@misc{PrestelMoeller2015, author = {Prestel, Andreas and M{\"o}ller, Heiko Michael}, title = {Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-89658}, pages = {701 -- 704}, year = {2015}, abstract = {The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.}, language = {en} } @article{KastlBraunPresteletal.2015, author = {Kastl, Johanna and Braun, Joachim and Prestel, Andreas and M{\"o}ller, Heiko Michael and Huhn, Thomas and Mayer, Thomas U.}, title = {Mad2 Inhibitor-1 (M2I-1): A Small Molecule Protein-Protein Interaction Inhibitor Targeting the Mitotic Spindle Assembly Checkpoint}, series = {ACS chemical biology}, volume = {10}, journal = {ACS chemical biology}, number = {7}, publisher = {American Chemical Society}, address = {Washington}, issn = {1554-8929}, doi = {10.1021/acschembio.5b00121}, pages = {1661 -- 1666}, year = {2015}, abstract = {The genetic integrity of each organism depends on the faithful segregation of its genome during mitosis. To meet this challenge, a cellular surveillance mechanism, termed the spindle assembly checkpoint (SAC), evolved that monitors the correct attachment of chromosomes and blocks progression through mitosis if corrections are needed. While the central role of the SAC for genome integrity is well established, its functional dissection has been hampered by the limited availability of appropriate small molecule inhibitors. Using a fluorescence polarization-based screen, we identify Mad2 inhibitor-1 (M2I-1), the first small molecule inhibitor targeting the binding of Mad2 to Cdc20, an essential protein-protein interaction (PPI) within the SAC. Based on computational and biochemical analyses, we propose that M2I-1 disturbs conformational dynamics of Mad2 critical for complex formation with Cdc20. Cellular studies revealed that M2I-1 weakens the SAC response, indicating that the compound might be active in cells. Thus, our study identifies the SAC specific complex formation between Mad2 and Cdc20 as a protein-protein interaction that can be targeted by small molecules.}, language = {en} } @article{PrestelMoeller2015, author = {Prestel, Andreas and M{\"o}ller, Heiko Michael}, title = {Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides}, series = {Chemical communications : ChemComm}, journal = {Chemical communications : ChemComm}, number = {52}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1364-548X}, doi = {10.1039/C5CC06848G}, pages = {701 -- 704}, year = {2015}, abstract = {The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.}, language = {en} } @phdthesis{Primus2015, author = {Primus, Philipp-Alexander}, title = {High resolution spectroscopy as a tool to unravel structure-reactivity relationships in Eu3+ doped ceria/ceria-zirconia based catalyst nanomaterials}, school = {Universit{\"a}t Potsdam}, pages = {89}, year = {2015}, language = {en} } @article{GuhaWarsinkeTientcheuetal.2015, author = {Guha, S. and Warsinke, A. and Tientcheu, Ch. M. and Schmalz, K. and Meliani, C. and Wenger, Ch.}, title = {Label free sensing of creatinine using a 6 GHz CMOS near-field dielectric immunosensor}, series = {The analyst : the analytical journal of the Royal Society of Chemistry}, volume = {9}, journal = {The analyst : the analytical journal of the Royal Society of Chemistry}, number = {140}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0003-2654}, doi = {10.1039/c4an02194k}, pages = {3019 -- 3027}, year = {2015}, abstract = {In this work we present a CMOS high frequency direct immunosensor operating at 6 GHz (C-band) for label free determination of creatinine. The sensor is fabricated in standard 0.13 μm SiGe:C BiCMOS process. The report also demonstrates the ability to immobilize creatinine molecules on a Si3N4 passivation layer of the standard BiCMOS/CMOS process, therefore, evading any further need of cumbersome post processing of the fabricated sensor chip. The sensor is based on capacitive detection of the amount of non-creatinine bound antibodies binding to an immobilized creatinine layer on the passivated sensor. The chip bound antibody amount in turn corresponds indirectly to the creatinine concentration used in the incubation phase. The determination of creatinine in the concentration range of 0.88-880 μM is successfully demonstrated in this work. A sensitivity of 35 MHz/10 fold increase in creatinine concentration (during incubation) at the centre frequency of 6 GHz is gained by the immunosensor. The results are compared with a standard optical measurement technique and the dynamic range and sensitivity is of the order of the established optical indication technique. The C-band immunosensor chip comprising an area of 0.3 mm2 reduces the sensing area considerably, therefore, requiring a sample volume as low as 2 μl. The small analyte sample volume and label free approach also reduce the experimental costs in addition to the low fabrication costs offered by the batch fabrication technique of CMOS/BiCMOS process.}, language = {en} } @misc{GuhaWarsinkeTientcheuetal.2015, author = {Guha, S. and Warsinke, A. and Tientcheu, Ch. M. and Schmalz, K. and Meliani, C. and Wenger, Ch.}, title = {Label free sensing of creatinine using a 6 GHz CMOS near-field dielectric immunosensor}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-81177}, year = {2015}, abstract = {In this work we present a CMOS high frequency direct immunosensor operating at 6 GHz (C-band) for label free determination of creatinine. The sensor is fabricated in standard 0.13 μm SiGe:C BiCMOS process. The report also demonstrates the ability to immobilize creatinine molecules on a Si3N4 passivation layer of the standard BiCMOS/CMOS process, therefore, evading any further need of cumbersome post processing of the fabricated sensor chip. The sensor is based on capacitive detection of the amount of non-creatinine bound antibodies binding to an immobilized creatinine layer on the passivated sensor. The chip bound antibody amount in turn corresponds indirectly to the creatinine concentration used in the incubation phase. The determination of creatinine in the concentration range of 0.88-880 μM is successfully demonstrated in this work. A sensitivity of 35 MHz/10 fold increase in creatinine concentration (during incubation) at the centre frequency of 6 GHz is gained by the immunosensor. The results are compared with a standard optical measurement technique and the dynamic range and sensitivity is of the order of the established optical indication technique. The C-band immunosensor chip comprising an area of 0.3 mm2 reduces the sensing area considerably, therefore, requiring a sample volume as low as 2 μl. The small analyte sample volume and label free approach also reduce the experimental costs in addition to the low fabrication costs offered by the batch fabrication technique of CMOS/BiCMOS process.}, language = {en} } @article{BartoloniJinMarcaidaetal.2015, author = {Bartoloni, Marco and Jin, Xian and Marcaida, Maria Jos{\´e} and Banha, Joao and Dibonaventura, Ivan and Bongoni, Swathi and Bartho, Kathrin and Gr{\"a}bner, Olivia and Sefkow, Michael and Darbre, Tamis and Reymond, Jean-Louis}, title = {Bridged bicyclic peptides as potential drug scaffolds}, series = {Chemical Science}, volume = {10}, journal = {Chemical Science}, number = {6}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2041-6520}, doi = {10.1039/C5SC01699A}, pages = {5473 -- 5490}, year = {2015}, abstract = {Double cyclization of short linear peptides obtained by solid phase peptide synthesis was used to prepare bridged bicyclic peptides (BBPs) corresponding to the topology of bridged bicyclic alkanes such as norbornane. Diastereomeric norbornapeptides were investigated by 1H-NMR, X-ray crystallography and CD spectroscopy and found to represent rigid globular scaffolds stabilized by intramolecular backbone hydrogen bonds with scaffold geometries determined by the chirality of amino acid residues and sharing structural features of β-turns and α-helices. Proteome profiling by capture compound mass spectrometry (CCMS) led to the discovery of the norbornapeptide 27c binding selectively to calmodulin as an example of a BBP protein binder. This and other BBPs showed high stability towards proteolytic degradation in serum.