@article{MichalikOnichimowskaKernRiedeletal.2017, author = {Michalik-Onichimowska, Aleksandra and Kern, Simon and Riedel, Jens and Panne, Ulrich and King, Rudibert and Maiwald, Michael}, title = {"Click" analytics for "click" chemistry - A simple method for calibration-free evaluation of online NMR spectra}, series = {Journal of magnetic resonance}, volume = {277}, journal = {Journal of magnetic resonance}, publisher = {Elsevier}, address = {San Diego}, issn = {1090-7807}, doi = {10.1016/j.jmr.2017.02.018}, pages = {154 -- 161}, year = {2017}, abstract = {Driven mostly by the search for chemical syntheses under biocompatible conditions, so called "click" chemistry rapidly became a growing field of research. The resulting simple one-pot reactions are so far only scarcely accompanied by an adequate optimization via comparably straightforward and robust analysis techniques possessing short set-up times. Here, we report on a fast and reliable calibration-free online NMR monitoring approach for technical mixtures. It combines a versatile fluidic system, continuous-flow measurement of H-1 spectra with a time interval of 20 s per spectrum, and a robust, fully automated algorithm to interpret the obtained data. As a proof-of-concept, the thiol-ene coupling between N-boc cysteine methyl ester and ally] alcohol was conducted in a variety of non-deuterated solvents while its time-resolved behaviour was characterized with step tracer experiments. Overlapping signals in online spectra during thiol-ene coupling could be deconvoluted with a spectral model using indirect hard modeling and were subsequently converted to either molar ratios (using a calibration free approach) or absolute concentrations (using 1-point calibration). For various solvents the kinetic constant k for pseudo-first order reaction was estimated to be 3.9 h(-1) at 25 degrees C. The obtained results were compared with direct integration of non-overlapping signals and showed good agreement with the implemented mass balance. (C) 2017 Elsevier Inc. All rights reserved.}, language = {en} } @article{VishnevetskayaHildebrandNiebuuretal.2017, author = {Vishnevetskaya, Natalya S. and Hildebrand, Viet and Niebuur, Bart-Jan and Grillo, Isabelle and Filippov, Sergey K. and Laschewsky, Andre and M{\"u}ller-Buschbaum, Peter and Papadakis, Christine M.}, title = {"Schizophrenic" Micelles from Doubly Thermoresponsive Polysulfobetaine-b-poly(N-isopropylmethacrylamide) Diblock Copolymers}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {50}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.7b00356}, pages = {3985 -- 3999}, year = {2017}, language = {en} } @misc{KoenigKellingSchildeetal.2017, author = {K{\"o}nig, Jana and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {[µ2-O,O′,Oʺ,Oʺ′-Bis(1,2-dithiooxalato-S,S′)nickel(II)]bis[-O,O′-bis(1,2-dithiooxalato-S,S′)-nickel(II)pentaquaholmium(III)]hydrate, [Ho2Ni3(dto)6(H2O)10]}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-400598}, pages = {5}, year = {2017}, abstract = {Planar bis(1,2-dithiooxalato)nickelate(II), [Ni(dto)]2- reacts in aqueous solutions with lanthanide ions (Ln3+) to form pentanuclear, hetero-bimetallic complexes of the general composition [{Ln(H2O)n}2{Ni(dto)2}3]·xH2O. (n = 4 or 5; x = 9-12). The complex [{Ho(H2O)5}2{Ni(dto)2}3]·10H2O, Ho2Ni3, was synthesized and characterized by single crystal X-ray structure analysis and powder diffraction. The Ho2Ni3 complex crystallizes as monoclinic crystals in the space group P21/c. The channels and cavities, appearing in the crystal packing of the complex molecules, are occupied by a varying amount of non-coordinated water molecules.}, language = {en} } @article{MeynersMertensWessigetal.2017, author = {Meyners, Christian and Mertens, Monique and Wessig, Pablo and Meyer-Almes, Franz-Josef}, title = {A Fluorescence-Lifetime-Based Binding Assay for Class IIa Histone Deacetylases}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, number = {13}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201605140}, pages = {3107 -- 3116}, year = {2017}, abstract = {Class IIa histone deacetylases (HDACs) show extremely low enzymatic activity and no commonly accepted endogenous substrate is known today. Increasing evidence suggests that these enzymes exert their effect rather through molecular recognition of acetylated proteins and recruiting other proteins like HDAC3 to the desired target location. Accordingly, class IIa HDACs like bromodomains have been suggested to act as "Readers" of acetyl marks, whereas enzymatically active HDACs of class I or IIb are called "Erasers" to highlight their capability to remove acetyl groups from acetylated histones or other proteins. Small-molecule ligands of class