TY - JOUR A1 - Schmidt, Marco F. A1 - Korb, Oliver A1 - Abell, Chris T1 - Antagonists of the miRNA-Argonaute 2 Protein Complex BT - Anti-miR-AGOs JF - Drug Target miRNA: Methods and Protocols N2 - microRNAs (miRNAs) have been identified as high-value drug targets. A widely applied strategy in miRNA inhibition is the use of antisense agents. However, it has been shown that oligonucleotides are poorly cell permeable because of their complex chemical structure and due to their negatively charged backbone. Consequently, the general application of oligonucleotides in therapy is limited. Since miRNAs’ functions are executed exclusively by the Argonaute 2 protein, we therefore describe a protocol for the design of a novel miRNA inhibitor class: antagonists of the miRNA-Argonaute 2 protein complex, so-called anti-miR-AGOs, that not only block the crucial binding site of the target miRNA but also bind to the protein’s active site. Due to their lower molecular weight and, thus, more drug-like chemical structure, the novel inhibitor class may show better pharmacokinetic properties than reported oligonucleotide inhibitors, enabling them for potential therapeutic use. KW - Drug design KW - microRNA KW - miRNA-Argonaute 2 protein complex KW - miRNA inhibitors KW - miRNA seed region Y1 - 2016 SN - 978-1-4939-6563-2 SN - 978-1-4939-6561-8 SN - 978-1-4939-8236-3 U6 - https://doi.org/10.1007/978-1-4939-6563-2_17 SN - 1064-3745 SN - 1940-6029 VL - 1517 SP - 239 EP - 249 PB - Springer CY - New York ER - TY - JOUR A1 - Selemani, Ramadhani Selemani Omari A1 - Nondo, Omari A1 - Moshi, Mainen Julius A1 - Erasto, Paul A1 - Masimba, Pax Jessey A1 - Machumi, Francis A1 - Kidukuli, Abdul Waziri A1 - Heydenreich, Matthias A1 - Zofou, Denis T1 - Anti-plasmodial activity of Norcaesalpin D and extracts of four medicinal plants used traditionally for treatment of malaria JF - BMC Complementary and Alternative Medicine volume N2 - Background: Malaria is an old life-threatening parasitic disease that is still affecting many people, mainly children living in sub-Saharan Africa. Availability of effective antimalarial drugs played a significant role in the treatment and control of malaria. However, recent information on the emergence of P. falciparum parasites resistant to one of the artemisinin-based combination therapies suggests the need for discovery of new drug molecules. Therefore, this study aimed to evaluate the antiplasmodial activity of extracts, fractions and isolated compound from medicinal plants traditionally used in the treatment of malaria in Tanzania. Methods: Dry powdered plant materials were extracted by cold macerations using different solvents. Norcaesalpin D was isolated by column chromatography from dichloromethane root extract of Caesalpinia bonducella and its structure was assigned based on the spectral data. Crude extracts, fractions and isolated compound were evaluated for antiplasmodial activity against chloroquine-sensitive P. falciparum (3D7), chloroquine-resistant P. falciparum (Dd2, K1) and artemisinin-resistant P. falciparum (IPC 5202 Battambang, IPC 4912 Mondolkiri) strains using the parasite lactate dehydrogenase assay. Results: The results indicated that extracts of Erythrina schliebenii, Holarrhena pubescens, Dissotis melleri and C. bonducella exhibited antiplasmodial activity against Dd2 parasites. Ethanolic root extract of E. schliebenii had an IC50 of 1.87 mu g/mL while methanolic and ethanolic root extracts of H. pubescens exhibited an IC50 = 2.05 mu g/mL and IC50 = 2.43 mu g/mL, respectively. Fractions from H. pubescens and C. bonducella roots were found to be highly active against K1, Dd2 and artemisinin-resistant parasites. Norcaesalpin D from C. bonducella root extract was active with IC50 of 0.98, 1.85 and 2.13 mu g/mL against 3D7, Dd2 and IPC 4912-Mondolkiri parasites, respectively. Conclusions: Antiplasmodial activity of norcaesalpin D and extracts of E. schliebenii, H. pubescens, D. melleri and C. bonducella reported in this study requires further attention for the discovery of antimalarial lead compounds for future drug development. KW - Antiplasmodial KW - norcaesalpin D KW - E. schliebenii KW - H. pubescens KW - D. melleri KW - C. bonducella Y1 - 2017 U6 - https://doi.org/10.1186/s12906-017-1673-8 SN - 1472-6882 VL - 17 PB - BioMed Central CY - London ER - TY - JOUR A1 - Muthaura, Charles N. A1 - Keriko, Joseph M. A1 - Mutai, Charles A1 - Yenesew, Abiy A1 - Heydenreich, Matthias A1 - Atilaw, Yoseph A1 - Gathirwa, Jeremiah W. A1 - Irungu, Beatrice N. A1 - Derese, Solomon T1 - Antiplasmodial, cytotoxicity and phytochemical constituents of four maytenus species used in traditional medicine in Kenya JF - The natural products journal N2 - Background: In Kenya, several species of the genus Maytenus are used in traditional medicine to treat many diseases including malaria. In this study, phytochemical constituents and extracts of Maytenus undata, M. putterlickioides, M. senegalensis and M. heterophylla were evaluated to determine compound/s responsible for antimalarial activity. Objective: To isolate antiplasmodial compounds from these plant species which could be used as marker compounds in the standardization of their extracts as a phytomedicine for malaria. Methods: Constituents were isolated through activity-guided fractionation of the MeOH/CHCl3 (1:1) extracts and in vitro inhibition of Plasmodium falciparum. Cytotoxicity was evaluated using Vero cells and the compounds were elucidated on the basis of NMR spectroscopy. Results: Fractionation of the extracts resulted in the isolation of ten known compounds. Compound 1 showed promising antiplasmodial activity with IC50, 3.63 and 3.95 ng/ml against chloroquine sensitive (D6) and resistant (W2) P. falciparum, respectively and moderate cytotoxicity (CC50, 37.5 ng/ml) against Vero E6 cells. The other compounds showed weak antiplasmodial (IC50 > 1.93 mu g/ml) and cytotoxic (CC50 > 39.52 mu g/ml) activities against P. falciparum and Vero E6 cells, respectively. Conclusion: (20 alpha)-3-hydroxy-2-oxo-24-nor-friedela-1(10),3,5,7-tetraen-carboxylic acid-(29)-methyl-ester (pristimerin) (1) was the most active marker and lead compound that warrants further investigation as a template for the development of new antimalarial drugs. Pristimerin is reported for the first time in M. putterlickioides. 3-Hydroxyolean-12-en-28-oic acid (oleanolic acid) (5), stigmast-5-en-3-ol (beta-sitosterol) (6), 3-oxo-28-friedelanoic acid (7), olean-12-en-3-ol (beta-amyrin) (8), lup-20(29)-en-3-ol (lupeol) (9) and lup-20(29)-en-3-one (lupenone) (10) are reported for the first time in M. undata. KW - Antimalarial plants KW - antiplasmodial KW - cytotoxicity KW - marker compound KW - Maytenus spp. KW - phytomedicine KW - pristimerin Y1 - 2017 U6 - https://doi.org/10.2174/2210315507666161206144050 SN - 2210-3155 SN - 2210-3163 VL - 7 IS - 2 SP - 144 EP - 152 PB - Bentham Science Publ. CY - Sharjah ER - TY - JOUR A1 - Klauß, André A1 - Conrad, Florian A1 - Hille, Carsten T1 - Binary phase masks for easy system alignment and basic aberration sensing with spatial light modulators in STED microscopy JF - Scientific reports Y1 - 2017 U6 - https://doi.org/10.1038/s41598-017-15967-5 SN - 2045-2322 VL - 7 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Zhang, Shuhao A1 - Bisterfeld, Carolin A1 - Bramski, Julia A1 - Vanparijs, Nane A1 - De Geest, Bruno G. A1 - Pietruszka, Jörg A1 - Böker, Alexander A1 - Reinicke, Stefan T1 - Biocatalytically Active Thin Films via Self-Assembly of 2-Deoxy-D-ribose-5-phosphate Aldolase-Poly(N-isopropylacrylamide) Conjugates JF - Bioconjugate chemistry N2 - 2-Deoxy-D-ribose-5-phosphate aldolase (DERA) is a biocatalyst that is capable of converting acetaldehyde and a second aldehyde as acceptor into enantiomerically pure mono- and diyhydroxyaldehydes, which are important structural motifs in a number of pharmaceutically active compounds. However, substrate as well as product inhibition requires a more-sophisticated process design for the synthesis of these motifs. One way to do so is to the couple aldehyde conversion with transport processes, which, in turn, would require an immobilization of the enzyme within a thin film that can be deposited on a membrane support. Consequently, we developed a fabrication process for such films that is based on the formation of DERA-poly(N-isopropylacrylamide) conjugates that are subsequently allowed to self-assemble at an air-water interface to yield the respective film. In this contribution, we discuss the conjugation conditions, investigate the interfacial properties of the conjugates, and, finally, demonstrate a successful film formation under the preservation of enzymatic activity. Y1 - 2017 U6 - https://doi.org/10.1021/acs.bioconjchem.7b00645 SN - 1043-1802 VL - 29 IS - 1 SP - 104 EP - 116 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Hardy, John G. A1 - Torres-Rendon, Jose Guillermo A1 - Leal-Egaña, Aldo A1 - Walther, Andreas A1 - Schlaad, Helmut A1 - Cölfen, Helmut A1 - Scheibel, Thomas R. T1 - Biomineralization of engineered spider silk protein-based composite materials for bone tissue engineering N2 - Materials based on biodegradable polyesters, such as poly(butylene terephthalate) (PBT) or poly(butylene terephthalate-co-poly(alkylene glycol) terephthalate) (PBTAT), have potential application as pro-regenerative scaffolds for bone tissue engineering. Herein, the preparation of films composed of PBT or PBTAT and an engineered spider silk protein, (eADF4(C16)), that displays multiple carboxylic acid moieties capable of binding calcium ions and facilitating their biomineralization with calcium carbonate or calcium phosphate is reported. Human mesenchymal stem cells cultured on films mineralized with calcium phosphate show enhanced levels of alkaline phosphatase activity suggesting that such composites have potential use for bone tissue engineering. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 359 KW - spider silk KW - recombinant protein KW - biodegradable polymers KW - biomaterials KW - biomineralization KW - bone tissue engineering Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-400519 ER - TY - THES A1 - Peh, Eddie K.W. T1 - Calcium carbonate formation BT - influence of various interfacial conditions Y1 - 2017 ER - TY - JOUR A1 - Hentrich, Doreen A1 - Brezesinski, Gerald A1 - Kuebel, Christian A1 - Bruns, Michael A1 - Taubert, Andreas T1 - Cholesteryl Hemisuccinate Monolayers Efficiently Control Calcium Phosphate Nucleation and Growth JF - Crystal growth & design : integrating the fields of crystal engineering and crystal growth for the synthesis and applications of new materials N2 - The article describes the phase behavior of cholesteryl hemisuccinate at the air-liquid interface and its effect on calcium phosphate (CP) mineralization. The amphiphile forms stable monolayers with phase transitions at the air-liquid interface from a gas to a tilted liquid-condensed (TLC) and finally to an untilted liquid-condensed (ULC) phase. CP mineralization beneath these monolayers leads to crumpled CP layers made from individual plates. The main crystal phase is octacalcium phosphate (OCP) along with a minor fraction of hydroxyapatite (HAP), as confirmed by X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, bright field transmission electron microscopy, and electron diffraction. Y1 - 2017 U6 - https://doi.org/10.1021/acs.cgd.7b00753 SN - 1528-7483 SN - 1528-7505 VL - 17 SP - 5764 EP - 5774 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Peh, Eddie A1 - Liedel, Clemens A1 - Taubert, Andreas A1 - Tauer, Klaus T1 - Composition inversion to form calcium carbonate mixtures JF - CrystEngComm N2 - Composition inversion takes place in equimolar solid mixtures of sodium or ammonium carbonate and calcium chloride with respect to the combination of anions and cations leading to the corresponding chloride and calcite in complete conversion. The transformation takes place spontaneously under a variety of different situations, even in a powdery mixture resting under ambient conditions. Powder X-ray diffraction data and scanning electron microscopy micrographs are presented to describe the course of the reaction and to characterize the reaction products. The incomplete reaction in the interspace between two compressed tablets of pure starting materials leads to an electric potential due to the presence of uncompensated charges. Y1 - 2017 U6 - https://doi.org/10.1039/c7ce00433h SN - 1466-8033 VL - 19 SP - 3573 EP - 3583 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Shainyan, Bagrat A. A1 - Kirpichenko, Svetlana V. A1 - Kleinpeter, Erich T1 - Conformational Preferences of the Phenyl Group in 1-Phenyl-1-X-1-silacyclo-hexanes (X = MeO, HO) and 3-Phenyl-3-X-3-silatetrahydropyrans (X = HO, H) by Low Temperature C-13 NMR Spectroscopy and Theoretical Calculations JF - The journal of organic chemistry N2 - New Si-phenyl-substituted silacyclohexanes and 3-silatetrahydropyrans have been synthesized and studied with respect to the conformational equilibria of the heterosix-membered ring by low temperature C-13 NMR spectroscopy and quantum chemical calculations. For 1-methoxy-1-phenylsilacyclohexane 1 and 3-phenyl-3-silatetrahydropyran 4 the conformational equilibria could be frozen and assigned. The Ph-ax reversible arrow Ph-eq equilibrium constants at 103 K are 2.21 for 1 and 4.59 for 4. In complete agreement with former studies of similar silicon compounds, molecules 1 and 4 prefer to adopt the Pheq conformation. The conformational equilibria of 1-hydroxy-1-phenylsilacydohexane 2 and 3-hydroxy-3-phenyl-3-silatetrahydropyran 3 could not be frozen at 100 K and proved to be heavily one-sided (if not anancomeric). Obviously, there is a general trend of predominance of Phax conformer in the gas phase and of Pheq in solution. For the isolated molecules of silanols 2 and 3, calculations allowed to explain the axial predominance of the phenyl group by a larger polarization of the Si-Ph than of the Si-O bond in the Phax conformer and additional destabilization of 3-Ph-eq conformer by repulsion of unidirectional dipoles of the endocyclic oxygen lone pair and of the highly polar axial Si-O bond. Y1 - 2017 U6 - https://doi.org/10.1021/acs.joc.7b02505 SN - 0022-3263 VL - 82 SP - 13414 EP - 13422 PB - American Chemical Society CY - Washington ER - TY - THES A1 - You, Zewang T1 - Conformational transition of peptide-functionalized cryogels enabling shape-memory capability Y1 - 