}, language = {en} } @misc{BartoloniJinMarcaidaetal.2015, author = {Bartoloni, Marco and Jin, Xian and Marcaida, Maria Jos{\´e} and Banha, Joao and Dibonaventura, Ivan and Bongoni, Swathi and Bartho, Kathrin and Gr{\"a}bner, Olivia and Sefkow, Michael and Darbre, Tamis and Reymond, Jean-Louis}, title = {Bridged bicyclic peptides as potential drug scaffolds}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-81239}, year = {2015}, abstract = {Double cyclization of short linear peptides obtained by solid phase peptide synthesis was used to prepare bridged bicyclic peptides (BBPs) corresponding to the topology of bridged bicyclic alkanes such as norbornane. Diastereomeric norbornapeptides were investigated by 1H-NMR, X-ray crystallography and CD spectroscopy and found to represent rigid globular scaffolds stabilized by intramolecular backbone hydrogen bonds with scaffold geometries determined by the chirality of amino acid residues and sharing structural features of β-turns and α-helices. Proteome profiling by capture compound mass spectrometry (CCMS) led to the discovery of the norbornapeptide 27c binding selectively to calmodulin as an example of a BBP protein binder. This and other BBPs showed high stability towards proteolytic degradation in serum.}, language = {en} } @book{BuddrusSchmidt2015, author = {Buddrus, Joachim and Schmidt, Bernd}, title = {Grundlagen der organischen Chemie}, edition = {5., {\"u}berarb. und aktualisierte Aufl.}, publisher = {de Gruyter}, address = {Berlin}, isbn = {978-3-11-030559-3}, publisher = {Universit{\"a}t Potsdam}, pages = {946}, year = {2015}, language = {de} } @article{MeyerRaberEbertetal.2015, author = {Meyer, S. and Raber, G. and Ebert, Franziska and Leffers, L. and M{\"u}ller, Sandra Marie and Taleshi, M. S. and Francesconi, Kevin A. and Schwerdtle, Tanja}, title = {In vitro toxicological characterisation of arsenic-containing fatty acids and three of their metabolites}, series = {Toxicology research}, volume = {5}, journal = {Toxicology research}, number = {4}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2045-4538}, doi = {10.1039/c5tx00122f}, pages = {1289 -- 1296}, year = {2015}, abstract = {Arsenic-containing fatty acids are a group of fat-soluble arsenic species (arsenolipids) which are present in marine fish and other seafood. Recently, it has been shown that arsenic-containing hydrocarbons, another group of arsenolipids, exert toxicity in similar concentrations comparable to arsenite although the toxic modes of action differ. Hence, a risk assessment of arsenolipids is urgently needed. In this study the cellular toxicity of a saturated (AsFA 362) and an unsaturated (AsFA 388) arsenic-containing fatty acid and three of their proposed metabolites (DMAV, DMAPr and thio-DMAPr) were investigated in human liver cells (HepG2). Even though both arsenic-containing fatty acids were less toxic as compared to arsenic-containing hydrocarbons and arsenite, significant effects were observable at μM concentrations. DMAV causes effects in a similar concentration range and it could be seen that it is metabolised to its highly toxic thio analogue thio-DMAV in HepG2 cells. Nevertheless, DMAPr and thio-DMAPr did not exert any cytotoxicity. In summary, our data indicate that risks to human health related to the presence of arsenic-containing fatty acids in marine food cannot be excluded. This stresses the need for a full in vitro and in vivo toxicological characterisation of these arsenolipids.}, language = {en} } @misc{MeyerRaberEbertetal.2015, author = {Meyer, S. and Raber, G. and Ebert, Franziska and Leffers, L. and M{\"u}ller, Sandra Marie and Taleshi, M. S. and Francesconi, Kevin A. and Schwerdtle, Tanja}, title = {In vitro toxicological characterisation of arsenic-containing fatty acids and three of their metabolites}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-82008}, year = {2015}, abstract = {Arsenic-containing fatty acids are a group of fat-soluble arsenic species (arsenolipids) which are present in marine fish and other seafood. Recently, it has been shown that arsenic-containing hydrocarbons, another group of arsenolipids, exert toxicity in similar concentrations comparable to arsenite although the toxic modes of action differ. Hence, a risk assessment of arsenolipids is urgently needed. In this study the cellular toxicity of a saturated (AsFA 362) and an unsaturated (AsFA 388) arsenic-containing fatty acid and three of their proposed metabolites (DMAV, DMAPr and thio-DMAPr) were investigated in human liver cells (HepG2). Even though both arsenic-containing fatty acids were less toxic as compared to arsenic-containing hydrocarbons and arsenite, significant effects were observable at μM concentrations. DMAV causes effects in a similar concentration range and it could be seen that it is metabolised to its highly toxic thio analogue thio-DMAV in HepG2 cells. Nevertheless, DMAPr and thio-DMAPr did not exert any cytotoxicity. In summary, our data indicate that risks to human health related to the presence of arsenic-containing fatty acids in marine food cannot be excluded. This stresses the need for a full in vitro and in vivo toxicological characterisation of these arsenolipids.}, language = {en} } @article{RoderHille2015, author = {Roder, Phillip and Hille, Carsten}, title = {A Multifunctional Frontloading Approach for Repeated Recycling of a Pressure-Controlled AFM Micropipette}, series = {PLoS ONE}, volume = {10}, journal = {PLoS ONE}, number = {12}, publisher = {Public Library of Science}, address = {Lawrence, Kan.}, issn = {1932-6203}, doi = {10.1371/journal.pone.0144157}, year = {2015}, abstract = {Fluid force microscopy combines the positional accuracy and force sensitivity of an atomic force microscope (AFM) with nanofluidics via a microchanneled cantilever. However, adequate loading and cleaning procedures for such AFM micropipettes are required for various application situations. Here, a new frontloading procedure is described for an AFM micropipette functioning as a force- and pressure-controlled microscale liquid dispenser. This frontloading procedure seems especially attractive when using target substances featuring high costs or low available amounts. Here, the AFM micropipette could be filled from the tip side with liquid from a previously applied droplet with a volume of only a few μL using a short low-pressure pulse. The liquid-loaded AFM micropipettes could be then applied for experiments in air or liquid environments. AFM micropipette frontloading was evaluated with the well-known organic fluorescent dye rhodamine 6G and the AlexaFluor647-labeled antibody goat anti-rat IgG as an example of a larger biological compound. After micropipette usage, specific cleaning procedures were tested. Furthermore, a storage method is described, at which the AFM micropipettes could be stored for a few hours up to several days without drying out or clogging of the microchannel. In summary, the rapid, versatile and cost-efficient frontloading and cleaning procedure for the repeated usage of a single AFM micropipette is beneficial for various application situations from specific surface modifications through to local manipulation of living cells, and provides a simplified and faster handling for already known experiments with fluid force microscopy.}, language = {en} } @misc{RoderHille2015, author = {Roder, Phillip and Hille, Carsten}, title = {A Multifunctional Frontloading Approach for Repeated Recycling of a Pressure-Controlled AFM Micropipette}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-86592}, year = {2015}, abstract = {Fluid force microscopy combines the positional accuracy and force sensitivity of an atomic force microscope (AFM) with nanofluidics via a microchanneled cantilever. However, adequate loading and cleaning procedures for such AFM micropipettes are required for various application situations. Here, a new frontloading procedure is described for an AFM micropipette functioning as a force- and pressure-controlled microscale liquid dispenser. This frontloading procedure seems especially attractive when using target substances featuring high costs or low available amounts. Here, the AFM micropipette could be filled from the tip side with liquid from a previously applied droplet with a volume of only a few μL using a short low-pressure pulse. The liquid-loaded AFM micropipettes could be then applied for experiments in air or liquid environments. AFM micropipette frontloading was evaluated with the well-known organic fluorescent dye rhodamine 6G and the AlexaFluor647-labeled antibody goat anti-rat IgG as an example of a larger biological compound. After micropipette usage, specific cleaning procedures were tested. Furthermore, a storage method is described, at which the AFM micropipettes could be stored for a few hours up to several days without drying out or clogging of the microchannel. In summary, the rapid, versatile and cost-efficient frontloading and cleaning procedure for the repeated usage of a single AFM micropipette is beneficial for various application situations from specific surface modifications through to local manipulation of living cells, and provides a simplified and faster handling for already known experiments with fluid force microscopy.