakes and iron carbide particles. The mesoporosity, strong magnetic moment, and high specific surface area of the composites make them attractive for water purification with facile magnetic separation. Moreover, Fe3Cfree graphite can be obtained via acid etching, providing access to fairly large amounts of graphite material. The current approach is versatile and scalable, and thus opens the door to ionothermal synthesis towards the larger-scale synthesis of materials that are, although not made via a sustainable process, useful for water treatment such as the removal of organic molecules. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 283 Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-99427 ER - TY - GEN A1 - Ehlert, Christopher A1 - Unger, Wolfgang E. S. A1 - Saalfrank, Peter T1 - C K-edge NEXAFS spectra of graphene with physical and chemical defects BT - a study based on density functional theory N2 - Recently, C K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of graphite (HOPG) surfaces have been measured for the pristine material, and for HOPG treated with either bromine or krypton plasmas (Lippitz et al., Surf. Sci., 2013, 611, L1). Changes of the NEXAFS spectra characteristic for physical (krypton) and/or chemical/physical modifications of the surface (bromine) upon plasma treatment were observed. Their molecular origin, however, remained elusive. In this work we study by density functional theory, the effects of selected point and line defects as well as chemical modifications on NEXAFS carbon K-edge spectra of single graphene layers. For Br-treated surfaces, also Br 3d X-ray Photoelectron Spectra (XPS) are simulated by a cluster approach, to identify possible chemical modifications. We observe that some of the defects related to plasma treatment lead to characteristic changes of NEXAFS spectra, similar to those in experiment. Theory provides possible microscopic origins for these changes. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 173 KW - absorbtion fine-structure KW - graphite Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-74429 SP - 14083 EP - 14095 ER - TY - GEN A1 - Wirth, Jonas A1 - Neumann, Rainer A1 - Antonietti, Markus A1 - Saalfrank, Peter T1 - Adsorption and photocatalytic splitting of water on graphitic carbon nitride BT - a combined first principles and semiempirical study N2 - Graphitic carbon nitride, g-C₃N₄, is a promising organic photo-catalyst for a variety of redox reactions. In order to improve its efficiency in a systematic manner, however, a fundamental understanding of the microscopic interaction between catalyst, reactants and products is crucial. Here we present a systematic study of water adsorption on g-C₃N₄ by means of density functional theory and the density functional based tight-binding method as a prerequisite for understanding photocatalytic water splitting. We then analyze this prototypical redox reaction on the basis of a thermodynamic model providing an estimate of the overpotential for both water oxidation and H⁺ reduction. While the latter is found to occur readily upon irradiation with visible light, we derive a prohibitive overpotential of 1.56 eV for the water oxidation half reaction, comparing well with the experimental finding that in contrast to H₂ production O₂ evolution is only possible in the presence of oxidation cocatalysts. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 172 KW - augmented-wave method KW - hydrogen KW - initio molecular-dynamics KW - oxidation KW - photooxidation KW - reduction KW - simulations KW - tight-binding KW - transition KW - visible-light Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-74391 SP - 15917 EP - 15926 ER - TY - GEN A1 - Vioux, André A1 - Taubert, Andreas T1 - Ionic liquids 2014 and selected papers from ILMAT 2013 BT - Highlighting the ever-growing potential of Ionic Liquids T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1055 KW - electrolytes KW - extraction KW - system Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-475062 SN - 1866-8372 IS - 1055 ER - TY - GEN A1 - Ermeydan, Mahmut Ali A1 - Cabane, Etienne A1 - Hass, Philipp A1 - Koetz, Joachim A1 - Burgert, Ingo T1 - Fully biodegradable modification of wood for improvement of dimensional stability and water absorption properties by poly(ε-caprolactone) grafting into the cell walls N2 - Materials derived from renewable resources are highly desirable in view of more sustainable manufacturing. Among the available natural materials, wood is one of the key candidates, because of its excellent mechanical properties. However, wood and wood-based materials in engineering applications suffer from various restraints, such as dimensional instability upon humidity changes. Several wood modification treatments increase water repellence, but the insertion of hydrophobic polymers can result in a composite material which cannot be considered as renewable anymore. In this study, we report on the grafting of the fully biodegradable poly(ε-caprolactone) (PCL) inside the wood cell walls by Sn(Oct)2 catalysed ring-opening polymerization (ROP). The presence of polyester chains within the wood cell wall structure is monitored by confocal Raman imaging and spectroscopy as well as scanning electron microscopy. Physical tests reveal that the modified wood is more hydrophobic due to the bulking of the cell wall structure with the polyester chains, which results in a novel fully biodegradable wood material with improved dimensional stability. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 270 KW - ring-opening polymerization KW - confocal raman microscopy KW - epsilon-caprolactone KW - mechanical-properties KW - structural-characterization KW - stannous octoate KW - copolymers KW - degradation KW - composites KW - cellulose Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-97265 SP - 3313 EP - 3321 ER - TY - GEN A1 - Ermeydan, Mahmut Ali A1 - Cabane, Etienne A1 - Gierlinger, Notburga A1 - Koetz, Joachim A1 - Burgert, Ingo T1 - Improvement of wood material properties via in situ polymerization of styrene into tosylated cell walls N2 - As an engineering material derived from renewable resources, wood possesses excellent mechanical properties in view of its light weight but also has some disadvantages such as low dimensional stability upon moisture changes and low durability against biological attack. Polymerization of hydrophobic monomers in the cell wall is one of the potential approaches to improve the dimensional stability of wood. A major challenge is to insert hydrophobic monomers into the hydrophilic environment of the cell walls, without increasing the bulk density of the material due to lumen filling. Here, we report on an innovative and simple method to insert styrene monomers into tosylated cell walls (i.e. –OH groups from natural wood polymers are reacted with tosyl chloride) and carry out free radical polymerization under relatively mild conditions, generating low wood weight gains. In-depth SEM and confocal Raman microscopy analysis are applied to reveal the distribution of the polystyrene in the cell walls and the lumen. The embedding of polystyrene in wood results in reduced water uptake by the wood cell walls, a significant increase in dimensional stability, as well as slightly improved mechanical properties measured by nanoindentation. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 274 Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-98736 ER - TY - GEN A1 - Sarauli, David A1 - Xu, Chenggang A1 - Dietzel, Birgit A1 - Schulz, Burkhard A1 - Lisdat, Fred T1 - A multilayered sulfonated polyaniline network with entrapped pyrroloquinoline quinone-dependent glucose dehydrogenase BT - tunable direct bioelectrocatalysis N2 - A feasible approach to construct multilayer films of sulfonated polyanilines – PMSA1 and PABMSA1 – containing different ratios of aniline, 2-methoxyaniline-5-sulfonic acid (MAS) and 3-aminobenzoic acid (AB), with the entrapped redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) on Au and ITO electrode surfaces, is described. The formation of layers has been followed and confirmed by electrochemical impedance spectroscopy (EIS), which demonstrates that the multilayer assembly can be achieved in a progressive and uniform manner. The gold and ITO electrodes subsequently modified with PMSA1:PQQ-GDH and PABMSA1 films are studied by cyclic voltammetry (CV) and UV-Vis spectroscopy which show a significant direct bioelectrocatalytical response to the oxidation of the substrate glucose without any additional mediator. This response correlates linearly with the number of deposited layers. Furthermore, the constructed polymer/enzyme multilayer system exhibits a rather good long-term stability, since the catalytic current response is maintained for more than 60% of the initial value even after two weeks of storage. This verifies that a productive interaction of the enzyme embedded in the film of substituted polyaniline can be used as a basis for the construction of bioelectronic units, which are useful as indicators for processes liberating glucose and allowing optical and electrochemical transduction. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 275 Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-98744 ER - TY - GEN A1 - Comminges, Clément A1 - Frasca, Stefano A1 - Sütterlin, Martin A1 - Wischerhoff, Erik A1 - Laschewsky, André A1 - Wollenberger, Ursula T1 - Surface modification with thermoresponsive polymer brushes for a switchable electrochemical sensor N2 - Elaboration of switchable surfaces represents an interesting way for the development of a new generation of electrochemical sensors. In this paper, a method for growing thermoresponsive polymer brushes from a gold surface pre-modified with polyethyleneimine (PEI), subsequent layer-by-layer polyelectrolyte assembly and adsorption of a charged macroinitiator is described. We propose an easy method for monitoring the coil-to-globule phase transition of the polymer brush using an electrochemical quartz crystal microbalance with dissipation (E-QCM-D). The surface of these polymer modified electrodes shows reversible switching from the swollen to the collapsed state with temperature. As demonstrated from E-QCM-D measurements using an original signal processing method, the switch is operating in three reversible steps related to different interfacial viscosities. Moreover, it is shown that the one electron oxidation of ferrocene carboxylic acid is dramatically affected by the change from the swollen to the collapsed state of the polymer brush, showing a spectacular 86% decrease of the charge transfer resistance between the two states. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 287 Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-99471 ER - TY - GEN A1 - Bald, Ilko A1 - Kopyra, Janina A1 - Keller, Adrian T1 - On the role of fluoro-substituted nucleosides in DNA radiosensitization for tumor radiation therapy N2 - Gemcitabine (2′,2′-difluorocytidine) is a well-known radiosensitizer routinely applied in concomitant chemoradiotherapy. During irradiation of biological media with high-energy radiation secondary low-energy (<10 eV) electrons are produced that can directly induce chemical bond breakage in DNA by dissociative electron attachment (DEA). Here, we investigate and compare DEA to the three molecules 2′-deoxycytidine, 2′-deoxy-5-fluorocytidine, and gemcitabine. Fluorination at specific molecular sites, i.e., nucleobase or sugar moiety, is found to control electron attachment and subsequent dissociation pathways. The presence of two fluorine atoms at the sugar ring results in more efficient electron attachment to the sugar moiety and subsequent bond cleavage. For the formation of the dehydrogenated nucleobase anion, we obtain an enhancement factor of 2.8 upon fluorination of the sugar, whereas the enhancement factor is 5.5 when the nucleobase is fluorinated. The observed fragmentation reactions suggest enhanced DNA strand breakage induced by secondary electrons when gemcitabine is incorporated into DNA. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 167 KW - low-energy electrons KW - single-strand breaks KW - gas-phase KW - chemoradiation therapy KW - molecular-mechanisms KW - resonant formation KW - damage KW - attachment KW - drugs Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-73412 SP - 6825 EP - 6829 ER - TY - GEN A1 - Pieper, Imke A1 - Wehe, Christoph A. A1 - Bornhorst, Julia A1 - Ebert, Franziska A1 - Leffers, Larissa A1 - Holtkamp, Michael A1 - Höseler, Pia A1 - Weber, Till A1 - Mangerich, Aswin A1 - Bürkle, Alexander A1 - Karst, Uwe A1 - Schwerdtle, Tanja T1 - Mechanisms of Hg species induced toxicity in cultured human astrocytes BT - genotoxicity and DNA-damage response N2 - The toxicologically most relevant mercury (Hg) species for human exposure is methylmercury (MeHg). Thiomersal is a common preservative used in some vaccine formulations. The aim of this study is to get further mechanistic insight into the yet not fully understood neurotoxic modes of action of organic Hg species. Mercury species investigated include MeHgCl and thiomersal. Additionally HgCl2 was studied, since in the brain mercuric Hg can be formed by dealkylation of the organic species. As a cellular system astrocytes were used. In vivo astrocytes provide the environment necessary for neuronal function. In the present study, cytotoxic effects of the respective mercuricals increased with rising alkylation level and correlated with their cellular bioavailability. Further experiments revealed for all species at subcytotoxic concentrations no induction of DNA strand breaks, whereas all species massively increased H2O2-induced DNA strand breaks. This co- genotoxic effect is likely due to a disturbance of the cellular DNA damage response. Thus, at nanomolar, sub-cytotoxic concentrations, all three mercury species strongly disturbed poly(ADP-ribosyl)ation, a signalling reaction induced by DNA strand breaks. Interestingly, the molecular mechanism behind this inhibition seems to be different for the species. Since chronic PARP-1 inhibition is also discussed to sacrifice neurogenesis and learning abilities, further experiments on neurons and in vivo studies could be helpful to clarify whether the inhibition of poly(ADP-ribosyl) ation contributes to organic Hg induced neurotoxicity. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - paper 171 KW - adduct formation KW - cell-death KW - exposure KW - manganese KW - methylmercury KW - neurodegenerative diseases KW - neurotoxicity KW - poly(ADP-ribose) polymerase-1 KW - repair KW - thimerosal Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-74379 SP - 662 EP - 671 ER -