2017 ER - TY - JOUR A1 - Schweighöfer, F. A1 - Moreno, J. A1 - Bobone, Sara A1 - Chiantia, Salvatore A1 - Herrmann, A. A1 - Hecht, S. A1 - Wachtveitl, Josef T1 - Connectivity pattern modifies excited state relaxation dynamics of fluorophore-photoswitch molecular dyads JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - In order to modulate the emission of BODIPY fluorophores, they were connected to a diarylethene (DAE) photoswitch via phenylene-ethynylene linkers of different lengths and orientations. The latter allowed for modulation of the electronic coupling in the prepared four BODIPY-DAE dyads, which were compared also to appropriate BODIPY and DAE model compounds by steady state as well as time-resolved spectroscopies. In their open isomers, all dyads show comparable luminescence behavior indicative of an unperturbed BODIPY fluorophore. In strong contrast, in the closed isomers the BODIPY emission is efficiently quenched but the deactivation mechanism depends on the nature of the linker. The most promising dyad was rendered water-soluble by means of micellar encapsulation and aqueous suspensions were investigated by fluorescence spectroscopy and microscopy. Our results (i) illustrate that the electronic communication between the BODIPY and DAE units can indeed be fine-tuned by the nature of the linker to achieve fluorescence modulation while maintaining photoswitchability and (ii) highlight potential applications to image and control biological processes with high spatio-temporal resolution. Y1 - 2016 U6 - https://doi.org/10.1039/c6cp07112k SN - 1463-9076 SN - 1463-9084 VL - 19 SP - 4010 EP - 4018 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Vacogne, Charlotte D. A1 - Schlaad, Helmut T1 - Controlled ring-opening polymerization of alpha-amino acid N-carboxyanhydrides in the presence of tertiary amines JF - Polymer : the international journal for the science and technology of polymers N2 - The mechanism of the primary ammonium/tertiary amine-mediated ring-opening polymerization of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) was investigated. Kinetic analyses revealed that the normal amine mechanism (NAM) together with a dormant-active chain end equilibrium were responsible for the controlled nature of this polymerization pathway, but that the polymerization also proceeded via the activated monomer mechanism (AMM). Mixtures of primary amines (1 equiv) and tertiary amines (0-1.5 equiv) were therefore tested to confirm the co-existence of the NAM and AMM and determine the limits for a controlled polymerization. For tertiary amine molar fractions smaller than 0.8 equiv, the reaction times were greatly reduced (compared to primary amine-initiated polymerization) without compromising the control of the reaction. Hence, the polymerization of NCA can proceed in a controlled manner even when the AMM contributes to the overall chain growth mechanism. (C) 2017 Elsevier Ltd. All rights reserved. KW - Ring-opening polymerization KW - Amino acid N-carboxyanhydride KW - NCA KW - Kinetics KW - Mechanism Y1 - 2017 U6 - https://doi.org/10.1016/j.polymer.2017.07.062 SN - 0032-3861 SN - 1873-2291 VL - 124 SP - 203 EP - 209 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Schilde, Uwe A1 - Paz, Christian A1 - Ortiz, Leandro T1 - Crystal structure of erioflorin isolated from Podanthus mitiqui (L.) JF - Acta Crystallographica Section E : Crystallographic Communications N2 - The title compound, erioflorin, C19H24O6 [systematic name: (1aR,3S,4Z,5aR,8aR,9R,10aR)-1a, 2,3,5a, 7,8,8a, 9,10,10a-decahydro-3-hydroxy-4,10a-dimethyl-8-methylidene-7-oxooxireno[5,6] cyclodeca[1,2-b]furan-9-yl methacrylate], is a tricyclic germacrane sesquiterpene lactone, which was isolated from Podanthus mitiqui (L.). The compound crystallizes in the space group P2(1)2(1)2(1), and its molecular structure consists of a methacrylic ester of a ten-membered ring sesquiterpenoid annelated with an epoxide and a butyrolactone. The structure is stabilized by one intramolecular C-H center dot center dot center dot O hydrogen bond. An O-H center dot center dot center dot O hydrogen bond and further C-H center dot center dot center dot O interactions can be observed in the packing. KW - crystal structure KW - germacrane sesquiterpene lactone KW - Podanthus mitiqui Y1 - 2017 U6 - https://doi.org/10.1107/S2056989017001700 VL - 73 IS - 3 SP - 334 EP - 337 PB - International Union of Crystallography CY - Chester ER - TY - GEN A1 - Schilde, Uwe A1 - Paz, Christian A1 - Ortiz, Leandro T1 - Crystal structure of erioflorin isolated from Podanthus mitiqui (L.) N2 - The title compound, erioflorin, C19H24O6 [systematic name: (1aR,3S,4Z,5aR,8aR,9R,10aR)-1a, 2,3,5a, 7,8,8a, 9,10,10a-decahydro-3-hydroxy-4,10a-dimethyl-8-methylidene-7-oxooxireno[5,6] cyclodeca[1,2-b]furan-9-yl methacrylate], is a tricyclic germacrane sesquiterpene lactone, which was isolated from Podanthus mitiqui (L.). The compound crystallizes in the space group P2(1)2(1)2(1), and its molecular structure consists of a methacrylic ester of a ten-membered ring sesquiterpenoid annelated with an epoxide and a butyrolactone. The structure is stabilized by one intramolecular C-H center dot center dot center dot O hydrogen bond. An O-H center dot center dot center dot O hydrogen bond and further C-H center dot center dot center dot O interactions can be observed in the packing. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 379 KW - Podanthus mitiqui KW - crystal structure KW - germacrane sesquiterpene lactone Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-401832 ER - TY - THES A1 - Jordan, Thomas T1 - CxNy-materials from supramolecular precursors for “All-Carbon” composite materials T1 - CxNy-Materialien aus supramolekularen Precursoren für „All-Carbon“-Komposit-Materialien N2 - Among modern functional materials, the class of nitrogen-containing carbons combines non-toxicity and sustainability with outstanding properties. The versatility of this materials class is based on the opportunity to tune electronic and catalytic properties via the nitrogen content and –motifs: This ranges from the electronically conducting N-doped carbon, where few carbon atoms in the graphitic lattice are substituted by nitrogen, to the organic semiconductor graphitic carbon nitride (g-C₃N₄), with a structure based on tri-s-triazine units. In general, composites can reveal outstanding catalytic properties due to synergistic behavior, e.g. the formation of electronic heterojunctions. In this thesis, the formation of an “all-carbon” heterojunction was targeted, i.e. differences in the electronic properties of the single components were achieved by the introduction of different nitrogen motives into the carbon lattice. Such composites are promising as metal-free catalysts for the photocatalytic water splitting. Here, hydrogen can be generated from water by light irradiation with the use of a photocatalyst. As first part of the heterojunction, the organic semiconductor g-C₃N₄ was employed, because of its suitable band structure for photocatalytic water splitting, high stability and non-toxicity. The second part was chosen as C₂N, a recently discovered semiconductor. Compared to g-C₃N₄, the less nitrogen containing C₂N has a smaller band gap and a higher absorption coefficient in the visible light range, which is expected to increase the optical absorption in the composite eventually leading to an enhanced charge carrier separation due to the formation of an electronic heterojunction. The aim of preparing an “all-carbon” composite included the research on appropriate precursors for the respective components g-C₃N₄ and C₂N, as well as strategies for appropriate structuring. This was targeted by applying precursors which can form supramolecular pre-organized structures. This allows for more control over morphology and atom patterns during the carbonization process. In the first part of this thesis, it was demonstrated how the photocatalytic activity of g-C₃N₄ can be increased by the targeted introduction of defects or surface terminations. This was achieved by using caffeine as a “growth stopping” additive during the formation of the hydrogen-bonded supramolecular precursor complexes. The increased photocatalytic activity of the obtained materials was demonstrated with dye degradation experiments. The second part of this thesis was focused on the synthesis of the second component C₂N. Here, a deep eutectic mixture from hexaketocyclohexane and urea was structured using the biopolymer chitosan. This scaffolding resulted in mesoporous nitrogen-doped carbon monoliths and beads. CO₂- and dye-adsorption experiments with the obtained monolith material revealed a high isosteric heat of CO₂-adsorption and showed the accessibility of the monolithic pore system to larger dye molecules. Furthermore, a novel precursor system for C₂N was explored, based on organic crystals from squaric acid and urea. The respective C₂N carbon with an unusual sheet-like morphology could be synthesized by carbonization of the crystals at 550 °C. With this precursor system, also microporous C₂N carbon with a BET surface area of 865 m²/g was obtained by “salt-templating” with ZnCl₂. Finally, the preparation of a g-C₃N₄/C₂N “all carbon” composite heterojunction was attempted by the self-assembly of g-C₃N₄ and C₂N nanosheets and tested for photocatalytic water splitting. Indeed, the composites revealed high rates of hydrogen evolution when compared to bulk g-C₃N₄. However, the increased catalytic activity was mainly attributed to the high surface area of the nanocomposites rather than to the composition. With regard to alternative composite synthesis ways, first experiments indicated N-Methyl-2-pyrrolidon to be suitable for higher concentrated dispersion of C₂N nanosheets. Eventually, the results obtained in this thesis provide precious synthetic contributions towards the preparation and processing of carbon/nitrogen compounds for energy applications. N2 - Eine interessante Materialklasse für technologische Anwendungen sind Kohlenstoff/Stickstoff-Materialien, die sich durch Ungiftigkeit und Umweltfreundlichkeit bei gleichzeitig interessanten katalytischen Eigenschaften auszeichnen. Die Vielseitigkeit dieser Materialkasse basiert auf der Möglichkeit ihre katalytischen und elektronischen Eigenschaften über Stickstoff-Anteil und –Funktionalitäten zu beeinflussen. Die vorliegende Arbeit fokussierte sich auf Komposite zwischen verschiedenen Kohlenstoff/Stickstoff-Derivaten, für welche aufgrund ihrer unterschiedlichen elektronischen Eigenschaften die Bildung elektronischer Heteroübergänge erwartet werden kann. Solche Komposite sind vielversprechende Materialien für die Erzeugung von Wasserstoff durch die photokatalytische Spaltung von Wasser. Für die eine Komponente des Komposits wurde das graphitische Kohlenstoffnitrid g-C₃N₄ eingesetzt, welches durch seine elektronische Struktur und Stabilität ein geeignetes Material für die photokatalytische Wasserspaltung ist. Für die andere Komponente des Komposits wurde eine erst kürzlich erstmalig beschriebene Kohlenstoff/Stickstoff Verbindung eingesetzt, das Kohlenstoffnitrid C₂N. Für dieses Komposit ist eine im Vergleich zu den einzelnen Komponenten stark erhöhte photokatalytische Aktivität zu erwarten. Neben dem Ziel der Herstellung eines solchen Komposits, fokussierte sich diese Arbeit auch darauf, neue Wege zur Synthese und Strukturierung der einzelnen Komponenten zu entwickeln. Dies sollte über supramolekulare Präkursor-Komplexe erfolgen, mit welchen eine erhöhte Einflussnahme auf Karbonisierungsprozesse erlangt werden kann. Im ersten Teil der Arbeit, welcher auf das graphitische Kohlenstoffnitrid g-C₃N₄ fokussiert war, wurde gezeigt wie die photokatalytische Aktivität dieser Komponente durch den gezielten Einbau von Defekten erhöht werden kann. Dies wurde über einen durch Koffein modifizierten supramolekularen Komplex als Präkursor erreicht. Die erhöhte photokatalytische Aktivität wurde über Farbstoff-Zersetzung nachgewiesen. Der zweite Teil der Arbeit war auf die Herstellung und Strukturierung der neuartigen Verbindung C₂N fokussiert. Hier wurde gezeigt, wie eine eutektische Mischung zwischen Hexaketocyclohexan und Harnstoff als C₂N-Präkursor mit dem Polysaccharid Chitosan strukturiert werden kann. Hierbei wurden poröse Stickstoffhaltige Kohlenstoff-Monolithen und -Perlen erhalten, die eine hohe Adsorptionswärme für die CO₂-Adsorption zeigten. Weiterhin wurde ein neuartiger Präkursor für C₂N vorgestellt, eine organisch-kristalline Verbindung zwischen Quadratsäure und Harnstoff. Durch Karbonisation dieser Verbindung bei 550 °C wurde ein Material mit einer Zusammensetzung von C₂N und einer ungewöhnlichen, schichtartigen Morphologie erhalten. Über eine eutektische Salzschmelze mit Zinkchlorid, konnte mit diesem Präkursor-System auch mikroporöser C₂N-Kohlenstoff mit einer BET-Oberfläche von 865 m²/g hergestellt werden. Im letzten Teil dieser Arbeit wurde die Herstellung des g-C₃N₄/C₂N-Komposits versucht, über die Selbstassemblierung von kolloidal dispergierten g-C₃N₄- und C₂N-Nanopartikeln. Die Nanopartikel wurden über Ultraschall-Behandlungen von Dispersionen dieser Komponenten hergestellt. Die erhaltenen Komposite zeigten eine hohe Aktivität zur photokatalytischen Wasserspaltung, wobei dies eher auf die hohe Oberfläche der Nanopartikel als auf ihre Zusammensetzung zurückgeführt wurde. Im Hinblick auf mögliche Alternativen zur Kompositherstellung, wurden erste Experimente zu höher konzentrierten kolloidalen Dispersionen von C₂N in dem organischen Lösungsmittel N-Methyl-2-pyrrolidon durchgeführt. Zusammenfassend, die Ergebnisse die in dieser Arbeit erhalten wurden, liefern einen wertvollen Beitrag zur Synthese und Strukturierung von Kohlenstoff/Stickstoff-Materialien sowie deren Anwendungen im Bereich alternative Energien. KW - carbon nitrides KW - supramolecular chemistry KW - porous materials KW - composite materials KW - photocatalysis KW - Kohlenstoffnitride KW - supramolekulare Chemie KW - poröse Materialien KW - Komposite KW - Photokatalyse Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-398855 ER - TY - JOUR A1 - Liebig, Ferenc A1 - Sarhan, Radwan Mohamed A1 - Sander, Mathias A1 - Koopman, Wouter-Willem Adriaan A1 - Schuetz, Roman A1 - Bargheer, Matias A1 - Koetz, Joachim T1 - Deposition of Gold Nanotriangles in Large Scale Close-Packed Monolayers for X-ray-Based Temperature Calibration and SERS Monitoring of Plasmon-Driven Catalytic Reactions JF - ACS applied materials & interfaces KW - gold nanotriangles KW - monolayer formation KW - SERS KW - dimerization KW - heat measurement Y1 - 2017 U6 - https://doi.org/10.1021/acsami.7b07231 SN - 1944-8244 VL - 9 SP - 20247 EP - 20253 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schwarze, Thomas A1 - Mueller, Holger A1 - Schmidt, Darya A1 - Riemer, Janine A1 - Holdt, Hans-Jürgen T1 - Design of Na+-Selective Fluorescent Probes: A Systematic Study of the Na+-Complex Stability and the Na+/K+ Selectivity in Acetonitrile and Water JF - Chemistry - a European journal N2 - There is a tremendous demand for highly Na+-selective fluoroionophores to monitor the top analyte Na+ in life science. Here, we report a systematic route to develop highly Na+/K+ selective fluorescent probes. Thus, we synthesized a set of fluoroionophores 1, 3, 4, 5, 8 and 9 (see Scheme 1) to investigate the Na+/K+ selectivity and Na(+-)complex stability in CH3CN and H2O. These Na+-probes bear different 15-crown-5 moieties to bind Na+ stronger than K+. In the set of the diethylaminocoumarin-substituted fluoroionophores 1-5, the following trend of fluorescence quenching 1 > 3 > 2 > 4 > 5 in CH3CN was observed. Therefore, the flexibility of the aza-15-crown-5 moieties in 1-4 determines the conjugation of the nitrogen lone pair with the aromatic ring. As a consequence, 1 showed in CH3CN the highest Na+-induced fluorescence enhancement (FE) by a factor of 46.5 and a weaker K+ induced FE of 3.7. The Na+-complex stability of 1-4 in CH3CN is enhanced in the following order of 2 > 4 > 3 > 1, assuming that the O-atom of the methoxy group in the ortho-position, as shown in 2, strengthened the Na+-complex formation. Furthermore, we found for the N( o-methoxyphenyl) aza-15-crown-5 substituted fluoroionophores 2, 8 and 9 in H2O, an enhanced Na+-complex stability in the following order 8 > 2 > 9 and an increased Na+/K+ selectivity in the reverse order 9 > 2 > 8. Notably, the Na+-induced FE of 8 (FEF = 10.9), 2 (FEF = 5.0) and 9 (FEF = 2.0) showed a similar trend associated with a decreased K+-induced FE [8 (FEF = 2.7) > 2 (FEF = 1.5) > 9 (FEF = 1.1)]. Here, the Na+-complex stability and Na+/K+ selectivity is also influenced by the fluorophore moiety. Thus, fluorescent probe 8 (K-d = 48 mm) allows high-contrast, sensitive, and selective Na+ measurements over extracellular K+ levels. A higher Na+/K+ selectivity showed fluorescent probe 9, but also a higher Kd value of 223 mm. Therefore, 9 is a suitable tool to measure Na+ concentrations up to 300 mm at a fluorescence emission of 614 nm. KW - crown compounds KW - fluorescence KW - fluorescent probes KW - potassium KW - sodium Y1 - 2017 U6 - https://doi.org/10.1002/chem.201605986 SN - 0947-6539 SN - 1521-3765 VL - 23 SP - 7255 EP - 7263 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Meiling, Till Thomas T1 - Development of a reliable and environmentally friendly synthesis for fluorescence carbon nanodots T1 - Entwicklung einer zuverlässigen und umweltfreundlichen Synthese für fluoreszierende Kohlenstoff-Nanopunkte BT - preparation and characterisation of excellent and well-defined carbon nanodots by a fast, simple and cost-efficient synthesis method; with special focus on future exploration and large scale applications BT - Herstellung und Charakterisierung von hochwertigen und klar definierten Kohlenstoff-Nanopunkten mit Hilfe einer schnellen, einfachen, und kosteneffizienten Synthesemethode; mit speziellem Fokus auf ihre zukünftige Erforschung und breite Anwendung N2 - Carbon nanodots (CNDs) have generated considerable attention due to their promising properties, e.g. high water solubility, chemical inertness, resistance to photobleaching, high biocompatibility and ease of functionalization. These properties render them ideal for a wide range of functions, e.g. electrochemical applications, waste water treatment, (photo)catalysis, bio-imaging and bio-technology, as well as chemical sensing, and optoelectronic devices like LEDs. In particular, the ability to prepare CNDs from a wide range of accessible organic materials makes them a potential alternative for conventional organic dyes and semiconductor quantum dots (QDs) in various applications. However, current synthesis methods are typically expensive and depend on complex and time-consuming processes or severe synthesis conditions and toxic chemicals. One way to reduce overall preparation costs is the use of biological waste as starting material. Hence, natural carbon sources such as pomelo peal, egg white and egg yolk, orange juice, and even eggshells, to name a few; have been used for the preparation of CNDs. While the use of waste is desirable, especially to avoid competition with essential food production, most starting-materials lack the essential purity and structural homogeneity to obtain homogeneous carbon dots. Furthermore, most synthesis approaches reported to date require extensive purification steps and have resulted in carbon dots with heterogeneous photoluminescent properties and indefinite composition. For this reason, among others, the relationship between CND structure (e.g. size, edge shape, functional groups and overall composition) and photophysical properties is yet not fully understood. This is particularly true for carbon dots displaying selective luminescence (one of their most intriguing properties), i.e. their PL emission wavelength can be tuned by varying the excitation wavelength. In this work, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain CNDs with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch, carboxylic acids and Tris-EDTA (TE) buffer as carbon- and nitrogen source, respectively. The presented microwave-assisted hydrothermal precursor carbonization (MW-hPC) is characterized by its cost-efficiency, simplicity, short reaction times, low environmental footprint, and high yields of approx. 80% (w/w). Furthermore, only a single synthesis step is necessary to obtain homogeneous water-soluble CNDs with no need for further purification. Depending on starting materials and reaction conditions different types of CNDs have been prepared. The as-prepared CNDs exhibit reproducible, highly homogeneous and favourable PL properties with narrow emission bands (approx. 70nm FWHM), are non-blinking, and are ready to use without need for further purification, modification or surface passivation agents. Furthermore, the CNDs are comparatively small (approx. 2.0nm to 2.4nm) with narrow size distributions; are stable over a long period of time (at least one year), either in solution or as a dried solid; and maintain their PL properties when re-dispersed in solution. Depending on CND type, the PL quantum yield (PLQY) can be adjusted from as low as 1% to as high as 90%; one of the highest reported PLQY values (for CNDs) so far. An essential part of this work was the utilization of a microwave synthesis reactor, allowing various batch sizes and precise control over reaction temperature and -time, pressure, and heating- and cooling rate, while also being safe to operate at elevated reaction conditions (e.g. 230 ±C and 30 bar). The hereby-achieved high sample throughput allowed, for the first time, the thorough investigation of a wide range of synthesis parameters, providing valuable insight into the CND formation. The influence of carbon- and nitrogen source, precursor concentration and -combination, reaction time and -temperature, batch size, and post-synthesis purification steps were carefully investigated regarding their influence on the optical properties of as-synthesized CNDs. In addition, the change in photophysical properties resulting from the conversion of CND solution into solid and back into the solution was investigated. Remarkably, upon freeze-drying the initial brown CND-solution turns into a non-fluorescent white/slightly yellow to brown solid which recovers PL in aqueous solution. Selected CND samples were also subject to EDX, FTIR, NMR, PL lifetime (TCSPC), particle size (TEM), TGA and XRD analysis. Besides structural characterization, the pH- and excitation dependent PL characteristics (i.e. selective luminescence) were examined; giving inside into the origin of photophysical properties and excitation dependent behaviour of CNDs. The obtained results support the notion that for CNDs the nature of the surface states determines the PL properties and that excitation dependent behaviour is caused by the “Giant Red-Edge Excitation Shift” (GREES). N2 - Kohlenstoff-Nanopunkte (CNDs, engl. carbon nanodots) haben im letzten Jahrzehnt insbesondere durch ihre vielversprechenden Eigenschaften immer mehr an Popularität gewonnen. CNDs zeichnen sich insbesondere durch ihre Wasserlöslichkeit, hohe chemische Stabilität, Biokompatibilität, hohe Resistenz gegen Photobleichen, und die Möglichkeit zur Oberflächenfunktionalisierung aus. Diese Eigenschaften machen sie somit ideal für eine breite Palette von Anwendungen: z.B. Abwasserbehandlung, (Foto-) Katalyse, Bioimaging und Biotechnologie, chemische Sensorik, sowie elektrochemische- und optoelektronische Anwendungen (z.B. LEDs). Insbesondere die Möglichkeit, CNDs aus einer Vielzahl organischer Materialien herzustellen, machen sie zu einer möglichen Alternative für herkömmliche organische Farbstoffe und Halbleiter-Quantenpunkte (QDs). Derzeitigen Synthesestrategien erweisen sich jedoch häufig als teuer, komplex und zeitaufwändig; bzw. benötigen toxischen Chemikalien und/oder drastische Reaktionsbedingungen. Eine Möglichkeit, die Herstellungskosten von CNDs zu reduzieren, ist die Verwendung von biologischem Abfall als Ausgangsmaterial. So wurden bereits eine Vielzahl an natürlichen Kohlenstoffquellen, z.B. Pomelo-Schale, Eiweiß und Eigelb, Orangensaft und sogar Eierschalen, für die Darstellung von CNDs verwendet. Während die Verwendung von biologischem Abfall wünschenswert ist, insbesondere um Wettbewerb mit der Nahrungsmittelproduktion zu vermeiden, fehlt den meisten Ausgangsmaterialien jedoch die notwendige Reinheit und strukturelle Homogenität um einheitliche CNDs zu erhalten. So führen bisherige Syntheseansätze oft zu CNDs mit heterogenen photophysikalischen Eigenschaften und unbestimmter Zusammensetzung. Für die Untersuchung des Zusammenhangs zwischen CND Struktur und photophysikalischen Eigenschaften werden aber möglichst homogene und vergleichbare Proben benötigt. In dieser Arbeit wird daher eine neue, zuverlässige, ökonomische und umweltfreundliche Einstufen-Synthese zur Darstellung von CNDs mit klar definierten und reproduzierbaren Photolumineszenz- (PL) -Eigenschaften vorgestellt. Die vorgestellte Methode basiert auf der mikrowellenunterstützten, hydrothermischen Behandlung (MW-hPC, engl. microwaveassisted hydrothermal precursor carbonization) wässriger Lösungen aus Stärke, Carbonsäuren (als Kohlenstoffquelle) und Tris-EDTA (TE) -Puffer (als Stickstoffquelle). Die MW-hPC zeichnet sich insbesondere durch die hohe Reproduzierbarkeit, einfache Handhabung, geringen Reaktionszeiten, geringe Umweltbelastung, Kosteneffizienz und die hohen Ausbeuten von ca. 80% (w/w) aus. Darüber hinaus wird nur ein einziger Syntheseschritt (ohne weitere Aufreinigung) benötigt um homogene, wasserlösliche CNDs zu erhalten. In Abhängig der gewählten Ausgangsmaterialen und Reaktionsbedingungen können verschiedene Typen an CNDs gewonnen werden. Die so gewonnen CNDs sind verhältnismäßig klein (ca. 2.0nm- 2.4nm); besitzen eine geringe Größenverteilung, hochgradig homogenen PL-Eigenschaften, und geringen Halbwertsbreiten (FWHM) von ca. 70nm. Darüber hinaus erwiesen sie sich als nicht blinkend; sind langzeitstabil (min. ein Jahr) sowohl in Lösung als auch als Feststoff; und sind direkt gebrauchsfertig, d.h. benötigen keine weitere Aufreinigung oder Oberflächenpassivierung. In Abhängigkeit vom CND-Typ kann die PL-Quantenausbeute zwischen 1% bis 90% betragen; einer der höchsten Werte der je (für CNDs) erreicht wurde. Ein wesentlicher Bestandteil dieser Arbeit war die Verwendung eines Mikrowellensynthese- Reaktors (MiWR) und die damit einhergehende präzise Kontrolle über die Reaktionstemperatur und -zeit, den Druck, und die Heiz- und Abkühlgeschwindigkeit. Des Weiteren ermöglichte der MiWR unterschiedliche Ansatzgrößen und das sichere Arbeiten bei erhöhten Reaktionsbedingungen (z.B. 230 ±C und 30 bar). Der hierdurch erreichte hohe Probendurchsatz ermöglichte somit erstmals die sorgfältige Untersuchung einer Vielzahl an Syntheseparametern hinsichtlich ihres Einflusses auf die photophysikalischen Eigenschaften der dargestellten CNDs. Die untersuchten Parameter reichen hierbei von der Reaktionstemperatur und -zeit über die Edukt-Konzentration und -Kombination (Kohlenstoff- und Stickstoffquelle) bis hin zur Ansatzgröße. Bemerkenswerterweise, und unabhängig vom CND-Typ, transformieren die ursprünglich braunen CND-Lösungen während der Trocknung zu einem nicht fluoreszierenden, weißen/leicht gelblich bis bräunlichen Feststoff; und regenerieren ihre photophysikalischen Eigenschaften verlustfrei in wässriger Lösung. Im Rahmen dieser Arbeit wurden ausgewählte CND-Proben der EDX-, FTIR-, NMR-, TCSPC-, Partikelgrößen (TEM)-, TGA- und XRD-Analyse unterzogen. Die hierbei gewonnenen Erkenntnisse stützen die Theorie, dass die photophysikalischen Eigenschaften der CNDs durch ihre Oberflächenzustände bestimmt werden und dass die s.g. ”Riesen-Rotkanten-Anregungsverschiebung” (GREES, engl. Giant Red Edge Excitation Shift) eine mögliche Ursache für die häufig beobachtete Anregungswellenlängenabhängigkeit der Emissionswellenlänge (bzw. selektive Lumineszenz) in CNDs ist. KW - carbon dots KW - carbon nanodots KW - fluorescence KW - high quantum yield KW - microwave synthesis KW - white carbon KW - Kohlenstoff-Punkte KW - Kohlenstoff-Nanopunkte KW - Fluoreszenz KW - hohe Quantenausbeute KW - mikrowellengestützte Synthese KW - weißer Kohlenstoff Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-410160 ER - TY - THES A1 - Dippel, Sandor T1 - Development of functional hydrogels for sensor applications T1 - Entwicklung funktionalisierter Hydrogele für Sensor Anwendungen N2 - In this work, a sensor system based on thermoresponsive materials is developed by utilizing a modular approach. By synthesizing three different key monomers containing either a carboxyl, alkene or alkyne end group connected with a spacer to the methacrylic polymerizable unit, a flexible copolymerization strategy has been set up with oligo ethylene glycol methacrylates. This allows to tune the lower critical