}, language = {en} } @misc{MegowRoehrSchmidtamBuschetal.2015, author = {Megow, J{\"o}rg and R{\"o}hr, Merle I. S. and Schmidt am Busch, Marcel and Renger, Thomas and Mitrić, Roland and Kirstein, Stefan and Rabe, J{\"u}rgen P. and May, Volkhard}, title = {Site-dependence of van der Waals interaction explains exciton spectra of double-walled tubular J-aggregates}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-79978}, pages = {6741 -- 6747}, year = {2015}, abstract = {The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.}, language = {en} } @article{MegowRoehrSchmidtamBuschetal.2015, author = {Megow, J{\"o}rg and R{\"o}hr, Merle I. S. and Schmidt am Busch, Marcel and Renger, Thomas and Mitrić, Roland and Kirstein, Stefan and Rabe, J{\"u}rgen P. and May, Volkhard}, title = {Site-dependence of van der Waals interaction explains exciton spectra of double-walled tubular J-aggregates}, series = {Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies}, volume = {17}, journal = {Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies}, number = {10}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9084}, doi = {10.1039/c4cp05945j}, pages = {6741 -- 6747}, year = {2015}, abstract = {The simulation of the optical properties of supramolecular aggregates requires the development of methods, which are able to treat a large number of coupled chromophores interacting with the environment. Since it is currently not possible to treat large systems by quantum chemistry, the Frenkel exciton model is a valuable alternative. In this work we show how the Frenkel exciton model can be extended in order to explain the excitonic spectra of a specific double-walled tubular dye aggregate explicitly taking into account dispersive energy shifts of ground and excited states due to van der Waals interaction with all surrounding molecules. The experimentally observed splitting is well explained by the site-dependent energy shift of molecules placed at the inner or outer side of the double-walled tube, respectively. Therefore we can conclude that inclusion of the site-dependent dispersive effect in the theoretical description of optical properties of nanoscaled dye aggregates is mandatory.}, language = {en} } @misc{HildebrandLaschewskyWischerhoff2015, author = {Hildebrand, Viet and Laschewsky, Andr{\´e} and Wischerhoff, Erik}, title = {Modulating the solubility of zwitterionic poly((3- methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-103040}, pages = {731 -- 740}, year = {2015}, abstract = {Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition-fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D2O than in H2O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass. Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments.}, language = {en} } @misc{PapeWessigBrunner2015, author = {Pape, Simon and Wessig, Pablo and Brunner, Heiko}, title = {A new and environmentally benign synthesis of aroylguanidines using iron trichloride}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102720}, pages = {101408 -- 101411}, year = {2015}, abstract = {A new synthetic approach for the guanylation of aroylthioureas using iron trichloride is presented. Our synthetic method distinguishes itself by benign reaction conditions, low costs and a broad product spectrum. The scope of the reaction and calorimetric studies are described.}, language = {en} } @misc{KumkeKlier2015, author = {Kumke, Michael Uwe and Klier, Dennis Tobias}, title = {Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102677}, pages = {67149 -- 67156}, year = {2015}, abstract = {In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP.}, language = {en} } @article{IrunguAdipoOrwaetal.2015, author = {Irungu, Beatrice N. and Adipo, Nicholas and Orwa, Jennifer A. and Kimani, Francis and Heydenreich, Matthias and Midiwo, Jacob O. and Bjoremark, Per Martin and Hakansson, Mikael and Yenesew, Abiy and Erdelyi, Mate}, title = {Antiplasmodial and cytotoxic activities of the constituents of Turraea robusta and Turraea nilotica}, series = {Journal of ethnopharmacology : an interdisciplinary journal devoted to bioscientific research on indigenous drugs}, volume = {174}, journal = {Journal of ethnopharmacology : an interdisciplinary journal devoted to bioscientific research on indigenous drugs}, publisher = {Elsevier}, address = {Clare}, issn = {0378-8741}, doi = {10.1016/j.jep.2015.08.039}, pages = {419 -- 425}, year = {2015}, abstract = {Ethnopharmacological relevance: Turraea robusta and Turraea nilotica are African medicinal plants used for the treatment of a wide variety of diseases, including malaria. The genus Turraea is rich in limonoids and other triterpenoids known to possess various biological activities. Materials and methods: From the stem bark of T. robusta six compounds, and from various parts of T nilotica eleven compounds were isolated by the use of a combination of chromatographic techniques. The structures of the isolated compounds were elucidated using NMR and MS, whilst the relative configuration of one of the isolated compounds, toonapubesin F, was established by X-ray crystallography. The antiplasmodial activities of the crude extracts and the isolated constituents against the D6 and W2 strains of Plasmodium falciparum were determined using the semiautomated micro dilution technique that measures the ability of the extracts to inhibit the incorporation of (G-H-3, where G is guanine) hypoxanthine into the malaria parasite. The cytotoxicity of the crude extracts and their isolated constituents was evaluated against the mammalian cell lines African monkey kidney (vero), mouse breast cancer (4T1) and human larynx carcinoma (HEp2). Results: The extracts showed good to moderate antiplasmodial activities, where the extract of the stem bark of T. robusta was also cytotoxic against the 4T1 and the HEp2 cells (IC50 < 10 mu g/ml). The compounds isolated from these extracts were characterized as limonoids, protolimonoids and phytosterol glucosides. These compounds showed good to moderate activities with the most active one being azadironolide, IC50 2.4 +/- 0.03 mu M and 1.1 +/- 0.01 mu M against the D6 and W2 strains of Plasmodium falciparum, respectively; all other compounds possessed IC50 14.4-40.5 mu M. None of the compounds showed significant cytotoxicity against vero cells, yet four of them were toxic against the 4T1 and HEp2 cancer cell lines with piscidinol A having IC50 8.0 +/- 0.03 and 8.4 +/- 0.01 mu M against the 4T1 and HEp2 cells, respectively. Diacetylation of piscidinol A resulted in reduced cytotoxicity. Conclusion: From the medicinal plants T. robusta and T. nilotica, twelve compounds were isolated and characterized; two of the isolated compounds, namely 11-epi-toonacilin and azadironolide showed good antiplasmodial activity with the highest selectivity indices. (C) 2015 The Authors. Published by Elsevier Ireland Ltd.}, language = {en} } @article{PrimusMenskiYesteetal.2015, author = {Primus, Philipp-Alexander and Menski, Antonia and Yeste, Maria Pilar and Cauqui, Miguel Angel and Kumke, Michael Uwe}, title = {Fluorescence Line-Narrowing Spectroscopy as a Tool to Monitor Phase Transitions and Phase Separation in Efficient Nanocrystalline CexZr1-xO2:Eu3+ Catalyst Materials}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {119}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {19}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b01271}, pages = {10682 -- 10692}, year = {2015}, abstract = {Despite the wide range of industrial applications for ceria-zirconia mixed oxides (CexZr1-xO2), the complex correlation between their atomic structure and catalytic performance is still under debate. Catalytically interesting CexZr1-xO2 nanomaterials can form homogeneous solid solutions and, depending on the composition, show phase separation under the formation of small domains. The characterization of homogeneity and atomic structure of these materials remains a major challenge. High-resolution emission spectroscopy recorded under cryogenic conditions using Eu3+ as a structural probe in doped CeZrO2 nanoparticles offers an effective way to identify the different atomic environments of the Eu3+ dopants and, subsequently, to monitor structural parameters of the ceria-zirconia mixed oxides. It is found that, in stoichiometric CeZrO2:Eu3+, phase separation occurs at elevated temperatures beginning with the gradual formation of (pseudo)cubic crystallites in the amorphous materials at 500 degrees C and a sudden phase separation into tetragonal, zirconia-rich and cubic, ceria-rich domains over 900 degrees C. The presented technique allows us to easily monitor subtle changes even in amorphous, high surface area samples, yielding structural information not accessible by conventional techniques such as X-ray diffraction (XRD) and Raman. Moreover, in reference experiments investigating the reducibility of largely unordered Ce0.2Zr0.8O2:Eu3+, the main reduction peak in temperature-programmed reduction measurements appeared at exceptionally low temperatures below 200 degrees C, thus suggesting the outstanding potential of this oxide to activate catalytic oxidation reactions. This effect was found to be dependent on the amount of Eu3+ dopant introduced into the CeZrO2 matrix as well as to be connected to the atomic structure of the catalyst material.