IIa histone deacetylases (HDACs) have gained tremendous attention during the last decade and have been suggested as pharmaceutical targets in several indication areas such as cancer, Huntington's disease and muscular atrophy. Up to now, only enzyme activity assays with artificial chemically activated trifluoroacetylated substrates are in use for the identification and characterization of new active compounds against class IIa HDACs. Here, we describe the first binding assay for this class of HDAC enzymes that involves a simple mix-and-measure procedure and an extraordinarily robust fluorescence lifetime readout based on [1,3]dioxolo[4,5-f]benzodioxole-based ligand probes. The principle of the assay is generic and can also be transferred to class I HDAC8.}, language = {en} } @article{RackwitzRankovićMilosavljevićetal.2017, author = {Rackwitz, Jenny and Ranković, Miloš Lj. and Milosavljević, Aleksandar R. and Bald, Ilko}, title = {A novel setup for the determination of absolute cross sections for low-energy electron induced strand breaks in oligonucleotides}, series = {The European physical journal : D, Atomic, molecular, optical and plasma physics}, volume = {71}, journal = {The European physical journal : D, Atomic, molecular, optical and plasma physics}, publisher = {Springer}, address = {New York}, issn = {1434-6060}, doi = {10.1140/epjd/e2016-70608-4}, pages = {9}, year = {2017}, abstract = {Low-energy electrons (LEEs) play an important role in DNA radiation damage. Here we present a method to quantify LEE induced strand breakage in well-defined oligonucleotide single strands in terms of absolute cross sections. An LEE irradiation setup covering electron energies <500 eV is constructed and optimized to irradiate DNA origami triangles carrying well-defined oligonucleotide target strands. Measurements are presented for 10.0 and 5.5 eV for different oligonucleotide targets. The determination of absolute strand break cross sections is performed by atomic force microscopy analysis. An accurate fluence determination ensures small margins of error of the determined absolute single strand break cross sections sigma SSB. In this way, the influence of sequence modification with the radiosensitive 5-Fluorouracil (U-5F) is studied using an absolute and relative data analysis. We demonstrate an increase in the strand break yields of U-5F containing oligonucleotides by a factor of 1.5 to 1.6 compared with non-modified oligonucleotide sequences when irradiated with 10 eV electrons.}, language = {en} } @article{LorenzSaalfrank2017, author = {Lorenz, U. and Saalfrank, Peter}, title = {A novel system-bath Hamiltonian for vibration-phonon coupling}, series = {Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature}, volume = {482}, journal = {Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature}, publisher = {Elsevier Science}, address = {Amsterdam}, issn = {0301-0104}, doi = {10.1016/j.chemphys.2016.06.004}, pages = {69 -- 80}, year = {2017}, abstract = {We present a rigorous method to set up a system-bath Hamiltonian for the coupling of adsorbate vibrations (the system) to surface phonons (the bath). The Hamiltonian is straightforward to derive and exact up to second order in the environment coordinates, thus capable of treating one- and two-phonon contributions to vibration-phonon coupling. The construction of the Hamiltonian uses orthogonal coordinates for system and bath modes, is based on an embedded cluster approach, and generalizes previous Hamiltonians of a similar type, but avoids several (additional) approximations. While the parametrization of the full Hamiltonian is in principle feasible by a first principles quantum mechanical treatment, here we adopt in the spirit of a QM/MM model a combination of density functional theory ("QM", for the system) and a semiempirical forcefield ("MM", for the bath). We apply the Hamiltonian to a fully H-covered Si(100)-(2 × 1) surface, using Fermi's Golden Rule to obtain vibrational relaxation rates of various H-Si bending modes of this system. As in earlier work it is found that the relaxation is dominated by two-phonon contributions because of an energy gap between the Si-H bending modes and the Si phonon bands. We obtain vibrational lifetimes (of the first excited state) on the order of 2 ps at K. The lifetimes depend only little on the type of bending mode (symmetric vs. antisymmetric, parallel vs. perpendicular to the Si2H2 dimers). They decrease by a factor of about two when heating the surface to 300 K. We also study isotope effects by replacing adsorbed H atoms by deuterium, D. The Si-D bending modes are shifted into the Si phonon band of the solid, opening up one-phonon decay channels and reducing the lifetimes to few hundred fs.