solution temperature (LCST) of the polymers in aqueous media. The molar masses are variable thanks to the excurse taken in polymerization in ionic liquids thus stretching molar masses from 25 to over 1000 kDa. The systems that were shown shown to be effective in aqueous solution could be immobilized on surfaces by copolymerizing photo crosslinkable units. The immobilized systems were formulated to give different layer thicknesses, swelling ratios and mesh sizes depending on the demand of the coupling reaction. The coupling of detector units or model molecules is approached via reactions of the click chemistry pool, and the reactions are evaluated on their efficiency under those aspects, too. These coupling reactions are followed by surface plasmon resonance spectroscopy (SPR) to judge efficiency. With these tools at hand, Salmonella saccharides could be selectively detected by SPR. Influenza viruses were detected in solution by turbidimetry in solution as well as by a copolymerized solvatochromic dye to track binding via the changes of the polymers’ fluorescence by said binding event. This effect could also be achieved by utilizing the thermoresponsive behavior. Another demonstrator consists of the detection system bound to a quartz surface, thus allowing the virus detection on a solid carrier. The experiments show the great potential of combining the concepts of thermoresponsive materials and click chemistry to develop technically simple sensors for large biomolecules and viruses. N2 - Diese Arbeit befasst sich mit der Entwicklung von Sensorsystemen für biologische Analyten wie Bakterien und Viren. Die Sensoren beruhen auf thermoresponsiven Polymeren und die Entwicklung wird Schritt für Schritt ausgehend von der Monomersynthese dargelegt. Die Grundidee ist es alle Einzelschritte so modular wie möglich zu halten. Die Kopplungseinheiten für die späteren Erkennungsgruppen bestehen aus Carboxyl, Alken und Alkinfunktionalitäten, die zuerst mit einem Ethylenglycolspacer mit variabler Länge verknüpft werden und dann mit der polymerisierbaren Methylmethacrylatgruppe versehen werden. Diese koppelbaren Monomere werden mit Di- oder (Oligoethylenglycol)methacrylaten copolymerisiert. Je nach Verhältnis ist so auch die untere kritische Entmischungstemperatur (LCST) einstellbar. Mit der Erweiterung der Polymerisationstechnik um ionische Flüssigkeiten als Lösemittel lassen sich Molmassen von 25 bis über 1000 kDa einstellen. Um die Polymere funktionell zu erweitern, lassen sich auch benzophenonhaltige Monomere zur Vernetzung oder Immobilisierung copolymerisieren. Naphthalsäureimidhaltige Monomere wiederum dienen als Signaleinheit, da sie durch Verändern der Polarität ihrer Umgebung solvatochrom reagieren. Durch Aufschleudern und UV-Vernetzen lassen sich Gelschichten mit guter Schichtdickenkontrolle herstellen. Dabei sind die Substrate nur auf den jeweiligen Zweck beschränkt. Dank des Baukastenprinzips kann auch die Maschenweite oder der Quellgrad der Gele eingestellt werden. Die Polymere oder Hydrogele werden mit Hilfe von effizienten Reaktionen swe sogenannten „Click Chemie“ umgesetzt und die Reaktionen werden durchleuchtet, ob sie diesen Ansprüchen gerecht werden. Je nach Möglichkeit wird das Anknüpfen mittels Oberflächenplasmonenresonanzspektroskopie(SPR) verfolgt, so wie zum Beispiel die Kopplung eines Phagen-Oberflächenproteins und das selektive Binden eines Membransaccharids des Salmonellen Bakteriums. Influenza Viren werden selektiv mit Hilfe eines Erkennungspeptids gebunden und mit Hilfe von Trübungsspektroskopie bzw. dem thermoresponsiven Verhalten des Trägerpolymers nachgewiesen. Ein weiterer dargelegter Ansatz ist das Nachweisen von geringen Virenkonzentrationen mit Hilfe eines Hydrogels oder von Polymeren in Lösung, die jeweils mit einem solvatochromen Farbstoff ausgestattet sind, der auf die Umgebungsänderung durch den Virus reagiert. Die Experimente zeigen das große Potential von geschickt kombinierten thermoresponsiven Materialien, die mittels Funktionalisierung durch Click-Chemie zu technisch einfachen Nachweissystemen für Biomoleküle und sogar ganze Zellen entwickelt werden können. KW - biosensors KW - polymer synthesis KW - lower critical solution temperature KW - surface modification KW - smart materials KW - Biosensoren KW - Polymersynthese KW - untere kritische Entmischungstemperatur KW - schaltbare Materialien Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-398252 ER - TY - JOUR A1 - Rumschoettel, Jens A1 - Kosmella, Sabine A1 - Prietzel, Claudia Christina A1 - Appelhans, Dietmar A1 - Koetz, Joachim T1 - DNA polyplexes with dendritic glycopolymer-entrapped gold nanoparticles JF - Colloids and surfaces : an international journal devoted to fundamental and applied research on colloid and interfacial phenomena in relation to systems of biological origin ; B, Biointerfaces N2 - Polyplexes, composed of Salmon DNA and very small gold nanoparticles embedded into a dendritic glycopolymer architecture of sugar-modified poly(ethyleneimine) (PEI-Mal) with a molar mass of about 25,000 g/mol, were characterized by dynamic light scattering (DLS), zeta potential measurements, micro differential scanning calorimetry (mu-DSC) and transmission electron microscopy (TEM). The PEI-Mal-entrapped gold nanoparticles of about 2 nm in diameter influence the polyplex formation of the hyperbranched PEI containing bulky maltose, and in consequence the DNA is more compactized in the inner part of spherical polyplex particles of about 150 nm in diameter. The resulting more compact core shell polyplex particles with embedded gold nanoparticles in the outer polymer shell will be used as components in forthcoming gene delivery experiments. (C) 2017 Elsevier B.V. All rights reserved. KW - DNA polyplexes KW - Gold nanoparticles KW - Maltose-modified poly(ethyleneimine) KW - TEM KW - mu-DSC Y1 - 2017 U6 - https://doi.org/10.1016/j.colsurfb.2017.03.001 SN - 0927-7765 SN - 1873-4367 VL - 154 SP - 74 EP - 81 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Tebaldi, Marli Luiza A1 - Charan, Himanshu A1 - Mavliutova, Liliia A1 - Böker, Alexander A1 - Glebe, Ulrich T1 - Dual-Stimuli Sensitive Hybrid Materials: Ferritin-PDMAEMA by Grafting-From Polymerization JF - Macromolecular chemistry and physics N2 - The combination of stimuli-responsive polymers and proteins that can transport drugs is a promising approach for drug delivery. The formation of ferritin-poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) conjugates by atom-transfer radical polymerization from the protein macroinitiator is described. PDMAEMA is a dual-stimuli-responsive polymer and the thermo- and pH-responsive properties of the resulting conjugates are studied in detail with dynamic light scattering (DLS). Additionally, it is demonstrated that the lower critical solution temperature (LCST) of the protein-polymer conjugates can be further adjusted by the ionic strength of the solution. The conjugates are also characterized by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), matrix-assisted laser desorption ionization-time of flight (MALDI-ToF) mass spectrometry, and NMR spectroscopy. The obtained MALDI-ToF mass spectra are exceptional for protein-polymer conjugates and have not been so often reported. KW - grafting-from KW - MALDI-ToF MS KW - polymerization KW - proteins KW - responsivity Y1 - 2017 U6 - https://doi.org/10.1002/macp.201600529 SN - 1022-1352 SN - 1521-3935 VL - 218 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Movahedifar, Fahimeh A1 - Modarresi-Alam, Ali Reza A1 - Kleinpeter, Erich A1 - Schilde, Uwe T1 - Dynamic H-1-NMR study of unusually high barrier to rotation about the partial C-N double bond in N,N-dimethyl carbamoyl 5-aryloxytetrazoles JF - Journal of molecular structure N2 - The synthesis of new N,N-dimethyl carbamoyl 5-aryloxytetrazoles have been reported. Their dynamic H-1-NMR via rotation about C-N bonds in moiety of urea group [a; CO-NMe2 and b; (2-tetrazolyl)N-CO rotations] in the solvents CDCl3 (223-333 K) and DMSO (298-363 K) is studied. Accordingly, the free energies of activation, obtained 16.5 and 16.9 kcal mol(-1) respectively, attributed to the conformational isomerization about the Me2N-C=O bond (a rotation). Moreover, a and b barrier to rotations in 5-((4-methylphenoxy)-N,N-dimethyl-2H-tetrazole-2-carboxamide (P) also were computed at level of B3LYP using 6-311++G** basis set. The optimized geometry parameters are in good agreement with X-ray structure data. The computation of energy barrier for a and b was determined 16.9 and 2.5 kcal mol(-1), respectively. The former is completely in agreement with the result obtained via dynamic NMR. X-ray structure analysis data demonstrate that just 2-acylated tetrazole was formed in the case of 5-(p-tolyloxy)-N,N-dimethyl-2H-tetrazole-2-carboxamide. X-ray data also revealed a planar trigonal orientation of the Me2N group which is coplanar to carbonyl group with the partial double-bond C-N character. It also demonstrates the synperiplanar position of C=O group with tetrazolyl ring. On average, in solution the plane containing carbonyl bond is almost perpendicular to the plane of the tetrazolyl ring (because of steric effects as confirmed by B3LY12/6-311++G**) while the plane containing Me2N group is coplanar with carbonyl bond which is in contrast with similar urea derivatives and it demonstrates the unusually high rotational energy barrier of these compounds. (C) 2016 Elsevier B.V. All rights reserved. KW - Dynamic H-1-NMR KW - Carbamoyl tetrazoles KW - Barrier to rotation about C-N bond KW - pi-Stacking KW - B3LYP/6-311++G** Y1 - 2017 U6 - https://doi.org/10.1016/j.molstruc.2016.12.010 SN - 0022-2860 SN - 1872-8014 VL - 1133 SP - 244 EP - 252 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Lippold, Holger A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Lippmann-Pipke, Johanna T1 - Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time JF - Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society N2 - Complexation with dissolved humic matter can be crucial in controlling the mobility of toxic or radioactive contaminant metals. For speciation and transport modelling, a dynamic equilibrium process is commonly assumed, where association and dissociation run permanently. This is, however, questionable in view of reported observations of a growing resistance to dissociation over time. In this study, the isotope exchange principle was employed to gain direct insight into the dynamics of the complexation equilibrium, including kinetic inertisation phenomena. Terbium(III), an analogue of trivalent actinides, was used as a representative of higher-valent metals. Isotherms of binding to (flocculated) humic acid, determined by means of Tb-160 as a radiotracer, were found to be identical regardless of whether the radioisotope was introduced together with the bulk of stable Tb-159 or subsequently after pre-equilibration for up to 3 months. Consequently, there is a permanent exchange of free and humic-bound Tb since all available binding sites are occupied in the plateau region of the isotherm. The existence of a dynamic equilibrium was thus evidenced. There was no indication of an inertisation under these experimental conditions. If the small amount of Tb-160 was introduced prior to saturation with Tb-159, the expected partial desorption of Tb-160 occurred at much lower rates than observed for the equilibration process in the reverse procedure. In addition, the rates decreased with time of pre-equilibration. Inertisation phenomena are thus confined to the stronger sites of humic molecules (occupied at low metal concentrations). Analysing the time-dependent course of isotope exchange according to first-order kinetics indicated that up to 3 years are needed to attain equilibrium. Since, however, metal-humic interaction remains reversible, exchange of metals between humic carriers and mineral surfaces cannot be neglected on the long time scale to be considered in predictive transport models. KW - Humic substances KW - Metal complexation KW - Kinetics KW - Reversibility KW - Isotope exchange KW - Dynamic equilibrium Y1 - 2016 U6 - https://doi.org/10.1016/j.gca.2016.10.019 SN - 0016-7037 SN - 1872-9533 VL - 197 SP - 62 EP - 70 PB - Elsevier CY - Oxford ER - TY - GEN A1 - Ihmels, Heiko A1 - Linker, Torsten A1 - Trofimov, Aleksei T1 - Editorial T2 - Journal of physical organic chemistry Y1 - 2017 U6 - https://doi.org/10.1002/poc.3745 SN - 0894-3230 SN - 1099-1395 VL - 30 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Schürmann, Robin Mathis A1 - Bald, Ilko T1 - Effect of adsorption kinetics on dissociation of DNA-nucleobases on gold nanoparticles under pulsed laser illumination JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Photothermal therapy is a novel approach to destroy cancer cells by an increase of temperature due to laser illumination of gold nanoparticles (GNPs) that are incorporated into the cells. Here, we study the decomposition of DNA nucleobases via irradiation of gold nanoparticles with ns-laser pulses. The kinetics of the adsorption and decomposition process is described by a theoretical model based on the Langmuir assumptions and correlated with experimentally determined reaction rates revealing a strong influence of the nucleobase specific adsorption. Beside the four nucleobases, their brominated analogs, which are potential radiosensitizers in cancer therapy, are also investigated and show a significant modification of the decomposition rates. The fastest decomposition rates are observed for adenine, 8-bromoadenine, 8-bromoguanine and 5-bromocytosine. These results are in good agreement with the relative adsorption rates that are determined from the aggregation kinetics of the GNPs taking the effect of an inhomogeneous surface into account. For adenine and its brominated analog, the decomposition products are further analyzed by surface enhanced Raman scattering (SERS) indicating a strong fragmentation of the molecules into their smallest subunits. Y1 - 2017 U6 - https://doi.org/10.1039/c6cp08433h SN - 1463-9076 SN - 1463-9084 VL - 19 SP - 10796 EP - 10803 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Hildebrand, Viet A1 - Laschewsky, Andre A1 - Päch, Michael A1 - Müller-Buschbaum, Peter A1 - Papadakis, Christine M. T1 - Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates) JF - Polymer Chemistry N2 - A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition–fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers’ precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate. Y1 - 2016 U6 - https://doi.org/10.1039/c6py01220e SN - 1759-9954 SN - 1759-9962 VL - 8 SP - 310 EP - 322 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Morgner, Frank A1 - Bennemann, Mark A1 - Cywiński, Piotr J. A1 - Kollosche, Matthias A1 - Górski, Krzysztof A1 - Pietraszkiewicz, Marek A1 - Geßner, André A1 - Löhmannsröben, Hans-Gerd T1 - Elastic FRET sensors for contactless pressure measurement JF - RSC Advances : an international journal to further the chemical sciences N2 - Contactless pressure monitoring based on Forster resonance energy transfer between donor/acceptor pairs immobilized within elastomers is demonstrated. The donor/acceptor energy transfer is employed by dispersing terbium(III) tris[(2-hydroxybenzoyl)-2-aminoethyl] amine complex (LLC, donor) and CdSe/ZnS quantum dots (QD655, acceptor) in styrene-ethylene/buthylene-styrene (SEBS) and poly(dimethylsiloxane) (PDMS). The continuous monitoring of QD luminescence showed a reversible intensity change as the pressure signal is alternated between two stable states indicating a pressure sensitivity of 6350 cps kPa(-1). Time-resolved measurements show the pressure impact on the FRET signal due to an increase of decay time (270 ms up to 420 ms) for the donor signal and parallel drop of decay time (170 mu s to 155 mu s) for the acceptor signal as the net pressure applied. The LLC/QD655 sensors enable a contactless readout as well as space resolved monitoring to enable miniaturization towards smaller integrated stretchable opto-electronics. Elastic FRET sensors can potentially lead to developing profitable analysis systems capable to outdo conventional wired electronic systems (inductive, capacitive, ultrasonic and photoelectric sensors) especially for point-of-care diagnostics, biological monitoring required for wearable electronics. Y1 - 2017 U6 - https://doi.org/10.1039/c7ra06379b SN - 2046-2069 VL - 7 SP - 50578 EP - 50583 PB - RSC Publishing CY - Cambridge ER - TY - JOUR A1 - Goulet-Hanssens, Alexis A1 - Utecht, Manuel A1 - Mutruc, Dragos A1 - Titov, Evgenii A1 - Schwarz, Jutta A1 - Grubert, Lutz A1 - Bleger, David A1 - Saalfrank, Peter A1 - Hecht, Stefan T1 - Electrocatalytic Z -> E Isomerization of Azobenzenes JF - Journal of the American Chemical Society N2 - A variety of azobenzenes were synthesized to study the behavior of their E and Z isomers upon electrochemical reduction. Our results show that the radical anion of the Z isomer is able to rapidly isomerize to the corresponding E configured counterpart with a dramatically enhanced rate as compared to the neutral species. Due to a subsequent electron transfer from the formed E radical anion to the neutral Z starting material the overall transformation is catalytic in electrons; i.e., a substoichiometric amount of reduced species can isomerize the entire mixture. This pathway greatly increases the efficiency of (photo)switching while also allowing one to reach photostationary state compositions that are not restricted to the spectral separation of the individual azobenzene isomers and their quantum yields. In addition, activating this radical isomerization pathway with photoelectron transfer agents allows us to override the intrinsic properties of an azobenzene species by triggering the reverse isomerization direction (Z -> E) by the same wavelength of light, which normally triggers E -> Z isomerization. The behavior we report appears to be general, implying that the metastable isomer of a photoswitch can be isomerized to the more stable one catalytically upon reduction, permitting the optimization of azobenzene switching in new as well as indirect ways. Y1 - 2017 U6 - https://doi.org/10.1021/jacs.6b10822 SN - 0002-7863 VL - 139 IS - 1 SP - 335 EP - 341 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Piluso, Susanna A1 - Lendlein, Andreas A1 - Neffe, Axel T. T1 - Enzymatic action as switch of bulk to surface degradation of clicked gelatin-based networks JF - Polymers for advanced technologies N2 - Polymer degradation occurs under physiological conditions in vitro and in vivo, especially when bonds susceptible to hydrolysis are present in the polymer. Understanding of the degradation mechanism, changes of material properties over time, and overall rate of degradation is a necessary prerequisite for the knowledge-based design of polymers with applications in biomedicine. Here, hydrolytic degradation studies of gelatin-based networks synthesized by copper-catalyzed azide-alkyne cycloaddition reaction are reported, which were performed with or without addition of an enzyme. In all cases, networks with a stilbene as crosslinker proofed to be more resistant to degradation than when an octyl diazide was used. Without addition of an enzyme, the rate of degradation was ruled by the crosslinking density of the network and proceeded via a bulk degradation mechanism. Addition of Clostridium histolyticum collagenase resulted in a much enhanced rate of degradation, which furthermore occurred via surface erosion. The mesh size of the hydrogels (>7nm) was in all cases larger than the hydrodynamic radius of the enzyme (4.5nm) so that even in very hydrophilic networks with large mesh size enzymes may be used to induce a fast surface degradation mechanism. This observation is of general interest when designing hydrogels to be applied in the presence of enzymes, as the degradation mechanism and material performance are closely interlinked. Copyright (c) 2016 John Wiley & Sons, Ltd. KW - Hydrogel KW - Biopolymer KW - Degradation Y1 - 2017 U6 - https://doi.org/10.1002/pat.3962 SN - 1042-7147 SN - 1099-1581 VL - 28 SP - 1318 EP - 1324 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Schöne, Anne-Christin A1 - Roch, Toralf A1 - Schulz, Burkhard A1 - Lendlein, Andreas T1 - Evaluating polymeric biomaterial-environment interfaces by Langmuir monolayer techniques JF - Interface : journal of the Royal Society N2 - Polymeric biomaterials are of specific relevance in medical and pharmaceutical applications due to their wide range of tailorable properties and functionalities. The knowledge about interactions of biomaterials with their biological environment is of crucial importance for developing highly sophisticated medical devices. To achieve optimal in vivo performance, a description at the molecular level is required to gain better understanding about the surface of synthetic materials for tailoring their properties. This is still challenging and requires the comprehensive characterization of morphological structures, polymer chain arrangements and degradation behaviour. The review discusses selected aspects for evaluating polymeric biomaterial-environment interfaces by Langmuir monolayer methods as powerful techniques for studying interfacial properties, such as morphological and degradation processes. The combination of spectroscopic, microscopic and scattering methods with the Langmuir techniques adapted to polymers can substantially improve the understanding of their in vivo behaviour. KW - Langmuir monolayer KW - biodegradable polymers KW - air - water interface KW - protein Langmuir layers Y1 - 2017 U6 - https://doi.org/10.1098/rsif.2016.1028 SN - 1742-5689 SN - 1742-5662 VL - 14 PB - Royal Society CY - London ER - TY - JOUR A1 - Paramonov, Guennaddi K. A1 - Kühn, Oliver A1 - Bandrauk, André D. T1 - Excitation of H+ 2 with one-cycle laser pulses BT - shaped post-laser-field electronic oscillations, generation of higher- and lower-order harmonics JF - Molecular physics : MP ; an international journal in the field of chemical physics N2 - Non-Born–Oppenheimer quantum dynamics of H+ 2 excited by shaped one-cycle laser pulses linearly polarised along the molecular axis have been studied by the numerical solution of the time-dependent Schrödinger equation within a three-dimensional model, including the internuclear separation, R, and the electron coordinates z and ρ. Laser carrier frequencies corresponding to the wavelengths λ l = 25 nm through λ l = 400 nm were used and the amplitudes of the pulses were chosen such that the energy of H+ 2 was close to its dissociation threshold at the end of any laser pulse applied. It is shown that there exists a characteristic oscillation frequency ωosc ≃ 0.2265 au (corresponding to the period of τosc ≃ 0.671 fs and the wavelength of λosc ≃ 201 nm) that manifests itself as a ‘carrier’ frequency of temporally shaped oscillations of the time-dependent expectation values ⟨z ⟩ and ⟨∂V/∂z ⟩ that emerge at the ends of the laser pulses and exist on a timescale of at least 50 fs. Time-dependent expectation values ⟨ρ⟩ and ⟨∂V /∂ρ⟩ of the optically passive degree of freedom, ρ, demonstrate post-laser-field oscillations at two basic frequencies ωρ 1 ≈ ωosc and ωρ 2 ≈ 2ωosc. Power spectra associated with the electronic motion show higher- and lower-order harmonics with respect to the driving field. KW - One-cycle laser pulses KW - post-laser-field electronic oscillations KW - generation of higher and lower harmonics Y1 - 2017 U6 - https://doi.org/10.1080/00268976.2017.1288938 SN - 0026-8976 SN - 1362-3028 VL - 115 IS - 15/16 SP - 1846 EP - 1860 PB - Taylor & Francis CY - London ER - TY - JOUR A1 - Hovestadt, Maximilian A1 - Bendt, Stephan A1 - Mondal, Suvendu Sekhar A1 - Behrens, Karsten A1 - Reif, Florian A1 - Dopken, Merle A1 - Holdt, Hans-Jürgen A1 - Keil, Frerich J. A1 - Hartmann, Martin T1 - Experimental and Theoretical Analysis of the Influence of Different Linker Molecules in Imidazolate Frameworks Potsdam (IFP-n) on the Separation of Olefin-Paraffin Mixtures JF - Langmuir N2 - Four metal organic frameworks with similar topology but different chemical environment inside the pore structure, namely, IFP-1, IFP-3, IFP-5, and IFP-7, have been investigated with respect to the separation potential for olefin paraffin mixtures as well as the influence of the different linkers on adsorption properties using experiments and Monte Carlo simulations. All IFP structures show a higher adsorption of ethane compared to ethene with the exception of IFP-7 which shows no selectivity in breakthrough experiments. For propane/propane separation, all adsorbents show a higher adsorption for the olefin. The experimental results agree quite well with the simulated values except for the IFP-7, which is presumably due to the flexibility of the structure. Moreover, the experimental and simulated isotherms were confirmed with breakthrough experiments that render IFP-1, IFP-3, and IFP-5 as suitable for the purification of ethene from ethane. Y1 - 2017 U6 - https://doi.org/10.1021/acs.langmuir.7b02016 SN - 0743-7463 VL - 33 SP - 11170 EP - 11179 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Wu, Lei A1 - Glebe, Ulrich A1 - Böker, Alexander T1 - Fabrication of Thermoresponsive Plasmonic Core-Satellite Nanoassemblies with a Tunable Stoichiometry via Surface-Initiated Reversible Addition-Fragmentation Chain Transfer Polymerization from Silica Nanoparticles JF - Advanced materials interfaces N2 - This work presents a fabrication of thermoresponsive plasmonic core-satellite nanoassemblies. The structure has a silica nanoparticle core surrounded by gold nanoparticle satellites using thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) chains as scaffolds. The thiol-terminated PNIPAM shell is densely grafted on the silica core via surface-initiated reversible addition-fragmentation chain transfer polymerization and used to anchor numerous gold nanoparticle satellites with a tunable stoichiometry. Below and above lower critical solution temperature, the chain conformation of PNIPAM reversibly changes between swollen and shrunken state. The reversible change of the polymer size varies the refractive index of the local medium surrounding the satellites and the distance between them. The two effects together lead to the thermoresponsive plasmonic properties of the nanoassemblies. Under different satellite densities, two distinctive plasmonic features appear. KW - gold KW - hybrid materials KW - polymeric materials KW - silica KW - surface plasmon resonance Y1 - 2017 U6 - https://doi.org/10.1002/admi.201700092 SN - 2196-7350 VL - 4 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Unuabonah, Emmanuel Iyayi A1 - Agunbiade, Foluso O. A1 - Alfred, Moses O. A1 - Adewumi, Thompson A. A1 - Okoli, Chukwunonso P. A1 - Omorogie, Martins O. A1 - Akanbi, Moses O. A1 - Ofomaja, Augustine E. A1 - Taubert, Andreas T1 - Facile synthesis of new amino-functionalized agrogenic hybrid composite clay adsorbents for phosphate capture and recovery from water JF - Journal of Cleaner Production N2 - New hybrid clay materials with good affinity for phosphate ions were developed from a combination of biomass-Carica papaya seeds (PS) and Musa paradisiaca (Plantain peels-PP), ZnCl2 and Kaolinite clay to produce iPS-HYCA and iPP-HYCA composite adsorbents respectively. Functionalization of these adsorbents with an organosilane produced NPS-HYCA and NPP-HYCA composite adsorbents. The pH(pzc) for the adsorbents were 7.83, 6.91, 7.66 and 6.55 for iPS-HYCA, NPS-HYCA, iPP-HYCA and NPP-HYCA respectively. Using the Brouer-Sotolongo isotherm model which best predict the adsorption capacity of composites for phosphate, iPP-HYCA, iPS-HYCA, NPP-HYCA, and NPS-HYCA composite adsorbents respectively. When compared with some commercial resins, the amino-functionalized adsorbents had better adsorption capacities. Furthermore, amino-functionalized adsorbents showed improved adsorption capacity and rate of phosphate uptake (as much as 40-fold), as well as retain 94% (for NPS-HYCA) and 84.1% (for NPP-HYCA) efficiency for phosphate adsorption after 5 adsorption-desorption cycles (96 h of adsorption time with 100 mg/L of phosphate ions) as against 37.5% (for iPS-HYCA) and 35% (for iPP-HYCA) under similar conditions. In 25 min desorption of phosphate ion attained equilibrium. These new amino-functionalized hybrid clay composite adsorbents, which were prepared by a simple means that is sustainable, have potentials for the efficient capture of phosphate ions from aqueous solution. They are quickly recovered from aqueous solution, non-biodegradable (unlike many biosorbent) with potentials to replace expensive adsorbents in the future. They have the further advantage of being useful in the recovery of phosphate for use in agriculture which could positively impact the global food security programme. (C) 2017 Elsevier