}, language = {en} } @article{PerezAnesRodriguesCaminadeetal.2015, author = {Perez-Anes, Alexandra and Rodrigues, Fernanda and Caminade, Anne-Marie and Stefaniu, Cristina and Tiersch, Brigitte and Turrin, Cedric-Olivier and Blanzat, Muriel}, title = {Influence of structural parameters on the self-association properties of anti-HIV catanionic dendrimers}, series = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, volume = {16}, journal = {ChemPhysChem : a European journal of chemical physics and physical chemistry}, number = {16}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1439-4235}, doi = {10.1002/cphc.201500484}, pages = {3433 -- 3437}, year = {2015}, abstract = {The self-association properties of anti-HIV catanionic dendrimers as multivalent galactosylceramide (GalCer)-derived inhibitors are presented. The study was designed to elucidate the origin of the relatively high cytotoxicity values of these antiHIV catanionic dendrimers, which have previously been found to exhibit in vitro anti-HIV activity in the submicromolar range. The physicochemical properties of these catanionic dendrimers were studied to tentatively correlate the structural parameters with self-association and biological properties. We can conclude from this study that the absence of correlation between the hydrophobicity and the cytotoxicity of the catanionic systems could be explained by the partial segregation of the different partners of the catanionic entities.}, language = {en} } @misc{KlaperWessigLinker2015, author = {Klaper, M. and Wessig, Pablo and Linker, Torsten}, title = {Base catalysed decomposition of anthracene endoperoxide}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-89676}, pages = {1210 -- 1213}, year = {2015}, abstract = {Catalytic amounts of a weak base are sufficient to induce the decomposition of anthracene endoperoxides to anthraquinone. The mechanism has been elucidated by isolation of intermediates in combination with DFT calculations. The whole process is suitable for the convenient generation of hydrogen peroxide under very mild conditions.}, language = {en} } @article{RadingSandmannSteupetal.2015, author = {Rading, M. Michael and Sandmann, Michael and Steup, Martin and Chiarugi, Davide and Valleriani, Angelo}, title = {Weak correlation of starch and volume in synchronized photosynthetic cells}, series = {Physical review : E, Statistical, nonlinear and soft matter physics}, volume = {91}, journal = {Physical review : E, Statistical, nonlinear and soft matter physics}, number = {1}, publisher = {American Physical Society}, address = {College Park}, issn = {1539-3755}, doi = {10.1103/PhysRevE.91.012711}, pages = {11}, year = {2015}, abstract = {In cultures of unicellular algae, features of single cells, such as cellular volume and starch content, are thought to be the result of carefully balanced growth and division processes. Single-cell analyses of synchronized photoautotrophic cultures of the unicellular alga Chlamydomonas reinhardtii reveal, however, that the cellular volume and starch content are only weakly correlated. Likewise, other cell parameters, e.g., the chlorophyll content per cell, are only weakly correlated with cell size. We derive the cell size distributions at the beginning of each synchronization cycle considering growth, timing of cell division and daughter cell release, and the uneven division of cell volume. Furthermore, we investigate the link between cell volume growth and starch accumulation. This work presents evidence that, under the experimental conditions of light-dark synchronized cultures, the weak correlation between both cell features is a result of a cumulative process rather than due to asymmetric partition of biomolecules during cell division. This cumulative process necessarily limits cellular similarities within a synchronized cell population.}, language = {en} } @unpublished{MegowKoerzdoerferRengeretal.2015, author = {Megow, J{\"o}rg and K{\"o}rzd{\"o}rfer, Thomas and Renger, Thomas and Sparenberg, Mino and Blumstengel, Sylke and May, Volkhard}, title = {Reply to "Comment on 'Calculating Optical Absorption Spectra of Thin Polycrystalline Organic Films: Structural Disorder and Site-Dependent van der Waals Interaction"}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {119}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {32}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b05536}, pages = {18818 -- 18820}, year = {2015}, language = {en} } @article{MegowKoerzdoerferRengeretal.2015, author = {Megow, J{\"o}rg and K{\"o}rzd{\"o}rfer, Thomas and Renger, Thomas and Sparenberg, Mino and Blumstengel, Sylke and Henneberger, Fritz and May, Volkhard}, title = {Calculating Optical Absorption Spectra of Thin Polycrystalline Organic Films: Structural Disorder and Site-Dependent van der Waals Interaction}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {119}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {10}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b01587}, pages = {5747 -- 5751}, year = {2015}, abstract = {We propose a new approach for calculating the change of the absorption spectrum of a molecule when moved from the gas phase to a crystalline morphology. The so-called gas-to-crystal shift Delta epsilon(m) is mainly caused by dispersion effects and depends sensitively on the molecules specific position in the nanoscopic setting. Using an extended dipole approximation, we are able to divide Delta epsilon(m)= -QW(m) in two factors, where Q depends only on the molecular species and accounts for all nonresonant electronic transitions contributing to the dispersion while W-m is a geometry factor expressing the site dependence of the shift in a given molecular structure. The ability of our approach to predict absorption spectra is demonstrated using the example of polycrystalline films of 3,4,9,10-perylenetetracarboxylic diimide (PTCDI).}, language = {en} } @article{WessigBudachThuenemann2015, author = {Wessig, Pablo and Budach, Dennis B. and Th{\"u}nemann, Andreas F.}, title = {Dendrimers with Oligospiroketal (OSK) Building Blocks: Synthesis and Properties}, series = {Chemistry - a European journal}, volume = {21}, journal = {Chemistry - a European journal}, number = {29}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201501386}, pages = {10466 -- 10471}, year = {2015}, abstract = {The development of novel dendrimers containing oligospiroketal (OSK) rods as building blocks is described. The linkage between the core unit (CU), branching units (BU), and OSK rods relies on the CuAAC reaction between terminal alkynes and azides. Two different strategies of dendrimer synthesis were investigated and it was found that the convergent approach is clearly superior to the divergent one. SAXS measurements and MD simulations indicate that the obtained dendrimer features a globular structure with very low density. Obviously, the OSK rods stabilize a rather loose mass-fractal structure.}, language = {en} } @phdthesis{Fettkenhauer2015, author = {Fettkenhauer, Christian}, title = {Ionothermale Synthese funktioneller Kohlenstoffnitrid basierter Materialien}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-78087}, school = {Universit{\"a}t Potsdam}, pages = {xii, 123}, year = {2015}, abstract = {Die Doktorarbeit behandelt die Synthese Kohlenstoffnitrid basierter Materialien in eutektischen Mischungen bivalenter Metallchloride. Der Fokus liegt dabei auf ZnCl2-, SnCl2- und CoCl2-haltigen eutektischen Mischungen, in denen die Kondensation gebr{\"a}uchlicher organischer Precursoren durchgef{\"u}hrt wird. Im Rahmen dessen wird untersucht wie durch die Reaktionsf{\"u}hrung in Salzschmelzen unterschiedlicher Lewis-Acidit{\"a}t, neben der Molek{\"u}lstruktur andere charakteristische Eigenschaften, wie Morphologie, Kristallinit{\"a}t und spezifische Oberfl{\"a}chen, der Materialien kontrolliert werden k{\"o}nnen. Dar{\"u}ber hinaus werden die optischen Eigenschaften der Materialien er{\"o}rtert und in diesem Zusammenhang die Eignung als Photokatalysatoren f{\"u}r den oxidativen Abbau organischer Farbstoffe und f{\"u}r die photokatalytische Wasserreduktion bzw. -oxidation untersucht. Zus{\"a}tzlich wird gezeigt, wie im System LiCl/KCl in einem einstufigen Prozess edelmetallfreie Kohlenstoffnitrid Komposite zur photokatalytischen Wasserreduktion hergestellt werden k{\"o}nnen.