}, language = {en} } @article{ThierbachNeissGallandietal.2017, author = {Thierbach, Adrian and Neiss, Christian and Gallandi, Lukas and Marom, Noa and Koerzdoerfer, Thomas and Goerling, Andreas}, title = {Accurate Valence Ionization Energies from Kohn-Sham Eigenvalues with the Help of Potential Adjustors}, series = {Journal of chemical theory and computation}, volume = {13}, journal = {Journal of chemical theory and computation}, publisher = {American Chemical Society}, address = {Washington}, issn = {1549-9618}, doi = {10.1021/acs.jctc.7b00490}, pages = {4726 -- 4740}, year = {2017}, abstract = {An accurate yet computationally very efficient and formally well justified approach to calculate molecular ionization potentials is presented and tested. The first as well as higher ionization potentials are obtained as the negatives of the Kohn-Sham eigenvalues of the neutral molecule after adjusting the eigenvalues by a recently [Gorling Phys. Rev. B 2015, 91, 245120] introduced potential adjustor for exchange-correlation potentials. Technically the method is very simple. Besides a Kohn-Sham calculation of the neutral molecule, only a second Kohn-Sham calculation of the cation is required. The eigenvalue spectrum of the neutral molecule is shifted such that the negative of the eigenvalue of the highest occupied molecular orbital equals the energy difference of the total electronic energies of the cation minus the neutral molecule. For the first ionization potential this simply amounts to a Delta SCF calculation. Then, the higher ionization potentials are obtained as the negatives of the correspondingly shifted Kohn-Sham eigenvalues. Importantly, this shift of the Kohn-Sham eigenvalue spectrum is not just ad hoc. In fact, it is formally necessary for the physically correct energetic adjustment of the eigenvalue spectrum as it results from ensemble density-functional theory. An analogous approach for electron affinities is equally well obtained and justified. To illustrate the practical benefits of the approach, we calculate the valence ionization energies of test sets of small- and medium-sized molecules and photoelectron spectra of medium-sized electron acceptor molecules using a typical semilocal (PBE) and two typical global hybrid functionals (B3LYP and PBE0). The potential adjusted B3LYP and PBE0 eigenvalues yield valence ionization potentials that are in very good agreement with experimental values, reaching an accuracy that is as good as the best G(0)W(0) methods, however, at much lower computational costs. The potential adjusted PBE eigenvalues result in somewhat less accurate ionization energies, which, however, are almost as accurate as those obtained from the most commonly used G(0)W(0) variants.}, language = {en} } @article{AbouserieZehbeMetzneretal.2017, author = {Abouserie, Ahed and Zehbe, Kerstin and Metzner, Philipp and Kelling, Alexandra and G{\"u}nter, Christina and Schilde, Uwe and Strauch, Peter and K{\"o}rzd{\"o}rfer, Thomas and Taubert, Andreas}, title = {Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201700826}, pages = {5640 -- 5649}, year = {2017}, abstract = {Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.}, language = {en} } @article{AbouserieZehbeMetzneretal.2017, author = {Abouserie, Ahed and Zehbe, Kerstin and Metzner, Philipp and Kelling, Alexandra and G{\"u}nter, Christina and Schilde, Uwe and Strauch, Peter and K{\"o}rzd{\"o}rfer, Thomas and Taubert, Andreas}, title = {Alkylpyridinium Tetrahalidometallate Ionic Liquids and Ionic Liquid Crystals: Insights into the Origin of Their Phase Behavior}, series = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, journal = {European journal of inorganic chemistry : a journal of ChemPubSoc Europe}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-1948}, doi = {10.1002/ejic.201700826}, pages = {5640 -- 5649}, year = {2017}, abstract = {Six N-alkylpyridinium salts [CnPy](2)[MCl4] (n = 4 or 12 and M = Co, Cu, Zn) were synthesized, and their structure and thermal properties were studied. The [C4Py](2)[MCl4] compounds are monoclinic and crystallize in the space group P2(1)/n. The crystals of the longer chain analogues [C12Py](2)[MCl4] are triclinic and crystallize in the space group P (1) over bar. Above the melting temperature, all compounds are ionic liquids (ILs). The derivatives with the longer C12 chain exhibit liquid crystallinity and the shorter chain compounds only show a melting transition. Consistent with single-crystal analysis, electron paramagnetic resonance spectroscopy suggests that the [CuCl4](2-) ions in the Cu-based ILs have a distorted tetrahedral geometry.