Ltd. All rights reserved. KW - Composite adsorbents KW - Sustainable KW - Phosphate recovery KW - Water KW - Desorption kinetics Y1 - 2017 U6 - https://doi.org/10.1016/j.jclepro.2017.06.160 SN - 0959-6526 SN - 1879-1786 VL - 164 SP - 652 EP - 663 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Taubert, Andreas A1 - Löbbicke, Ruben A1 - Kirchner, Barbara A1 - Leroux, Fabrice T1 - First examples of organosilica-based ionogels BT - synthesis and electrochemical behavior JF - Beilstein journal of nanotechnology N2 - The article describes the synthesis and properties of new ionogels for ion transport. A new preparation process using an organic linker, bis(3-(trimethoxysilyl) propyl) amine (BTMSPA), yields stable organosilica matrix materials. The second ionogel component, the ionic liquid 1-methyl-3-(4-sulfobutyl) imidazolium 4-methylbenzenesulfonate, [BmimSO(3)H][PTS], can easily be prepared with near-quantitative yields. [BmimSO(3)H][PTS] is the proton conducting species in the ionogel. By combining the stable organosilica matrix with the sulfonated ionic liquid, mechanically stable, and highly conductive ionogels with application potential in sensors or fuel cells can be prepared. KW - ionic liquids KW - ionogels KW - organosilica KW - proton conductivity Y1 - 2017 U6 - https://doi.org/10.3762/bjnano.8.77 SN - 2190-4286 VL - 8 SP - 736 EP - 751 PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften CY - Frankfurt, Main ER - TY - JOUR A1 - Olejko, Lydia A1 - Bald, Ilko T1 - FRET efficiency and antenna effect in multi-color DNA origami-based light harvesting systems JF - RSC Advances N2 - Artificial light harvesting complexes find applications in artificial photosynthesis, photovoltaics and light harvesting chemical sensors. They are used to enhance the absorption of light of a reaction center which is often represented by a single acceptor. Here, we present different light harvesting systems on DNA origami structures and analyze systematically the light harvesting efficiency. By changing the number and arrangement of different fluorophores (FAM as donor, Cy3 as transmitter and Cy5 as acceptor molecules) the light harvesting efficiency is optimized to create a broadband absorption and to improve the antenna effect 1 (including two energy transfer steps) from 0.02 to 1.58, and the antenna effect 2 (including a single energy transfer step) from 0.04 to 8.7, i.e. the fluorescence emission of the acceptor is significantly higher when the light-harvesting antenna is excited at lower wavelength compared to direct excitation of the acceptor. The channeling of photo energy to the acceptor proceeds by Forster Resonance Energy Transfer (FRET) and we carefully analyze also the FRET efficiency of the different light harvesting systems. Accordingly, the antenna effect can be tuned by modifying the stoichiometry of donor, transmitter and acceptor dyes, whereas the FRET efficiency is mainly governed by the spectroscopic properties of dyes and their distances. Y1 - 2017 U6 - https://doi.org/10.1039/c7ra02114c SN - 2046-2069 VL - 7 IS - 39 SP - 23924 EP - 23934 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Ryabchun, Alexander A1 - Sakhno, Oksana A1 - Stumpe, Joachim A1 - Bobrovsky, Alexey T1 - Full-Polymer Cholesteric Composites for Transmission and Reflection Holographic Gratings JF - Advanced optical materials N2 - A new type of self-organized materials based on cholesteric networks filled with photoactive side-chain copolymer is being developed. Supramolecular helical structure of cholesteric polymer network resulting in the selective reflection is used as a photonic scaffold. Photochromic azobenzene-containing nematic copolymer is embedded in cholesteric scaffold and utilized as a photoactive media for optical pattering. 1D and 2D transmission diffraction gratings are successfully recorded in composite films by holographic technique. For the first time the possibility to create selective reflection gratings in cholesteric material mimicking the natural optical properties of cholesteric mesophase is demonstrated. That enables the coexistence of two selective gratings, where one has an intrinsic cholesteric periodic helical structure and the other is a holographic grating generated in photochromic polymer. The full-polymer composites provide high light-induced optical anisotropy due to effective photo-orientation of side-chain fragments of the azobenzene-containing liquid crystalline polymer, and prevent the degradation of the helical superstructure maintaining all optical properties of cholesteric mesophase. The proposed class of optical materials could be easily applied to a broad range of polymeric materials with specific functionality. The versatility of the adjustment and material preprogramming combined with high optical performance makes these materials a highly promising candidate for modern optical and photonic applications. KW - azobenzene KW - cholesteric scaffolds KW - holography KW - LC polymer KW - polarization diffraction grating KW - reflection grating Y1 - 2017 U6 - https://doi.org/10.1002/adom.201700314 SN - 2195-1071 VL - 5 SP - 376 EP - 379 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Mbaya Mani, Christian T1 - Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes T1 - Funktionale nanoporöse Kohlenstoffmaterialien auf Basis von Oxokohlenstoff-Metal Koordinationskomplexe N2 - Nanoporous carbon based materials are of particular interest for both science and industry due to their exceptional properties such as a large surface area, high pore volume, high electroconductivity as well as high chemical and thermal stability. Benefiting from these advantageous properties, nanoporous carbons proved to be useful in various energy and environment related applications including energy storage and conversion, catalysis, gas sorption and separation technologies. The synthesis of nanoporous carbons classically involves thermal carbonization of the carbon precursors (e.g. phenolic resins, polyacrylonitrile, poly(vinyl alcohol) etc.) followed by an activation step and/or it makes use of classical hard or soft templates to obtain well-defined porous structures. However, these synthesis strategies are complicated and costly; and make use of hazardous chemicals, hindering their application for large-scale production. Furthermore, control over the carbon materials properties is challenging owing to the relatively unpredictable processes at the high carbonization temperatures. In the present thesis, nanoporous carbon based materials are prepared by the direct heat treatment of crystalline precursor materials with pre-defined properties. This synthesis strategy does not require any additional carbon sources or classical hard- or soft templates. The highly stable and porous crystalline precursors are based on coordination compounds of the squarate and croconate ions with various divalent metal ions including Zn2+, Cu2+, Ni2+, and Co2+, respectively. Here, the structural properties of the crystals can be controlled by the choice of appropriate synthesis conditions such as the crystal aging temperature, the ligand/metal molar ratio, the metal ion, and the organic ligand system. In this context, the coordination of the squarate ions to Zn2+ yields porous 3D cube crystalline particles. The morphology of the cubes can be tuned from densely packed cubes with a smooth surface to cubes with intriguing micrometer-sized openings and voids which evolve on the centers of the low index faces as the crystal aging temperature is raised. By varying the molar ratio, the particle shape can be changed from truncated cubes to perfect cubes with right-angled edges. These crystalline precursors can be easily transformed into the respective carbon based materials by heat treatment at elevated temperatures in a nitrogen atmosphere followed by a facile washing step. The resulting carbons are obtained in good yields and possess a hierarchical pore structure with well-organized and interconnected micro-, meso- and macropores. Moreover, high surface areas and large pore volumes of up to 1957 m2 g-1 and 2.31 cm3 g-1 are achieved, respectively, whereby the macroscopic structure of the precursors is preserved throughout the whole synthesis procedure. Owing to these advantageous properties, the resulting carbon based materials represent promising supercapacitor electrode materials for energy storage applications. This is exemplarily demonstrated by employing the 3D hierarchical porous carbon cubes derived from squarate-zinc coordination compounds as electrode material showing a specific capacitance of 133 F g-1 in H2SO4 at a scan rate of 5 mV s-1 and retaining 67% of this specific capacitance when the scan rate is increased to 200 mV s-1. In a further application, the porous carbon cubes derived from squarate-zinc coordination compounds are used as high surface area support material and decorated with nickel nanoparticles via an incipient wetness impregnation. The resulting composite material combines a high surface area, a hierarchical pore structure with high functionality and well-accessible pores. Moreover, owing to their regular micro-cube shape, they allow for a good packing of a fixed-bed flow reactor along with high column efficiency and a minimized pressure drop throughout the packed reactor. Therefore, the composite is employed as heterogeneous catalyst in the selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking. Thinking about the rational design of 3D carbon geometries, the functions and properties of the resulting carbon-based materials can be further expanded by the rational introduction of heteroatoms (e.g. N, B, S, P, etc.) into the carbon structures in order to alter properties such as wettability, surface polarity as well as the electrochemical landscape. In this context, the use of crystalline materials based on oxocarbon-metal ion complexes can open a platform of highly functional materials for all processes that involve surface processes. N2 - Nanoporöse Kohlenstoffmaterialien zeichnen sich u. a. durch ihre außergewöhnlichen Eigenschaften aus wie z. B. hohe Oberfläche, hohes Porenvolumen, hohe elektrische Leitfähigkeit und auch hohe chemische und thermische Stabilität. Aufgrund dessen finden sie Anwendung in den unterschiedlichsten Bereichen von der Speicherung elektrischer Energie bis hin zur Katalyse und Gasspeicherung. Die klassische Synthese von porösen Kohlenstoffmaterialien basiert u. a. auf der Nutzung von sogenannten anorganischen bzw. organischen Templaten und/oder chemischen Aktivierungsagenzien. Allerdings gelten diese Methoden eher als kompliziert, kostspielig und umweltschädlich. Außerdem wird eine gezielte Kontrolle der Produkteigenschaften durch die zahlreichen Prozesse erschwert, die sich bei den hohen Karbonisierungstemperaturen abspielen und folglich die Materialeigenschaften unvorhersehbar verändern können. In der vorliegenden Arbeit wird ein alternatives Konzept für die Synthese von nanoporösen Kohlenstoffmaterialien mit gezielt einstellbaren Eigenschaften vorgestellt. Diese basiert auf der Nutzung von kristallinen Vorläufermaterialien, die aus der Koordination von den Anionen der Quadratsäure bzw. der Krokonsäure mit verschiedenen Metallionen (Zn2+, Cu2+, Ni2+ und Co2+) resultieren. Diese haben den Vorteil, dass Eigenschaften wie z. B. die Partikelmorphologie und Porosität gezielt durch die Wahl geeigneter Syntheseparameter (z. B. Temperatur, molares Verhältnis, Metallion und Ligand) eingestellt werden können. Beispielsweise führen Koordinationskomplexe von der Quadratsäure mit Zn2+ in Wasser zu porösen 3D würfelförmigen Mikrokristallen, die durch einfache thermische Behandlung unter Schutzgasatmosphäre zu den entsprechenden Kompositen umgewandelt werden. Ein anschließender Waschschritt führt zu den entsprechenden Kohlenstoffmaterialien unter Erhalt der makroskopischen Struktur der kristallinen Vorläufermaterialien. In diesem Zusammenhang weisen die resultierenden Kohlenstoffe ebenfalls eine 3D Würfelform mit einer hierarchischen Porenstruktur bestehend aus vernetzten Mikro-, Meso- und Makroporen auf. Ferner besitzen die Kohlenstoffe hohe Oberflächen und Porenvolumen von bis zu 1.957 m2 g-1 bzw. 2,31 cm3 g-1. Um die Vorteile dieser Eigenschaften zu demonstrieren, werden sie als Elektrodenmaterial für Superkondensatoren getestet und zeigen dabei vielversprechende Kapazitäten. Außerdem, werden sie auch als Trägermaterial für die Immobilisierung von Nickel-Nanopartikel verwendet und als heterogene Katalysatoren in der selektiven Hydrierung von 5-hydroxymethylfurfural zu 2,5-dimethylfuran in einem Festbettreaktor eingesetzt. Dabei wird eine gute Katalysatorleistung (Produktivität) bei minimalem Druckabfall in der Reaktorsäule erreicht. KW - squaric acid KW - Quadratsäure KW - mesocrystals KW - Mesokristalle KW - nanoporöser Kohlenstoffpartikel KW - nanoporous carbon particles KW - Nanopartikel KW - nanoparticles KW - Koordinationskomplexe KW - coordination complexes KW - oxocarbon KW - Oxo-Kohlenstoff Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-407866 ER - TY - THES A1 - Zhang, Weiyi T1 - Functional Poly(ionic liquid) Materials based on Poly(1,2,4-triazolium)s Y1 - 2017 ER - TY - THES A1 - Olejko, Lydia T1 - Förster resonance energy transfer (FRET)-based nanophotonics using DNA origami structures T1 - Förster-Resonanzenergietransfer (FRET) basierende Nanophotonik auf DNA Origami Strukturen N2 - The field of nanophotonics focuses on the interaction between electromagnetic radiation and matter on the nanometer scale. The elements of nanoscale photonic devices can transfer excitation energy non-radiatively from an excited donor molecule to an acceptor molecule by Förster resonance energy transfer (FRET). The efficiency of this energy transfer is highly dependent on the donor-acceptor distance. Hence, in these nanoscale photonic devices it is of high importance to have a good control over the spatial assembly of used fluorophores. Based on molecular self-assembly processes, various nanostructures can be produced. Here, DNA nanotechnology and especially the DNA origami technique are auspicious self-assembling methods. By using DNA origami nanostructures different fluorophores can be introduced with a high local control to create a variety of nanoscale photonic objects. The applications of such nanostructures range from photonic wires and logic gates for molecular computing to artificial light harvesting systems for artificial photosynthesis. In