}, language = {de} } @phdthesis{Grygiel2015, author = {Grygiel, Konrad}, title = {Poly(ionic liquid) stabilizers and new synthetic approaches}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-80367}, school = {Universit{\"a}t Potsdam}, pages = {vii, 126}, year = {2015}, abstract = {The main focus of the present thesis was to investigate the stabilization ability of poly(ionic liquid)s (PILs) in several examples as well as develop novel chemical structures and synthetic routes of PILs. The performed research can be specifically divided into three parts that include synthesis and application of hybrid material composed of PIL and cellulose nanofibers (CNFs), thiazolium-containing PILs, and main-chain imidazolium-type PILs. In the first chapter, a vinylimidazolium-type IL was polymerized in water in the presence of CNFs resulting in the in situ electrostatic grafting of polymeric chains onto the surface of CNFs. The synthesized hybrid material merged advantages of its two components, that is, superior mechanical strength of CNFs and anion dependent solution properties of PILs. In contrast to unmodified CNFs, the hybrid could be stabilized and processed in organic solvents enabling its application as reinforcing agent for porous polyelectrolyte membranes. In the second part, PILs and ionic polymers containing two types of thiazolium repeating units were synthesized. Such polymers displayed counterion dependent thermal stability and solubility in organic solvents of various dielectric constants. This new class of PILs was tested as stabilizers and phase transfer agents for carbon nanotubes in aqueous and organic media, and as binder materials to disperse electroactive powders and carbon additives in solid electrode in lithium-ion batteries. The incorporation of S and N atoms into the polymeric structures make such PILs also potential precursors for S, N - co-doped carbons. In the last chapter, reactants originating from biomass were successfully harnessed to synthesize main-chain imidazolium-type PILs. An imidazolium-type diester IL obtained via a modified Debus-Radziszewski reaction underwent transesterification with diol in a polycondensation reaction. This yielded a polyester-type PIL which CO2 sorption properties were investigated. In the next step, the modified Debus-Radziszewski reaction was further applied to synthesize main-chain PILs according to a convenient, one-step protocol, using water as a green solvent and simple organic molecules as reagents. Depending on the structure of the employed diamine, the synthesized PILs after anion exchange showed superior thermal stability with unusually high carbonization yields. Overall, the outcome of these studies will actively contribute to the current research on PILs by introducing novel PIL chemical structures, improved synthetic routes, and new examples of stabilized materials. The synthesis of main-chain imidazolium-type PILs by a modified Debus-Radziszewski reaction is of a special interest for the future work on porous ionic liquid networks as well as colloidal PIL nanoparticles.}, language = {en} } @misc{VacogneBrosnanMasicetal.2015, author = {Vacogne, Charlotte D. and Brosnan, Sarah M. and Masic, Admir and Schlaad, Helmut}, title = {Fibrillar gels via the self-assembly of poly(L-glutamate)-based statistical copolymers}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102289}, pages = {5040 -- 5052}, year = {2015}, abstract = {Polypeptides having secondary structures often undergo self-assembly which can extend over multiple length scales. Poly(γ-benzyl-L-glutamate) (PBLG), for example, folds into α-helices and forms physical organogels, whereas poly(L-glutamic acid) (PLGA at acidic pH) or poly(L-glutamate) (PLG at neutral/basic pH) do not form hydrogels. We explored the gelation of modified PBLG and investigated the deprotection of the carboxylic acid moieties in such gels to yield unique hydrogels. This was accomplished through photo-crosslinking gelation of poly(γ-benzyl-L-glutamate-co-allylglycine) statistical copolymers in toluene, tetrahydrofuran, and 1,4-dioxane. Unlike most polymer-based chemical gels, our gels were prepared from dilute solutions (<20 g L-1, i.e., <2\% w/v) of low molar mass polymers. Despite such low concentrations and molar masses, our dioxane gels showed high mechanical stability and little shrinkage; remarkably, they also exhibited a porous fibrillar network. Deprotection of the carboxylic acid moieties in dioxane gels yielded pH responsive and highly absorbent PLGA/PLG-based hydrogels (swelling ratio of up to 87), while preserving the network structure, which is an unprecedented feature in the context of crosslinked PLGA gels. These outstanding properties are highly attractive for biomedical materials.}, language = {en} } @misc{TasiorBaldDeperasińskaetal.2015, author = {Tasior, Mariusz and Bald, Ilko and Deperasińska, Irena and Cywiński, Piotr J. and Gryko, Daniel T.}, title = {An internal charge transfer-dependent solvent effect in V-shaped azacyanines}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102704}, pages = {11714 -- 11720}, year = {2015}, abstract = {New V-shaped non-centrosymmetric dyes, possessing a strongly electron-deficient azacyanine core, have been synthesized based on a straightforward two-step approach. The key step in this synthesis involves palladium-catalysed cross-coupling of dibromo-N,N′-methylene-2,2′-azapyridinocyanines with arylacetylenes. The resulting strongly polarized π-expanded heterocycles exhibit green to orange fluorescence and they strongly respond to changes in solvent polarity. We demonstrate that differently electron-donating peripheral groups have a significant influence on the internal charge transfer, hence on the solvent effect and fluorescence quantum yield. TD-DFT calculations confirm that, in contrast to the previously studied bis(styryl)azacyanines, the proximity of S1 and T2 states calculated for compounds bearing two 4-N,N-dimethylaminophenylethynyl moieties establishes good conditions for efficient intersystem crossing and is responsible for its low fluorescence quantum yield. Non-linear properties have also been determined for new azacyanines and the results show that depending on peripheral groups, the synthesized dyes exhibit small to large two-photon absorption cross sections reaching 4000 GM.}, language = {en} } @misc{VacogneSchlaad2015, author = {Vacogne, Charlotte D. and Schlaad, Helmut}, title = {Primary ammonium/tertiary amine-mediated controlled ring opening polymerisation of amino acid N-carboxyanhydrides}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-102718}, pages = {15645 -- 15648}, year = {2015}, abstract = {Stable commercial primary ammonium chlorides were combined with tertiary amines to initiate the controlled ring opening polymerisation of amino acid N-carboxyanhydrides to yield polypeptides with defined end group structure, predetermined molar mass and narrow molar mass distribution.}, language = {en} } @article{OlejkoCywinskiBald2015, author = {Olejko, Lydia and Cywinski, Piotr J. and Bald, Ilko}, title = {Ion-Selective formation of a guanine quadruplex on DNA origami structures}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {54}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {2}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201409278}, pages = {673 -- 677}, year = {2015}, abstract = {DNA origami nanostructures are a versatile tool that can be used to arrange functionalities with high local control to study molecular processes at a single-molecule level. Here, we demonstrate that DNA origami substrates can be used to suppress the formation of specific guanine (G) quadruplex structures from telomeric DNA. The folding of telomeres into G-quadruplex structures in the presence of monovalent cations (e.g. Na+ and K+) is currently used for the detection of K+ ions, however, with insufficient selectivity towards Na+. By means of FRET between two suitable dyes attached to the 3- and 5-ends of telomeric DNA we demonstrate that the formation of G-quadruplexes on DNA origami templates in the presence of sodium ions is suppressed due to steric hindrance. Hence, telomeric DNA attached to DNA origami structures represents a highly sensitive and selective detection tool for potassium ions even in the presence of high concentrations of sodium ions.