}, language = {en} } @article{LutzeBanaresPitaetal.2017, author = {Lutze, Jana and Ba{\~n}ares, Miguel A. and Pita, Marcos and Haase, Andrea and Luch, Andreas and Taubert, Andreas}, title = {alpha-((4-Cyanobenzoyl)oxy)-omega-methyl poly(ethylene glycol)}, series = {Beilstein journal of nanotechnology}, volume = {8}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {2190-4286}, doi = {10.3762/bjnano.8.67}, pages = {627 -- 635}, year = {2017}, abstract = {The article describes the synthesis and properties of alpha-((4-cyanobenzoyl)oxy)-omega-methyl poly(ethylene glycol), the first poly(ethylene glycol) stabilizer for metal nanoparticles that is based on a cyano rather than a thiol or thiolate anchor group. The silver particles used to evaluate the effectiveness of the new stabilizer typically have a bimodal size distribution with hydrodynamic diameters of ca. 13 and ca. 79 nm. Polymer stability was evaluated as a function of the pH value both for the free stabilizer and for the polymers bound to the surface of the silver nanoparticles using H-1 NMR spectroscopy and zeta potential measurements. The polymer shows a high stability between pH 3 and 9. At pH 12 and higher the polymer coating is degraded over time suggesting that alpha-((4-cyanobenzoyl) oxy)-omega-methyl poly(ethylene glycol) is a good stabilizer for metal nanoparticles in aqueous media unless very high pH conditions are present in the system. The study thus demonstrates that cyano groups can be viable alternatives to the more conventional thiol/thiolate anchors.}, language = {en} } @article{SchmidtKorbAbell2017, author = {Schmidt, Marco F. and Korb, Oliver and Abell, Chris}, title = {Antagonists of the miRNA-Argonaute 2 Protein Complex}, series = {Drug Target miRNA: Methods and Protocols}, volume = {1517}, journal = {Drug Target miRNA: Methods and Protocols}, publisher = {Springer}, address = {New York}, isbn = {978-1-4939-6563-2}, issn = {1064-3745}, doi = {10.1007/978-1-4939-6563-2_17}, pages = {239 -- 249}, year = {2017}, abstract = {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.}, language = {en} } @article{SelemaniNondoMoshietal.2017, author = {Selemani, Ramadhani Selemani Omari and Nondo, Omari and Moshi, Mainen Julius and Erasto, Paul and Masimba, Pax Jessey and Machumi, Francis and Kidukuli, Abdul Waziri and Heydenreich, Matthias and Zofou, Denis}, title = {Anti-plasmodial activity of Norcaesalpin D and extracts of four medicinal plants used traditionally for treatment of malaria}, series = {BMC Complementary and Alternative Medicine volume}, volume = {17}, journal = {BMC Complementary and Alternative Medicine volume}, publisher = {BioMed Central}, address = {London}, issn = {1472-6882}, doi = {10.1186/s12906-017-1673-8}, pages = {8}, year = {2017}, abstract = {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.}, language = {en} } @article{MuthauraKerikoMutaietal.2017, author = {Muthaura, Charles N. and Keriko, Joseph M. and Mutai, Charles and Yenesew, Abiy and Heydenreich, Matthias and Atilaw, Yoseph and Gathirwa, Jeremiah W. and Irungu, Beatrice N. and Derese, Solomon}, title = {Antiplasmodial, cytotoxicity and phytochemical constituents of four maytenus species used in traditional medicine in Kenya}, series = {The natural products journal}, volume = {7}, journal = {The natural products journal}, number = {2}, publisher = {Bentham Science Publ.}, address = {Sharjah}, issn = {2210-3155}, doi = {10.2174/2210315507666161206144050}, pages = {144 -- 152}, year = {2017}, abstract = {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.}, language = {en} } @article{KlaussConradHille2017, author = {Klauß, Andr{\´e} and Conrad, Florian and Hille, Carsten}, title = {Binary phase masks for easy system alignment and basic aberration sensing with spatial light modulators in STED microscopy}, series = {Scientific reports}, volume = {7}, journal = {Scientific reports}, publisher = {Nature Publ. Group}, address = {London}, issn = {2045-2322}, doi = {10.1038/s41598-017-15967-5}, pages = {11}, year = {2017}, language = {en} } @article{ZhangBisterfeldBramskietal.2017, author = {Zhang, Shuhao and Bisterfeld, Carolin and Bramski, Julia and Vanparijs, Nane and De Geest, Bruno G. and Pietruszka, J{\"o}rg and B{\"o}ker, Alexander and Reinicke, Stefan}, title = {Biocatalytically Active Thin Films via Self-Assembly of 2-Deoxy-D-ribose-5-phosphate Aldolase-Poly(N-isopropylacrylamide) Conjugates}, series = {Bioconjugate chemistry}, volume = {29}, journal = {Bioconjugate chemistry}, number = {1}, publisher = {American Chemical Society}, address = {Washington}, issn = {1043-1802}, doi = {10.1021/acs.bioconjchem.7b00645}, pages = {104 -- 116}, year = {2017}, abstract = {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.