the present cumulative doctoral thesis, different FRET systems on DNA origami structures have been designed and thoroughly analyzed. Firstly, the formation of guanine (G) quadruplex structures from G rich DNA sequences has been studied based on a two-color FRET system (Fluorescein (FAM)/Cyanine3 (Cy3)). Here, the influences of different cations (Na+ and K+), of the DNA origami structure and of the DNA sequence on the G-quadruplex formation have been analyzed. In this study, an ion-selective K+ sensing scheme based on the G-quadruplex formation on DNA origami structures has been developed. Subsequently, the reversibility of the G-quadruplex formation on DNA origami structures has been evaluated. This has been done for the simple two-color FRET system which has then been advanced to a switchable photonic wire by introducing additional fluorophores (FAM/Cy3/Cyanine5 (Cy5)/IRDye®700). In the last part, the emission intensity of the acceptor molecule (Cy5) in a three-color FRET cascade has been tuned by arranging multiple donor (FAM) and transmitter (Cy3) molecules around the central acceptor molecule. In such artificial light harvesting systems, the excitation energy is absorbed by several donor and transmitter molecules followed by an energy transfer to the acceptor leading to a brighter Cy5 emission. Furthermore, the range of possible excitation wavelengths is extended by using several different fluorophores (FAM/Cy3/Cy5). In this part of the thesis, the light harvesting efficiency (antenna effect) and the FRET efficiency of different donor/transmitter/acceptor assemblies have been analyzed and the artificial light harvesting complex has been optimized in this respect. N2 - Nanotechnologie hat in den letzten Jahrzehnten durch die Herstellung von Materialien mit außergewöhnlichen Eigenschaften für Anwendungen im Bereich der Medizin und Materialwissenschaften immer mehr an Popularität gewonnen. Die Herstellungsmethoden von Nanostrukturen sind weit gefächert. Auch Desoxyribonukleinsäure (DNS bzw. engl. DNA, deoxyribonucleic acid) kann für die Herstellung von Strukturen im Nanometerbereich genutzt werden. Diese sogenannte DNA-Nanotechnologie wurde in den frühen 1980er Jahren von Nadrian C. Seeman begründet. Ungefähr 30 Jahre später wurde eine neue Methodik für die Herstellung von DNA-Nanostrukturen von Paul W. K. Rothemund entwickelt, die er „scaffold DNA origami“ (Gerüst-DNA-Origami) nannte. DNA-Origami-Nanostrukturen können relativ einfach hergestellt werden und eignen sich perfekt für die Anordnung unterschiedlicher Moleküle (zum Beispiel Fluorophore) mit hoher räumlicher Kontrolle und Präzision. Daher können sie als Substrate genutzt werden, um verschiedene Förster-Resonanzenergietransfer (FRET) Systeme zu entwerfen und zu untersuchen. FRET ist ein strahlungsloser Energietransfer, bei dem die Anregungsenergie von einem Donor- auf ein Akzeptor-Molekül übertragen wird. In dieser kumulativen Doktorarbeit wurden verschiedene FRET-Systeme auf DNA-Origami-Nanostrukturen entwickelt und mithilfe der Fluoreszenzspektroskopie untersucht. Hierbei wurde zuerst die durch einwertige Kationen (Kalium oder Natrium) induzierte Guanin-Quadruplex-Faltung von freier Telomer-DNA und Telomer-DNA auf DNA-Origami-Strukturen mittels FRET analysiert. Diese Untersuchungen haben gezeigt, dass die freie umgedrehte menschliche Telomer-Sequenz (RevHumTel, 5'-(GGG ATT)4) generell sensitiver auf K+ als auf Na+ reagiert. Durch die Immobilisierung der Telomer-DNA auf DNA-Origami-Strukturen kann eine vollständige Selektivität für K+ erreicht werden. Interessanterweise wird die Ionenselektivität aufgehoben, wenn die menschliche Telomer-Sequenz (HumTel, 5'-(TTA GGG)4) verwendet wird. Basierend auf der G-Quadruplex-Faltung konnten schaltbare FRET-Systeme entwickelt werden, da sich die G-Quadruplexe wieder entfalten, wenn die Kationen mithilfe von zum Beispiel Kryptanden entfernt werden. In den hier untersuchten FRET-Systemen konnte zwischen hoher FRET-Effizienz (gefalteter G-Quadruplex) und niedriger FRET-Effizienz (entfalteter DNA Einzelstrang) durch Zugabe KCl bzw. cryptand gewechselt werden. Da sich DNA-Origami-Strukturen recht einfach modifizieren lassen, wurde das ursprüngliche zwei-Farben-FRET-System durch Hinzufügen eines weiteren etwas rotverschobenen Farbstoffes erweitert (drei-Farben-FRET-Kaskade). Schließlich konnte ein schaltbarer photonischer Draht durch Einfügen eines vierten Farbstoffes entwickelt werden. Die Emissionsintensität des finalen Akzeptors ist in einer einfachen drei-Farben-FRET-Kaskade (ein Donor, ein Transmitter und ein Akzeptor) verhältnismäßig gering und kann durch das Anordnen von mehreren Donor- und Transmitter-Molekülen um ein zentrales Akzeptor-Molekül herum stark erhöht werden. In diesen sogenannten künstlichen Lichtsammelkomplexen absorbieren die Donor-Moleküle das Anregungslicht und übertragen dieses über mehrere FRET-Stufen zum Akzeptor-Molekül. Dadurch wird der Wellenlängenbereich der elektromagnetischen Strahlung, welcher vom Akzeptor absorbiert werden kann, vergrößert und die Emissionsintensität des Akzeptors verstärkt. In diesem Teil der Arbeit wurde die Anzahl der Farbstoffe und die Anordnung dieser unterschiedlichen Farbstoffe variiert und die Lichtsammeleffizienz und FRET-Effizienz bestimmt. Hierbei wurden diese Parameter optimiert und aufgrund der gefundenen Ergebnisse konnten Design-Regeln für solche künstlichen Lichtsammelkomplexe aufgestellt werden. KW - DNA origami KW - FRET KW - Förster resonance energy transfer KW - DNA Origami KW - FRET KW - Förster-Resonanzenergietransfer Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-396747 ER - TY - JOUR A1 - Sung, Jian-Ke A1 - Kochovski, Zdravko A1 - Zhang, Wei-Yi A1 - Kirmse, Holm A1 - Lu, Yan A1 - Antonietti, Markus A1 - Yuan, Jiayin T1 - General Synthetic Route toward Highly Dispersed Metal Clusters Enabled by Poly(ionic liquid)s JF - Journal of the American Chemical Society N2 - The ability to synthesize a broad spectrum of metal clusters (MCs) with their size controllable on a subnanometer scale presents an enticing prospect for exploring nanosize-dependent properties. Here we report an innovative design of a capping agent from a polytriazolium poly(ionic liquid) (PIL) in a vesicular form in solution that allows for crafting a variety of MCs including transition metals, noble metals, and their bimetallic alloy with precisely controlled sizes (similar to 1 nm) and record-high catalytic performance. The ultrastrong stabilization power is a result of an unusual synergy between the conventional binding sites in the heterocyclic cations in PIL and an in situ generated polycarbene structure induced simultaneously to the reduction reaction. Y1 - 2017 U6 - https://doi.org/10.1021/jacs.7b03357 SN - 0002-7863 VL - 139 SP - 8971 EP - 8976 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Heck, Christian T1 - Gold and silver nanolenses self-assembled by DNA origami T1 - Gold- und Silbernanolinsen, selbstassembliert durch DNA-Origami N2 - Nanolenses are linear chains of differently-sized metal nanoparticles, which can theoretically provide extremely high field enhancements. The complex structure renders their synthesis challenging and has hampered closer analyses so far. Here, the technique of DNA origami was used to self-assemble DNA-coated 10 nm, 20 nm, and 60 nm gold or silver nanoparticles into gold or silver nanolenses. Three different geometrical arrangements of gold nanolenses were assembled, and for each of the three, sets of single gold nanolenses were investigated in detail by atomic force microscopy, scanning electron microscopy, dark-field scattering and Raman spectroscopy. The surface-enhanced Raman scattering (SERS) capabilities of the single nanolenses were assessed by labelling the 10 nm gold nanoparticle selectively with dye molecules. The experimental data was complemented by finite-difference time-domain simulations. For those gold nanolenses which showed the strongest field enhancement, SERS signals from the two different internal gaps were compared by selectively placing probe dyes on the 20 nm or 60 nm gold particles. The highest enhancement was found for the gap between the 20 nm and 10 nm nanoparticle, which is indicative of a cascaded field enhancement. The protein streptavidin was labelled with alkyne groups and served as a biological model analyte, bound between the 20 nm and 10 nm particle of silver nanolenses. Thereby, a SERS signal from a single streptavidin could be detected. Background peaks observed in SERS measurements on single silver nanolenses could be attributed to amorphous carbon. It was shown that the amorphous carbon is generated in situ. N2 - Nanolinsen sind Strukturen aus linear angeordneten, unterschiedlich großen metallischen Nanopartikeln. Elektromagnetische Felder können durch sie theoretisch extrem verstärkt werden, aufgrund ihres komplexen Aufbaus sind sie bislang aber wenig erforscht. Im Rahmen dieser Dissertation wurden Nanolinsen mit Hilfe der DNA-Origami-Technik aus DNA-beschichteten 10 nm-, 20 nm- und 60 nm-Gold- oder Silbernanopartikeln hergestellt. Für Goldnanolinsen sind die Partikel dabei in drei unterschiedlichen Geometrien angeordnet worden. Einzelne Goldnanolinsen wurden mittels Rasterkraftmikroskopie, Rasterelektronenmikroskopie, Dunkelfeld- und Ramanspektroskopie untersucht. Um die Raman-Verstärkung quantifizieren zu können, trugen dabei jeweils die 10 nm-Goldpartikel Farbstoffmoleküle in ihrer Beschichtung. Die Interpretation der Messdaten wurde durch numerische Simulationen unterstützt. Nanolinsen zeichnen sich durch eine stufenweise Feldverstärkung aus. Dieser Effekt konnte experimentell bestätigt werden, indem selektiv die 20 nm- oder 60 nm-Partikel von Goldnanolinsen mit Farbstoffen markiert und die resultierenden Raman-Signale verglichen wurden. Ein mit Alkingruppen markiertes Protein ist ortsselektiv in Silbernanolinsen integriert worden. Es war möglich, das für das Alkin charakteristische oberflächenverstärkte Raman-Signal im Spektrum einer einzelnen Nanolinse und damit eines einzelnen Proteins zu beobachten. Bei den Messungen mit Silbernanolinsen sind für amorphe Kohlenstoffspezies charakterstische Hintergrundsignale beobachtet worden. Durch zeitabhängige Messungen konnte gezeigt werden, dass diese Spezies erst in situ gebildet werden. KW - DNA origami KW - gold nanoparticles KW - silver nanoparticles KW - SERS KW - self-assembly KW - plasmonics KW - nanolenses KW - DNA-Origami KW - Goldnanopartikel KW - Silbernanopartikel KW - SERS KW - Selbstassemblierung KW - Plasmonik KW - Nanolinsen Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-409002 ER - TY - JOUR A1 - Heck, Christian A1 - Prinz, Julia A1 - Dathe, Andre A1 - Merk, Virginia A1 - Stranik, Ondrej A1 - Fritzsche, Wolfgang A1 - Kneipp, Janina A1 - Bald, Ilko T1 - Gold Nanolenses Self-Assembled by DNA Origami JF - ACS Photonics N2 - Nanolenses are self-similar chains of metal nanoparticles, which can theoretically provide extremely high field enhancements. Yet, the complex structure renders their synthesis challenging and has hampered closer analyses so far. Here, DNA origami is used to self-assemble 10, 20, and 60 nm gold nanoparticles as plasmonic gold nanolenses (AuNLs) in solution and in billions of copies. Three different geometrical arrangements are assembled, and for each of the three designs, surface-enhanced Raman scattering (SERS) capabilities of single AuNLs are assessed. For the design which shows the best properties, SERS signals from the two different internal gaps are compared by selectively placing probe dyes. The highest Raman enhancement is found for the gap between the small and medium nanoparticle, which is indicative of a cascaded field enhancement. KW - plasmonics KW - DNA origami KW - SERS KW - nanolenses KW - gold nanoparticles Y1 - 2017 U6 - https://doi.org/10.1021/acsphotonics.6b00946 SN - 2330-4022 VL - 4 SP - 1123 EP - 1130 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Andrews, N. L. P. A1 - Ferguson, T. A1 - Rangaswamy, A. M. M. A1 - Bernicky, A. R. A1 - Henning, N. A1 - Dudelzak, A. A1 - Reich, Oliver A1 - Barnes, Jack A. A1 - Loock, Hans-Peter T1 - Hadamard-Transform Fluorescence Excitation-Emission-Matrix Spectroscopy JF - Analytical chemistry N2 - We present a fluorescence excitation-emission-matrix spectrometer with superior data acquisition rates over previous instruments. Light from a white light emitting diode (LED) source is dispersed onto a digital micromirror array (DMA) and encoded using binary n-size Walsh functions ("barcodes"). The encoded excitation light is used to irradiate the liquid sample and its fluorescence is dispersed and detected using a conventional array spectrometer. After exposure to excitation light encoded in n different ways, the 2-dimensional excitation-emission-matrix (EEM) spectrum is obtained by inverse Hadamard transformation. Using this technique we examined the kinetics of the fluorescence of rhodamine B as a function of temperature and the acid-driven demetalation of chlorophyll into pheophytin-a. For these experiments, EEM spectra with 31 excitation channels and 2048 emission channels were recorded every 15 s. In total, data from over 3000 EEM spectra were included in this report. It is shown that the increase in data acquisition rate can be as high as [{n(n + 1)}/2]-fold over conventional EEM spectrometers. Spectral acquisition rates of more than two spectra per second were demonstrated. Y1 - 2017 U6 - https://doi.org/10.1021/acs.analchem.7b02400 SN - 0003-2700 SN - 1520-6882 VL - 89 SP - 8554 EP - 8564 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - von Klitzing, Regine A1 - Stehl, Dimitrij A1 - Pogrzeba, Tobias A1 - Schomaäcker, Reinhard A1 - Minullina, Renata A1 - Panchal, Abhishek A1 - Konnova, Svetlana A1 - Fakhrullin, Rawil A1 - Koetz, Joachim A1 - Moehwald, Helmuth A1 - Lvov, Yuri T1 - Halloysites Stabilized Emulsions for Hydroformylation of Long Chain Olefins JF - Advanced materials interfaces N2 - Halloysites as tubular alumosilicates are introduced as inexpensive natural nanoparticles to form and stabilize oil-water emulsions. This stabilized emulsion is shown to enable efficient interfacial catalytic reactions. Yield, selectivity, and product separation can be tremendously enhanced, e.g., for the hydroformylation reaction of dodecene to tridecanal. In perspective, this type of formulation may be used for oil spill dispersions. The key elements of the described formulations are