}, language = {en} } @article{GuietGoebelKlinganetal.2015, author = {Guiet, Amandine and Goebel, Caren and Klingan, Katharina and Lublow, Michael and Reier, Tobias and Vainio, Ulla and Kraehnert, Ralph and Schlaad, Helmut and Strasser, Peter and Zaharieva, Ivelina and Dau, Holger and Driess, Matthias and Polte, Joerg and Fischer, Anna}, title = {Hydrophobic Nanoreactor Soft-Templating: A Supramolecular Approach to Yolk@Shell Materials}, series = {Advanced functional materials}, volume = {25}, journal = {Advanced functional materials}, number = {39}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.201502388}, pages = {6228 -- 6240}, year = {2015}, abstract = {Due to their unique morphology-related properties, yolk@shell materials are promising materials for catalysis, drug delivery, energy conversion, and storage. Despite their proven potential, large-scale applications are however limited due to demanding synthesis protocols. Overcoming these limitations, a simple soft-templated approach for the one-pot synthesis of yolk@shell nanocomposites and in particular of multicore metal nanoparticle@metal oxide nanostructures (M-NP@MOx) is introduced. The approach here, as demonstrated for Au-NP@ITOTR (ITOTR standing for tin-rich ITO), relies on polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) inverse micelles as two compartment nanoreactor templates. While the hydrophilic P4VP core incorporates the hydrophilic metal precursor, the hydrophobic PS corona takes up the hydrophobic metal oxide precursor. As a result, interfacial reactions between the precursors can take place, leading to the formation of yolk@shell structures in solution. Once calcined these micelles yield Au-NP@ITOTR nanostructures, composed of multiple 6 nm sized Au NPs strongly anchored onto the inner surface of porous 35 nm sized ITOTR hollow spheres. Although of multicore nature, only limited sintering of the metal nanoparticles is observed at high temperatures (700 degrees C). In addition, the as-synthesized yolk@shell structures exhibit high and stable activity toward CO electrooxidation, thus demonstrating the applicability of our approach for the design of functional yolk@shell nanocatalysts.}, language = {en} } @article{VogelRackwitzSchuermanetal.2015, author = {Vogel, Stefanie and Rackwitz, Jenny and Schuerman, Robin and Prinz, Julia and Milosavljevic, Aleksandar R. and Refregiers, Matthieu and Giuliani, Alexandre and Bald, Ilko}, title = {Using DNA origami nanostructures to determine absolute cross sections for UV photon-induced DNA strand breakage}, series = {The journal of physical chemistry letters}, volume = {6}, journal = {The journal of physical chemistry letters}, number = {22}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.5b02238}, pages = {4589 -- 4593}, year = {2015}, abstract = {We have characterized ultraviolet (UV) photon-induced DNA strand break processes by determination of absolute cross sections for photoabsorption and for sequence-specific DNA single strand breakage induced by photons in an energy range from 6.50 to 8.94 eV. These represent the lowest-energy photons able to induce DNA strand breaks. Oligonudeotide targets are immobilized on a UV transparent substrate in controlled quantities through attachment to DNA origami templates. Photon-induced dissociation of single DNA strands is visualized and quantified using atomic force microscopy. The obtained quantum yields for strand breakage vary between 0.06 and 0.5, indicating highly efficient DNA strand breakage by UV photons, which is clearly dependent on the photon energy. Above the ionization threshold strand breakage becomes clearly the dominant form of DNA radiation damage, which is then also dependent on the nucleotide sequence.}, language = {en} } @article{SeckerBrosnanLimbergetal.2015, author = {Secker, Christian and Brosnan, Sarah M. and Limberg, Felix Rolf Paul and Braun, Ulrike and Trunk, Matthias and Strauch, Peter and Schlaad, Helmut}, title = {Thermally Induced Crosslinking of Poly(N-Propargyl Glycine)}, series = {Macromolecular chemistry and physics}, volume = {216}, journal = {Macromolecular chemistry and physics}, number = {21}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1352}, doi = {10.1002/macp.201500223}, pages = {2080 -- 2085}, year = {2015}, abstract = {As polypeptoids become increasingly popular, they present a more soluble and processable alternative to natural and synthetic polypeptides; the breadth of their potential functionality slowly comes into focus. This report analyzes the ability of an alkyne-functionalized polypeptoid, poly(N-propargyl glycine), to crosslink upon heating. The crosslinking process is analyzed by thermal analysis (differential scanning calorimetry and thermogravimetric analysis), Fourier-transform infrared, electron paramagnetic resonance, and solid-state NMR spectroscopy. While a precise mechanism cannot be confidently assigned, it is clear that the reaction proceeds by a radical mechanism that exclusively involves the alkyne functionality, which, upon crosslinking, yields alkene and aromatic products.}, language = {en} } @article{MadaanRomriellTuscanoetal.2015, author = {Madaan, Nitesh and Romriell, Naomi and Tuscano, Joshua and Schlaad, Helmut and Linford, Matthew R.}, title = {Introduction of thiol moieties, including their thiol-ene reactions and air oxidation, onto polyelectrolyte multilayer substrates}, series = {Journal of colloid and interface science}, volume = {459}, journal = {Journal of colloid and interface science}, publisher = {Elsevier}, address = {San Diego}, issn = {0021-9797}, doi = {10.1016/j.jcis.2015.08.017}, pages = {199 -- 205}, year = {2015}, language = {en} } @article{KoshkinaLangThiermannetal.2015, author = {Koshkina, Olga and Lang, Thomas and Thiermann, Raphael and Docter, Dominic and Stauber, Roland H. and Secker, Christian and Schlaad, Helmut and Weidner, Steffen and Mohr, Benjamin and Maskos, Michael and Bertin, Annabelle}, title = {Temperature-Triggered Protein Adsorption on Polymer-Coated Nanoparticles in Serum}, series = {Langmuir}, volume = {31}, journal = {Langmuir}, number = {32}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.5b00537}, pages = {8873 -- 8881}, year = {2015}, abstract = {The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mu m. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanopartides and proteins and the accumulation of nanoparticles in a targeted body region.}, language = {en} } @article{SeckerBrosnanLuxenhoferetal.2015, author = {Secker, Christian and Brosnan, Sarah M. and Luxenhofer, Robert and Schlaad, Helmut}, title = {Poly(alpha-Peptoid)s Revisited: Synthesis, Properties, and Use as Biomaterial}, series = {Macromolecular bioscience}, volume = {15}, journal = {Macromolecular bioscience}, number = {7}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-5187}, doi = {10.1002/mabi.201500023}, pages = {881 -- 891}, year = {2015}, abstract = {Polypeptoids have been of great interest in the polymer science community since the early half of the last century; however, they had been basically forgotten materials until the last decades in which they have enjoyed an exciting revival. In this mini-review, we focus on the recent developments in polypeptoid chemistry, with particular focus on polymers synthesized by the ring-opening polymerization (ROP) of amino acid N-carboxyanhydrides (NCAs). Specifically, we will review traditional monomer synthesis (such as Leuchs, Katchalski, and Kricheldorf) and recent advances in polymerization methods to yield both linear, cyclic, and functional polymers, solution and bulk thermal properties, and preliminary results on the use of polypeptoids as biomaterials (i.e immunogenicity, biodistribution, degradability, and drug delivery).}, language = {en} } @article{BrosnanSchlaadAntonietti2015, author = {Brosnan, Sarah M. and Schlaad, Helmut and Antonietti, Markus}, title = {Aqueous Self-Assembly of Purely Hydrophilic Block Copolymers into Giant Vesicles}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {54}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {33}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201502100}, pages = {9715 -- 9718}, year = {2015}, abstract = {Self-assembly of macromolecules is fundamental to life itself, and historically, these systems have been primitively mimicked by the development of amphiphilic systems, driven by the hydrophobic effect. Herein, we demonstrate that self-assembly of purely hydrophilic systems can be readily achieved with similar ease and success. We have synthesized double hydrophilic block copolymers from polysaccharides and poly(ethylene oxide) or poly(sarcosine) to yield high molar mass diblock copolymers through oxime chemistry. These hydrophilic materials can easily assemble into nanosized (<500nm) and microsized (>5m) polymeric vesicles depending on concentration and diblock composition. Because of the solely hydrophilic nature of these materials, we expect them to be extraordinarily water permeable systems that would be well suited for use as cellular mimics.