}, language = {en} } @misc{HardyTorresRendonLealEganaetal.2017, author = {Hardy, John G. and Torres-Rendon, Jose Guillermo and Leal-Ega{\~n}a, Aldo and Walther, Andreas and Schlaad, Helmut and C{\"o}lfen, Helmut and Scheibel, Thomas R.}, title = {Biomineralization of engineered spider silk protein-based composite materials for bone tissue engineering}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-400519}, pages = {13}, year = {2017}, abstract = {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.}, language = {en} } @phdthesis{Peh2017, author = {Peh, Eddie K.W.}, title = {Calcium carbonate formation}, school = {Universit{\"a}t Potsdam}, pages = {133}, year = {2017}, language = {en} } @article{HentrichBrezesinskiKuebeletal.2017, author = {Hentrich, Doreen and Brezesinski, Gerald and Kuebel, Christian and Bruns, Michael and Taubert, Andreas}, title = {Cholesteryl Hemisuccinate Monolayers Efficiently Control Calcium Phosphate Nucleation and Growth}, series = {Crystal growth \& design : integrating the fields of crystal engineering and crystal growth for the synthesis and applications of new materials}, volume = {17}, journal = {Crystal growth \& design : integrating the fields of crystal engineering and crystal growth for the synthesis and applications of new materials}, publisher = {American Chemical Society}, address = {Washington}, issn = {1528-7483}, doi = {10.1021/acs.cgd.7b00753}, pages = {5764 -- 5774}, year = {2017}, abstract = {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.}, language = {en} } @article{PehLiedelTaubertetal.2017, author = {Peh, Eddie and Liedel, Clemens and Taubert, Andreas and Tauer, Klaus}, title = {Composition inversion to form calcium carbonate mixtures}, series = {CrystEngComm}, volume = {19}, journal = {CrystEngComm}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1466-8033}, doi = {10.1039/c7ce00433h}, pages = {3573 -- 3583}, year = {2017}, abstract = {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.}, language = {en} } @article{ShainyanKirpichenkoKleinpeter2017, author = {Shainyan, Bagrat A. and Kirpichenko, Svetlana V. and Kleinpeter, Erich}, title = {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}, series = {The journal of organic chemistry}, volume = {82}, journal = {The journal of organic chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {0022-3263}, doi = {10.1021/acs.joc.7b02505}, pages = {13414 -- 13422}, year = {2017}, abstract = {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.}, language = {en} } @phdthesis{You2017, author = {You, Zewang}, title = {Conformational transition of peptide-functionalized cryogels enabling shape-memory capability}, school = {Universit{\"a}t Potsdam}, pages = {144}, year = {2017}, language = {en} } @article{SchweighoeferMorenoBoboneetal.2017, author = {Schweigh{\"o}fer, F. and Moreno, J. and Bobone, Sara and Chiantia, Salvatore and Herrmann, A. and Hecht, S. and Wachtveitl, Josef}, title = {Connectivity pattern modifies excited state relaxation dynamics of fluorophore-photoswitch molecular dyads}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {19}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c6cp07112k}, pages = {4010 -- 4018}, year = {2017}, abstract = {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.}, language = {en} } @article{VacogneSchlaad2017, author = {Vacogne, Charlotte D. and Schlaad, Helmut}, title = {Controlled ring-opening polymerization of alpha-amino acid N-carboxyanhydrides in the presence of tertiary amines}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {124}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2017.07.062}, pages = {203 -- 209}, year = {2017}, abstract = {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.}, language = {en} } @article{SchildePazOrtiz2017, author = {Schilde, Uwe and Paz, Christian and Ortiz, Leandro}, title = {Crystal structure of erioflorin isolated from Podanthus mitiqui (L.)}, series = {Acta Crystallographica Section E : Crystallographic Communications}, volume = {73}, journal = {Acta Crystallographica Section E : Crystallographic Communications}, number = {3}, publisher = {International Union of Crystallography}, address = {Chester}, doi = {10.1107/S2056989017001700}, pages = {334 -- 337}, year = {2017}, abstract = {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.}, language = {en} } @misc{SchildePazOrtiz2017, author = {Schilde, Uwe and Paz, Christian and Ortiz, Leandro}, title = {Crystal structure of erioflorin isolated from Podanthus mitiqui (L.)}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-401832}, pages = {4}, year = {2017}, abstract = {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.