clay nanotubes (halloysites) which are highly anisometric, can be filled by helper molecules, and are abundantly available in thousands of tons, making this technology scalable for industrial applications. Y1 - 2016 U6 - https://doi.org/10.1002/admi.201600435 SN - 2196-7350 VL - 4 IS - 1 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Dippong, Martin A1 - Carl, Peter A1 - Lenz, Christine A1 - Schenk, Jörg A. A1 - Hoffmann, Katrin A1 - Schwaar, Timm A1 - Schneider, Rudolf J. A1 - Kuhne, Maren T1 - Hapten-Specific Single-Cell Selection of Hybridoma Clones by Fluorescence-Activated Cell Sorting for the Generation of Monoclonal Antibodies JF - Analytical chemistry Y1 - 2017 U6 - https://doi.org/10.1021/acs.analchem.6b04569 SN - 0003-2700 SN - 1520-6882 VL - 89 SP - 4007 EP - 4012 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Braun, Max T1 - Heterogeneous Catalysis for the Conversion of Fructose to Chemicals and Fuel in a Continuous Flow Process T1 - Umsetzung von Fruktose zu Chemikalien und Treibstoff mittels heterogener Katalysatoren in einem kontinuierlichen Prozess N2 - Die Umsetzung von Zucker (Kohlenhydrate) in einem kontinuierlichen Prozess eröffnet Möglichkeiten der Synthese diverser Chemikalien und Treibstoff aus erneuerbaren Ressourcen, welche heute überwiegend aus fossilen Quellen stammen. Passend zum Konzept der Bioraffinerie und der „grünen Chemie“, liegt der Fokus dieser Arbeit auf der Umsetzung von in Ethanol gelöster Fruktose in einem kontinuierlichen Verfahren, mit Hilfe eigens entwickelter heterogener Katalysatoren. Die Dehydratisierung von Fruktose wird mit einem heterogenen Säurekatalysator realisiert, während die Folgeprodukte mittels einer Hydrodesoxygenierung umgesetzt werden. Für den zweiten Schritt kommen Metallkatalysatoren auf Basis von Nickel und Wolframcarbid (WC) zum Einsatz, wodurch der Einsatz teurer Edelmetalle vermieden werden kann. Hauptprodukte des zweistufigen Verfahrens sind 2,5-Dimethylfuran (DMF) und Ethyllevulinat (EL). Beide Moleküle sind vielversprechende alternative Treibstoffe, bzw. können gebräuchlichen Treibstoffen beigemischt werden, um deren Einsatz zu reduzieren und schrittweise zu substituieren. Alternativ können die Zwischenprodukte der Dehydratisierung, sowie DMF und EL weiter zu Chemikalien umgesetzt werden, welche in der Polymersynthese, als Lösungsmittel oder als Grundchemikalien eingesetzt werden können. Die Entwicklung der jeweiligen Katalysatoren für Dehydratisierungs- und Hydrodesoxygenierungsreaktionen erfolgt auf Basis von karbonisierter Biomasse, sowie Wolframcarbid. Die jeweiligen Reaktivitäten werden durch Standardreaktionen getestet, wobei sich Wolframcarbid in Nanopartikelform, in Kombination mit Wasserstoff als sehr aktiv erwiesen hat. Der selbst entwickelte aktivierte Kohlenstoff, das kommerzielle Amberlyst 15, sowie Wolframcarbid mit zusätzlichen Nickel-Nanopartikeln werden für weiterführende Reaktionen in einem kontinuierlichen Prozess herangezogen und kombiniert. Um den Umsatz von Fruktose zu DMF in einer „zwei Reaktoren Anlage“ zu ermöglichen, wird eine Erweiterung eines kommerziellen Reaktorsystems um einen weiteren Reaktor vorgenommen. Die Verweilzeit in der Reaktoranlage beträgt somit ca. 14 Minuten, wobei 11 Minuten auf die erste Säule (Dehydratisierung) und 3 Minuten auf die zweite Säule (Hydrodesoxygenierung) entfallen. In diesem kontinuierlichen und zweistufigen System lassen sich Ausbeuten von 38.5 % DMF und 47 % EL erzielen. Ein kontinuierlicher Lauf von sieben Stunden zeigt die Stabilität der eingesetzten Katalysatoren, auch wenn eine geringe Deaktivierung des Dehydratisierungskatalysators beobachtet werden kann. Der Ni@WC Katalysator zeigte hingegen keine Abnahme der Nickel Konzentration und somit kommt es zu keiner Auswaschung des Metalls. Das gebildete EL wurde hingegen nicht umgesetzt und verbleibt unverändert in Lösung. Das zweistufige System wurde schließlich in einem Mischkatalysatorsystem kombiniert, wobei auf aktivierten und sulfonierten Kohlenstoff zurückgegriffen wurde. Dieser zeigte bereits eine Transferhydrodesoxygenierungsaktivität. Diese Beobachtung ist deshalb bemerkenswert, da erst seit kurzem bekannt ist, dass Graphenstrukturen an sich katalytisch aktiv sein können. Um diese Aktivität weiter zu steigern, wurde der aktivierte Kohlenstoff mit 10 wt% Ni@WC gemischt, sodass beide Katalysatoren in einer Säule vorliegen. Die ursprünglichen 2 % DMF Ausbeute mit reinem aktivierten Kohlenstoff können somit auf 12 % gesteigert werden, da das Folgeprodukt EL hierbei vermieden wird und das Zwischenprodukt „HMF Derivat“ direkt zu DMF weiter reagieren kann. Dieses Ergebnis zeigt das Potential der „ein Reaktor Umsetzung“, weshalb eine kontinuierliche Durchflussreaktoranlage im Litermaßstab als Scale-Up des vorhergehenden Labormaßstabs realisiert wurde. Der 800 mm x 28.5 mm Reaktor bedient eine maximale Flussrate von 50 mL min-1, Drücke von 100 bar und Temperaturen bis zu 500 °C. N2 - The valorization of carbohydrates is one of the most promising fields in green chemistry, as it enables to produce bulk chemicals and fuels out of renewable and abundant resources, instead of further exploiting fossil feedstocks. The focus in this thesis is the conversion of fructose, using dehydration and hydrodeoxygenation reactions. The main goal is to find an easy continuous process, including the solubility of the sugar in a green solvent, the conversion over a solid acid as well as over a metal@tungsten carbide catalyst. At the beginning of this thesis, solid acid catalysts are synthesized by using carbohydrate material like glucose and starch at high temperatures (up to 600 °C). Additionally a third carbon is synthesized, using an activation method based on Ca(OH)2. After carbonization and further sulfonation, using fuming sulfuric acid, the three resulting catalysts are characterized together with sulfonated carbon black and Amberlyst 15 as references. In order to test all solid acid catalysts in reaction, a 250 mm x 4.6 mm stainless steel column is used as a fixed-bed continuous reactor. The temperature (110 °C to 250 °C) and residence time (2 to 30 minutes) is varied, and a direct relationship between contact time and selectivity is determined. The reaction mechanism, as well as the product distribution is showing a dehydration step of fructose towards 5-hydroxymethylfurfural (HMF). These furan-ring molecules are considered as “sleeping giants”, due to the possibility of using them as fuel, but also for upgrading them to chemicals like terephthalic acid or p-xylene. Consecutive reactions are producing levulinic acid, as well as condensation products with ethanol and formic acid. The activated carbon is additionally showing a 2 % yield of 2,5-Dimethylfuran (DMF) production, pointing towards the extraordinary properties of this catalyst. Without a metal catalyst present, what is normally necessary for hydrogenation reactions, a transferhydrogenation (with formic acid) is observed. The active catalyst was therefore carbon itself, what activated the hydrogen on its surface. This phenomenon was just very rarely observed so far. Expensive noble metals are the material of choice, when it comes to hydrogenation reactions nowadays and cheaper alternatives are necessary. By postulating a similar electronic structure of tungsten carbide (WC) to platinum by Lewy and Boudart, research is focusing on the replacement of Pt. The production of nano-sized tungsten carbide particles (7.5 ± 2.5 nm, 70 m2 g-1) is enabled by the so called “urea glass route” and its catalytic performances are compared to commercial material. It is shown, that the activity is strongly dependent on the size of the particles as well as the surface area. Nano-sized tungsten carbide is showing activity for hydrogenation reactions under mild conditions (maximum 150 °C, 30 bar). This material therefore opens up new possibilities for replacing the rare and expensive platinum with tungsten carbide based catalysts. Additionally different metal nanoparticles of palladium, copper and nickel are deposited on top of WC to further promote its reactivity. The nickel nanoparticles are strongly connected to WC and showed the best activity as well as selectivity for upgrading HMF with hydrodeoxygenation. The Ni@WC is not leaching and is showing very good hydrodeoxygenation properties with DMF yields up to 90 percent. Copper@WC is not showing good activity and palladium@WC enables undesired consecutive reactions, hydrogenating the furan ring system. In order to enable the upgrade of fructose to DMF directly in a continuous system, the current H CUBE Pro TM hydrogenation system is customized with a second reaction column. A 250 mm x 4.6 mm stainless steel reactor column is connected ahead of the hydrogen insertion, enabling the dehydration of fructose to HMF derivatives, before pumping these products into the second column for hydrogenation. The overall residence time in the two column reactor system is 14 minutes. The overall results are an almost full conversion with a yield of 38.5 % DMF and 47 % yield of EL. The main disadvantage is the formation of higher mass products, so called humins, which start depositing on top of the catalysts, blocking their active sites. In general it can be stated, that a two column system goes along with a higher investment as well as more maintenance costs, compared to a one column catalytic approach. To develop a catalyst, which is on the one hand able to dehydrate as well as hydrodeoxygenate the reactants, is aimed for at the last part of the thesis. The activated carbon however shows already activity for hydrodeoxygenation without any metal present and offers itself therefore as an alternative to overcome the temperature instability of Amberlyst 15 (max. 120 °C) for a combined DMF production directly from fructose. The activity for the upgrade to DMF is increased from 2 % to 12 % DMF yield in one mixed continuous column. In order to scale up the entire one column approach, an 800 mm x 28.5 mm inner diameter column was planned and manufactured. The system is scaled up and assembled, whereas this flow reactor system is able to be run with 50 mL min-1 maximum flow rate, to stand a pressure of maximum 100 bar and be heated to around 500 °C. The tubing and connections, as well as the used devices are planned according to be safe and easy in use. The scaled-up approach offers a reaction column 120 times bigger (510 ml) then the first extension of the commercial system. This further extension offers the possibility of ranging between 1 and 1000 mL min-1, making it possible to use the approach in pilot plant applications. KW - Biorefinery KW - Catalysis KW - Hydroxymethylfurfural KW - Upgrade of Fructose KW - Bioraffinerie KW - Katalyse KW - Hydroxymethylfurfural KW - Aufarbeitung von Fruktose Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-410370 ER - TY - JOUR A1 - Schwarze, Thomas A1 - Mertens, Monique A1 - Mueller, Peter A1 - Riemer, Janine A1 - Wessig, Pablo A1 - Holdt, Hans-Jürgen T1 - Highly K+-Selective Fluorescent Probes for Lifetime Sensing of K+ in Living Cells JF - Chemistry - a European journal N2 - The new K+-selective fluorescent probes 1 and 2 were obtained by Cu-I-catalyzed 1,3-dipolar azide alkyne cycloaddition (CuAAC) reactions of an alkyne-substituted [1,3]dioxolo[4,5-f][1,3]benzodioxole (DBD) ester fluorophore with azido-functionalized N-phenylaza-18-crown-6 ether and N-(o-isopropoxy) phenylaza-18-crown-6 ether, respectively. Probes 1 and 2 allow the detection of K+ in the presence of Na+ in water by fluorescence enhancement (2.2 for 1 at 2000mm K+ and 2.5 for 2 at 160mm K+). Fluorescence lifetime measurements in the absence and presence of K+ revealed bi-exponential decay kinetics with similar lifetimes, however with different proportions changing the averaged fluorescence decay times ((f(av))). For 1 a decrease of (f(av)) from 12.4 to 9.3ns and for 2 an increase from 17.8 to 21.8ns was observed. Variation of the substituent in ortho position of the aniline unit of the N-phenylaza-18-crown-6 host permits the modulation of the K-d value for a certain K+ concentration. For example, substitution of H in 1 by the isopropoxy group (2) decreased the K-d value from >300mm to 10mm. 2 was chosen for studying the efflux of K+ from human red blood cells (RBC). Upon addition of the Ca2+ ionophor ionomycin to a RBC suspension in a buffer containing Ca2+, the fluorescence of 2 slightly rose within 10min, however, after 120min a significant increase was observed. KW - electron transfer KW - fluorescence lifetime KW - fluorescent probes KW - living cells KW - potassium Y1 - 2017 U6 - https://doi.org/10.1002/chem.201704368 SN - 0947-6539 SN - 1521-3765 VL - 23 SP - 17186 EP - 17190 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Yang, Guang A1 - Ding, Hong-ming A1 - Kochovski, Zdravko A1 - Hu, Rongting A1 - Lu, Yan A1 - Ma, Yu-qiang A1 - Chen, Guosong A1 - Jiang, Ming T1 - Highly Ordered Self-Assembly of Native Proteins into 1D, 2D, and 3D Structures Modulated by the Tether Length of Assembly-Inducing Ligands JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - In nature, proteins self-assemble into various structures with different dimensions. To construct these nanostructures in laboratories, normally proteins with different symmetries are selected. However, most of these approaches are engineering-intensive and highly dependent on the accuracy of the protein design. Herein, we report that a simple native protein LecA assembles into one-dimensional nanoribbons and nanowires, two-dimensional nanosheets, and three-dimensional layered structures controlled mainly by small-molecule assembly-inducing ligands RnG (n = 1, 2, 3, 4, 5) with varying numbers of ethylene oxide repeating units. To understand the formation mechanism of the different morphologies controlled by the small-molecule structure, molecular simulations were performed from microscopic and mesoscopic view, which presented a clear relationship between the molecular structure of the ligands and the assembled patterns. These results introduce an easy strategy to control the assembly structure and dimension, which could shed light on controlled protein assembly. KW - carbohydrate-protein interactions KW - dual non-covalent interactions KW - molecular simulations KW - protein self-assembly Y1 - 2017 U6 - https://doi.org/10.1002/anie.201703052 SN - 1433-7851 SN - 1521-3773 VL - 56 SP - 10691 EP - 10695 PB - Wiley-VCH CY - Weinheim ER -