}, language = {en} } @article{ZouSchlaad2015, author = {Zou, Hua and Schlaad, Helmut}, title = {Thermoresponsive PNIPAM/Silica Nanoparticles by Direct Photopolymerization in Aqueous Media}, series = {Journal of polymer science : A, Polymer chemistry}, volume = {53}, journal = {Journal of polymer science : A, Polymer chemistry}, number = {10}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0887-624X}, doi = {10.1002/pola.27593}, pages = {1260 -- 1267}, year = {2015}, abstract = {This article presents a simple and facile method to fabricate thermoresponsive polymer-grafted silica particles by direct surface-initiated photopolymerization of N-isopropylacrylamide (NIPAM). This method is based on silica particles bearing thiol functionalities, which are transformed into thiyl radicals by irradiation with UV light to initiate the polymerization of NIPAM in aqueous media at room temperature. The photopolymerization of NIPAM could be applied to smaller thiol-functionalized particles (approximate to 48 nm) as well as to larger particles (approximate to 692 nm). Hollow poly(NIPAM) capsules could be formed after etching away the silica cores from the composite particles. It is possible to produce tailor-made composite particles or capsules for particular applications by extending this approach to other vinyl monomers. (c) 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015, 53, 1260-1267}, language = {en} } @article{KedrackiFilippovGouretal.2015, author = {Kedracki, Dawid and Filippov, Sergey K. and Gour, Nidhi and Schlaad, Helmut and Nardin, Corinne}, title = {Formation of DNA-Copolymer Fibrils Through an Amyloid-Like Nucleation Polymerization Mechanism}, series = {Macromolecular rapid communications}, volume = {36}, journal = {Macromolecular rapid communications}, number = {8}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201400728}, pages = {768 -- 773}, year = {2015}, abstract = {Conjugation of a hydrophobic poly(2-oxazoline) bearing tertiary amide groups along its backbone with a short single stranded nucleotide sequence results in an amphiphilic comb/graft copolymer, which organizes in fibrils upon direct dissolution in water. Supported by circular dichroism, atomic force microscopy, transmission electron microscopy, and scattering data, fibrils are formed through inter- and intramolecular hydrogen bonding between hydrogen accepting amide groups along the polymer backbone and hydrogen donating nucleic acid grafts leading to the formation of hollow tubes.}, language = {en} } @article{VacogneBrosnanMasicetal.2015, author = {Vacogne, Charlotte D. and Brosnan, Sarah M. and Masic, Admir and Schlaad, Helmut}, title = {Fibrillar gels via the self-assembly of poly(L-glutamate)-based statistical copolymers}, series = {Polymer Chemistry}, volume = {6}, journal = {Polymer Chemistry}, number = {28}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1759-9954}, doi = {10.1039/c5py00491h}, pages = {5040 -- 5052}, year = {2015}, abstract = {Polypeptides having secondary structures often undergo self-assembly which can extend over multiple length scales. Poly(gamma-benzyl-L-glutamate) (PBLG), for example, folds into a-helices and forms physical organogels, whereas poly(L-glutamic acid) (PLGA at acidic pH) or poly(L-glutamate) (PLG at neutral/basic pH) do not form hydrogels. We explored the gelation of modified PBLG and investigated the deprotection of the carboxylic acid moieties in such gels to yield unique hydrogels. This was accomplished through photo-crosslinking gelation of poly(gamma-benzyl-L-glutamate-co-allylglycine) statistical copolymers in toluene, tetrahydrofuran, and 1,4-dioxane. Unlike most polymer-based chemical gels, our gels were prepared from dilute solutions (<20 g L-1, i.e., <2\% w/v) of low molar mass polymers. Despite such low concentrations and molar masses, our dioxane gels showed high mechanical stability and little shrinkage; remarkably, they also exhibited a porous fibrillar network. Deprotection of the carboxylic acid moieties in dioxane gels yielded pH responsive and highly absorbent PLGA/PLG-based hydrogels (swelling ratio of up to 87), while preserving the network structure, which is an unprecedented feature in the context of crosslinked PLGA gels. These outstanding properties are highly attractive for biomedical materials.}, language = {en} } @article{TritschlerBeckSchlaadetal.2015, author = {Tritschler, U. and Beck, F. and Schlaad, Helmut and C{\"o}lfen, Helmut}, title = {Electrochromic properties of self-organized multifunctional V2O5-polymer hybrid films}, series = {Journal of materials chemistry : C, Materials for optical and electronic devices}, volume = {3}, journal = {Journal of materials chemistry : C, Materials for optical and electronic devices}, number = {5}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-7526}, doi = {10.1039/c4tc02138j}, pages = {950 -- 954}, year = {2015}, abstract = {Bio-inspired V2O5-polymer hybrid films were prepared following a one-step self-organization procedure based on liquid crystal formation of organic and inorganic components. These materials were previously reported to exhibit advantageous mechanical properties, comparable to biomaterials, such as human bone and dentin. Here, we show that these hybrid films prepared via a fast and simple synthesis procedure have an additional function as an electrochromic material, exhibiting a long-term cycle stability under alternating potentials. The structures were found to remain intact without visible changes after more than hundred switching cycles and storing the devices for several weeks. Consequently, this multifunctional V2O5-polymer hybrid system shows great promise for various technical applications.}, language = {en} } @article{SeckerRobinsonSchlaad2015, author = {Secker, Christian and Robinson, Joshua W. and Schlaad, Helmut}, title = {Alkyne-X modification of polypeptoids}, series = {European polymer journal}, volume = {62}, journal = {European polymer journal}, publisher = {Elsevier}, address = {Oxford}, issn = {0014-3057}, doi = {10.1016/j.eurpolymj.2014.08.028}, pages = {394 -- 399}, year = {2015}, abstract = {Poly(N-propargyl glycine) (PNPG) can be readily prepared by ring-opening polymerization of N-propargyl glycine N-carboxyanhydride (NCA) and modified using various addition reactions such as copper catalyzed [3+2] cycloaddition of azide, radical (photo-)addition of thiol, nucleophilic addition of ethylene oxide, and thermal induced cross-linking. It is demonstrated that PNPG can serve as a modular platform to produce a bibliography of novel functional polypeptoid or pseudopeptide materials, including polypeptoid ionic liquids and graft copolymers.}, language = {en} } @article{VacogneSchlaad2015, author = {Vacogne, Charlotte D. and Schlaad, Helmut}, title = {Primary ammonium/tertiary amine-mediated controlled ring opening polymerisation of amino acid N-carboxyanhydrides}, series = {Chemical communications}, volume = {51}, journal = {Chemical communications}, number = {86}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1359-7345}, doi = {10.1039/c5cc06905j}, pages = {15645 -- 15648}, year = {2015}, abstract = {Stable commercial primary ammonium chlorides were combined with tertiary amines to initiate the controlled ring opening polymerisation of amino acid N-carboxyanhydrides to yield polypeptides with defined end group structure, predetermined molar mass and narrow molar mass distribution.}, language = {en} } @misc{NoechelReddyWangetal.2015, author = {N{\"o}chel, Ulrich and Reddy, Chaganti Srinivasa and Wang, Ke and Cui, Jing and Zizak, Ivo and Behl, Marc and Kratz, Karl and Lendlein, Andreas}, title = {Nanostructural changes in crystallizable controlling units determine the temperature-memory of polymers}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-81124}, pages = {8284 -- 8293}, year = {2015}, abstract = {Temperature-memory polymers remember the temperature, where they were deformed recently, enabled by broad thermal transitions. In this study, we explored a series of crosslinked poly[ethylene-co-(vinyl acetate)] networks (cPEVAs) comprising crystallizable polyethylene (PE) controlling units exhibiting a pronounced temperature-memory effect (TME) between 16 and 99 °C related to a broad melting transition (∼100 °C). The nanostructural changes in such cPEVAs during programming and activation of the TME were analyzed via in situ X-ray scattering and specific annealing experiments. Different contributions to the mechanism of memorizing high or low deformation temperatures (Tdeform) were observed in cPEVA, which can be associated to the average PE crystal sizes. At high deformation temperatures (>50 °C), newly formed PE crystals, which are established during cooling when fixing the temporary shape, dominated the TME mechanism. In contrast, at low Tdeform (<50 °C), corresponding to a cold drawing scenario, the deformation led preferably to a disruption of existing large crystals into smaller ones, which then fix the temporary shape upon cooling. The observed mechanism of memorizing a deformation temperature might enable the prediction of the TME behavior and the knowledge based design of other TMPs with crystallizable controlling units.