}, language = {en} } @phdthesis{Jordan2017, author = {Jordan, Thomas}, title = {CxNy-materials from supramolecular precursors for "All-Carbon" composite materials}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-398855}, school = {Universit{\"a}t Potsdam}, pages = {157}, year = {2017}, abstract = {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.}, language = {en} } @article{LiebigSarhanSanderetal.2017, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Sander, Mathias and Koopman, Wouter-Willem Adriaan and Schuetz, Roman and Bargheer, Matias and Koetz, Joachim}, title = {Deposition of Gold Nanotriangles in Large Scale Close-Packed Monolayers for X-ray-Based Temperature Calibration and SERS Monitoring of Plasmon-Driven Catalytic Reactions}, series = {ACS applied materials \& interfaces}, volume = {9}, journal = {ACS applied materials \& interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.7b07231}, pages = {20247 -- 20253}, year = {2017}, language = {en} } @article{SchwarzeMuellerSchmidtetal.2017, author = {Schwarze, Thomas and Mueller, Holger and Schmidt, Darya and Riemer, Janine and Holdt, Hans-J{\"u}rgen}, title = {Design of Na+-Selective Fluorescent Probes: A Systematic Study of the Na+-Complex Stability and the Na+/K+ Selectivity in Acetonitrile and Water}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201605986}, pages = {7255 -- 7263}, year = {2017}, abstract = {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.}, language = {en} } @phdthesis{Meiling2017, author = {Meiling, Till Thomas}, title = {Development of a reliable and environmentally friendly synthesis for fluorescence carbon nanodots}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-410160}, school = {Universit{\"a}t Potsdam}, pages = {198}, year = {2017}, abstract = {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).}, language = {en} } @phdthesis{Dippel2017, author = {Dippel, Sandor}, title = {Development of functional hydrogels for sensor applications}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-398252}, school = {Universit{\"a}t Potsdam}, pages = {127}, year = {2017}, abstract = {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.}, language = {en} } @article{RumschoettelKosmellaPrietzeletal.2017, author = {Rumschoettel, Jens and Kosmella, Sabine and Prietzel, Claudia Christina and Appelhans, Dietmar and Koetz, Joachim}, title = {DNA polyplexes with dendritic glycopolymer-entrapped gold nanoparticles}, series = {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}, volume = {154}, journal = {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}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0927-7765}, doi = {10.1016/j.colsurfb.2017.03.001}, pages = {74 -- 81}, year = {2017}, abstract = {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.}, language = {en} } @article{TebaldiCharanMavliutovaetal.2017, author = {Tebaldi, Marli Luiza and Charan, Himanshu and Mavliutova, Liliia and B{\"o}ker, Alexander and Glebe, Ulrich}, title = {Dual-Stimuli Sensitive Hybrid Materials: Ferritin-PDMAEMA by Grafting-From Polymerization}, series = {Macromolecular chemistry and physics}, volume = {218}, journal = {Macromolecular chemistry and physics}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1352}, doi = {10.1002/macp.201600529}, pages = {6}, year = {2017}, abstract = {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.}, language = {en} } @article{MovahedifarModarresiAlamKleinpeteretal.2017, author = {Movahedifar, Fahimeh and Modarresi-Alam, Ali Reza and Kleinpeter, Erich and Schilde, Uwe}, title = {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}, series = {Journal of molecular structure}, volume = {1133}, journal = {Journal of molecular structure}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0022-2860}, doi = {10.1016/j.molstruc.2016.12.010}, pages = {244 -- 252}, year = {2017}, abstract = {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.}, language = {en} } @article{LippoldEidnerKumkeetal.2017, author = {Lippold, Holger and Eidner, Sascha and Kumke, Michael Uwe and Lippmann-Pipke, Johanna}, title = {Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time}, series = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, volume = {197}, journal = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, publisher = {Elsevier}, address = {Oxford}, issn = {0016-7037}, doi = {10.1016/j.gca.2016.10.019}, pages = {62 -- 70}, year = {2017}, abstract = {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.