}, language = {en} } @article{NoechelReddyWangetal.2015, author = {N{\"o}chel, Ulrich and Reddy, Chaganti Srinivasa and Wang, Ke and Cui, Jing and Zizak, Ivo and Behl, Marc and Kratz, Karl and Lendlein, Andreas}, title = {Nanostructural changes in crystallizable controlling units determine the temperature-memory of polymers}, series = {Journal of Materials Chemistry A, Materials for energy and sustainability}, volume = {16}, journal = {Journal of Materials Chemistry A, Materials for energy and sustainability}, number = {3}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-7488}, doi = {10.1039/c4ta06586g}, pages = {8284 -- 8293}, year = {2015}, abstract = {Temperature-memory polymers remember the temperature, where they were deformed recently, enabled by broad thermal transitions. In this study, we explored a series of crosslinked poly[ethylene-co-(vinyl acetate)] networks (cPEVAs) comprising crystallizable polyethylene (PE) controlling units exhibiting a pronounced temperature-memory effect (TME) between 16 and 99 °C related to a broad melting transition (∼100 °C). The nanostructural changes in such cPEVAs during programming and activation of the TME were analyzed via in situ X-ray scattering and specific annealing experiments. Different contributions to the mechanism of memorizing high or low deformation temperatures (Tdeform) were observed in cPEVA, which can be associated to the average PE crystal sizes. At high deformation temperatures (>50 °C), newly formed PE crystals, which are established during cooling when fixing the temporary shape, dominated the TME mechanism. In contrast, at low Tdeform (<50 °C), corresponding to a cold drawing scenario, the deformation led preferably to a disruption of existing large crystals into smaller ones, which then fix the temporary shape upon cooling. The observed mechanism of memorizing a deformation temperature might enable the prediction of the TME behavior and the knowledge based design of other TMPs with crystallizable controlling units.}, language = {en} } @article{WangKratzBehletal.2015, author = {Wang, Weiwei and Kratz, Karl and Behl, Marc and Yan, Wan and Liu, Yue and Xu, Xun and Baudis, Stefan and Li, Zhengdong and Kurtz, Andreas and Lendlein, Andreas and Ma, Nan}, title = {The interaction of adipose-derived human mesenchymal stem cells and polyether ether ketone}, series = {Clinical hemorheology and microcirculation : blood flow and vessels}, volume = {61}, journal = {Clinical hemorheology and microcirculation : blood flow and vessels}, number = {2}, publisher = {IOS Press}, address = {Amsterdam}, issn = {1386-0291}, doi = {10.3233/CH-152001}, pages = {301 -- 321}, year = {2015}, abstract = {Polyether ether ketone (PEEK) as a high-performance, thermoplastic implant material entered the field of medical applications due to its structural function and commercial availability. In bone tissue engineering, the combination of mesenchymal stem cells (MSCs) with PEEK implants may accelerate the bone formation and promote the osseointegration between the implant and the adjacent bone tissue. In this concept the question how PEEK influences the behaviour and functions of MSCs is of great interest. Here the cellular response of human adipose-derived MSCs to PEEK was evaluated and compared to tissue culture plate (TCP) as the reference material. Viability and morphology of cells were not altered when cultured on the PEEK film. The cells on PEEK presented a high proliferation activity in spite of a relatively lower initial cell adhesion rate. There was no significant difference on cell apoptosis and senescence between the cells on PEEK and TCP. The inflammatory cytokines and VEGF secreted by the cells on these two surfaces were at similar levels. The cells on PEEK showed up-regulated BMP2 and down-regulated BMP4 and BMP6 gene expression, whereas no conspicuous differences were observed in the committed osteoblast markers (BGLAP, COL1A1 and Runx2). With osteoinduction the cells on PEEK and TCP exhibited a similar osteogenic differentiation potential. Our results demonstrate the biofunctionality of PEEK for human MSC cultivation and differentiation. Its clinical benefits in bone tissue engineering may be achieved by combining MSCs with PEEK implants. These data may also provide useful information for further modification of PEEK with chemical or physical methods to regulate the cellular processes of MSCs and to consequently improve the efficacy of MSC-PEEK based therapies.}, language = {en} } @article{NoechelReddyWangetal.2015, author = {N{\"o}chel, Ulrich and Reddy, Chaganti Srinivasa and Wang, Ke and Cui, Jing and Zizak, Ivo and Behl, Marc and Kratz, Karl and Lendlein, Andreas}, title = {Nanostructural changes in crystallizable controlling units determine the temperature-memory of polymers}, series = {Journal of materials chemistry : A, Materials for energy and sustainability}, volume = {3}, journal = {Journal of materials chemistry : A, Materials for energy and sustainability}, number = {16}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-7488}, doi = {10.1039/c4ta06586g}, pages = {8284 -- 8293}, year = {2015}, abstract = {Temperature-memory polymers remember the temperature, where they were deformed recently, enabled by broad thermal transitions. In this study, we explored a series of crosslinked poly[ethylene-co-(vinyl acetate)] networks (cPEVAs) comprising crystallizable polyethylene (PE) controlling units exhibiting a pronounced temperature-memory effect (TME) between 16 and 99 degrees C related to a broad melting transition (similar to 100 degrees C). The nanostructural changes in such cPEVAs during programming and activation of the TME were analyzed via in situ X-ray scattering and specific annealing experiments. Different contributions to the mechanism of memorizing high or low deformation temperatures (T-deform) were observed in cPEVA, which can be associated to the average PE crystal sizes. At high deformation temperatures (>50 degrees C), newly formed PE crystals, which are established during cooling when fixing the temporary shape, dominated the TME mechanism. In contrast, at low T-deform (<50 degrees C), corresponding to a cold drawing scenario, the deformation led preferably to a disruption of existing large crystals into smaller ones, which then fix the temporary shape upon cooling. The observed mechanism of memorizing a deformation temperature might enable the prediction of the TME behavior and the knowledge based design of other TMPs with crystallizable controlling units.}, language = {en} } @article{ZhangSauterFangetal.2015, author = {Zhang, Quanchao and Sauter, Tilman and Fang, Liang and Kratz, Karl and Lendlein, Andreas}, title = {Shape-Memory Capability of Copolyetheresterurethane Microparticles Prepared via Electrospraying}, series = {Macromolecular materials and engineering}, volume = {300}, journal = {Macromolecular materials and engineering}, number = {5}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1438-7492}, doi = {10.1002/mame.201400267}, pages = {522 -- 530}, year = {2015}, abstract = {Multifunctional thermo-responsive and degradable microparticles exhibiting a shapememory effect (SME) have attracted widespread interest in biomedicine as switchable delivery vehicles or microactuators. In this work almost spherical solid microparticles with an average diameter of 3.9 +/- 0.9 mm are prepared via electrospraying of a copolyetheresterurethane named PDC, which is composed of crystallizable oligo(p-dioxanone) (OPDO) hard and oligo(e-caprolactone) (OCL) switching segments. The PDC microparticles are programmed via compression at different pressures and their shapememory capability is explored by off-line and online heating experiments. When a low programming pressure of 0.2 MPa is applied a pronounced thermally-induced shape-memory effect is achieved with a shape recovery ratio about 80\%, while a high programming pressure of 100 MPa resulted in a weak shape-memory performance. Finally, it is demonstrated that an array of PDC microparticles deposited on a polypropylene (PP) substrate can be successfully programmed into a smart temporary film, which disintegrates upon heating to 60 degrees C.}, language = {en} }