}, language = {en} } @misc{IhmelsLinkerTrofimov2017, author = {Ihmels, Heiko and Linker, Torsten and Trofimov, Aleksei}, title = {Editorial}, series = {Journal of physical organic chemistry}, volume = {30}, journal = {Journal of physical organic chemistry}, publisher = {Wiley}, address = {Hoboken}, issn = {0894-3230}, doi = {10.1002/poc.3745}, pages = {1}, year = {2017}, language = {en} } @article{SchuermannBald2017, author = {Sch{\"u}rmann, Robin Mathis and Bald, Ilko}, title = {Effect of adsorption kinetics on dissociation of DNA-nucleobases on gold nanoparticles under pulsed laser illumination}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {19}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c6cp08433h}, pages = {10796 -- 10803}, year = {2017}, abstract = {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.}, language = {en} } @article{HildebrandLaschewskyPaechetal.2017, author = {Hildebrand, Viet and Laschewsky, Andre and P{\"a}ch, Michael and M{\"u}ller-Buschbaum, Peter and Papadakis, Christine M.}, title = {Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)}, series = {Polymer Chemistry}, volume = {8}, journal = {Polymer Chemistry}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1759-9954}, doi = {10.1039/c6py01220e}, pages = {310 -- 322}, year = {2017}, abstract = {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.}, language = {en} } @article{MorgnerBennemannCywińskietal.2017, author = {Morgner, Frank and Bennemann, Mark and Cywiński, Piotr J. and Kollosche, Matthias and G{\´o}rski, Krzysztof and Pietraszkiewicz, Marek and Geßner, Andr{\´e} and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Elastic FRET sensors for contactless pressure measurement}, series = {RSC Advances : an international journal to further the chemical sciences}, volume = {7}, journal = {RSC Advances : an international journal to further the chemical sciences}, publisher = {RSC Publishing}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c7ra06379b}, pages = {50578 -- 50583}, year = {2017}, abstract = {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.}, language = {en} } @article{GouletHanssensUtechtMutrucetal.2017, author = {Goulet-Hanssens, Alexis and Utecht, Manuel and Mutruc, Dragos and Titov, Evgenii and Schwarz, Jutta and Grubert, Lutz and Bleger, David and Saalfrank, Peter and Hecht, Stefan}, title = {Electrocatalytic Z -> E Isomerization of Azobenzenes}, series = {Journal of the American Chemical Society}, volume = {139}, journal = {Journal of the American Chemical Society}, number = {1}, publisher = {American Chemical Society}, address = {Washington}, issn = {0002-7863}, doi = {10.1021/jacs.6b10822}, pages = {335 -- 341}, year = {2017}, abstract = {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.}, language = {en} } @article{PilusoLendleinNeffe2017, author = {Piluso, Susanna and Lendlein, Andreas and Neffe, Axel T.}, title = {Enzymatic action as switch of bulk to surface degradation of clicked gelatin-based networks}, series = {Polymers for advanced technologies}, volume = {28}, journal = {Polymers for advanced technologies}, publisher = {Wiley}, address = {Hoboken}, issn = {1042-7147}, doi = {10.1002/pat.3962}, pages = {1318 -- 1324}, year = {2017}, abstract = {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.}, language = {en} } @misc{SchoeneRochSchulzetal.2017, author = {Sch{\"o}ne, Anne-Christin and Roch, Toralf and Schulz, Burkhard and Lendlein, Andreas}, title = {Evaluating polymeric biomaterial-environment interfaces by Langmuir monolayer techniques}, series = {Interface : journal of the Royal Society}, volume = {14}, journal = {Interface : journal of the Royal Society}, publisher = {Royal Society}, address = {London}, issn = {1742-5689}, doi = {10.1098/rsif.2016.1028}, pages = {18}, year = {2017}, abstract = {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.}, language = {en} } @article{ParamonovKuehnBandrauk2017, author = {Paramonov, Guennaddi K. and K{\"u}hn, Oliver and Bandrauk, Andr{\´e} D.}, title = {Excitation of H+ 2 with one-cycle laser pulses}, series = {Molecular physics : MP ; an international journal in the field of chemical physics}, volume = {115}, journal = {Molecular physics : MP ; an international journal in the field of chemical physics}, number = {15/16}, publisher = {Taylor \& Francis}, address = {London}, issn = {0026-8976}, doi = {10.1080/00268976.2017.1288938}, pages = {1846 -- 1860}, year = {2017}, abstract = {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 Schr{\"o}dinger 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.}, language = {en} } @article{HovestadtBendtMondaletal.2017, author = {Hovestadt, Maximilian and Bendt, Stephan and Mondal, Suvendu Sekhar and Behrens, Karsten and Reif, Florian and Dopken, Merle and Holdt, Hans-J{\"u}rgen and Keil, Frerich J. and Hartmann, Martin}, title = {Experimental and Theoretical Analysis of the Influence of Different Linker Molecules in Imidazolate Frameworks Potsdam (IFP-n) on the Separation of Olefin-Paraffin Mixtures}, series = {Langmuir}, volume = {33}, journal = {Langmuir}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.7b02016}, pages = {11170 -- 11179}, year = {2017}, abstract = {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.}, language = {en} } @article{WuGlebeBoeker2017, author = {Wu, Lei and Glebe, Ulrich and B{\"o}ker, Alexander}, title = {Fabrication of Thermoresponsive Plasmonic Core-Satellite Nanoassemblies with a Tunable Stoichiometry via Surface-Initiated Reversible Addition-Fragmentation Chain Transfer Polymerization from Silica Nanoparticles}, series = {Advanced materials interfaces}, volume = {4}, journal = {Advanced materials interfaces}, publisher = {Wiley}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.201700092}, pages = {10}, year = {2017}, abstract = {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.}, language = {en} } @article{UnuabonahAgunbiadeAlfredetal.2017, author = {Unuabonah, Emmanuel Iyayi and Agunbiade, Foluso O. and Alfred, Moses O. and Adewumi, Thompson A. and Okoli, Chukwunonso P. and Omorogie, Martins O. and Akanbi, Moses O. and Ofomaja, Augustine E. and Taubert, Andreas}, title = {Facile synthesis of new amino-functionalized agrogenic hybrid composite clay adsorbents for phosphate capture and recovery from water}, series = {Journal of Cleaner Production}, volume = {164}, journal = {Journal of Cleaner Production}, publisher = {Elsevier}, address = {Oxford}, issn = {0959-6526}, doi = {10.1016/j.jclepro.2017.06.160}, pages = {652 -- 663}, year = {2017}, abstract = {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.}, language = {en} } @article{TaubertLoebbickeKirchneretal.2017, author = {Taubert, Andreas and L{\"o}bbicke, Ruben and Kirchner, Barbara and Leroux, Fabrice}, title = {First examples of organosilica-based ionogels}, series = {Beilstein journal of nanotechnology}, volume = {8}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {2190-4286}, doi = {10.3762/bjnano.8.77}, pages = {736 -- 751}, year = {2017}, abstract = {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.}, language = {en} } @article{OlejkoBald2017, author = {Olejko, Lydia and Bald, Ilko}, title = {FRET efficiency and antenna effect in multi-color DNA origami-based light harvesting systems}, series = {RSC Advances}, volume = {7}, journal = {RSC Advances}, number = {39}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c7ra02114c}, pages = {23924 -- 23934}, year = {2017}, abstract = {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.}, language = {en} } @article{RyabchunSakhnoStumpeetal.2017, author = {Ryabchun, Alexander and Sakhno, Oksana and Stumpe, Joachim and Bobrovsky, Alexey}, title = {Full-Polymer Cholesteric Composites for Transmission and Reflection Holographic Gratings}, series = {Advanced optical materials}, volume = {5}, journal = {Advanced optical materials}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2195-1071}, doi = {10.1002/adom.201700314}, pages = {376 -- 379}, year = {2017}, abstract = {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.}, language = {en} } @phdthesis{MbayaMani2017, author = {Mbaya Mani, Christian}, title = {Functional nanoporous carbon-based materials derived from oxocarbon-metal coordination complexes}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-407866}, school = {Universit{\"a}t Potsdam}, pages = {IV, 135}, year = {2017}, abstract = {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.}, language = {en} } @phdthesis{Zhang2017, author = {Zhang, Weiyi}, title = {Functional Poly(ionic liquid) Materials based on Poly(1,2,4-triazolium)s}, school = {Universit{\"a}t Potsdam}, pages = {108}, year = {2017}, language = {en} } @phdthesis{Olejko2017, author = {Olejko, Lydia}, title = {F{\"o}rster resonance energy transfer (FRET)-based nanophotonics using DNA origami structures}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-396747}, school = {Universit{\"a}t Potsdam}, year = {2017}, abstract = {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 F{\"o}rster 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.}, language = {en} } @article{SungKochovskiZhangetal.2017, author = {Sung, Jian-Ke and Kochovski, Zdravko and Zhang, Wei-Yi and Kirmse, Holm and Lu, Yan and Antonietti, Markus and Yuan, Jiayin}, title = {General Synthetic Route toward Highly Dispersed Metal Clusters Enabled by Poly(ionic liquid)s}, series = {Journal of the American Chemical Society}, volume = {139}, journal = {Journal of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0002-7863}, doi = {10.1021/jacs.7b03357}, pages = {8971 -- 8976}, year = {2017}, abstract = {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.}, language = {en} } @phdthesis{Heck2017, author = {Heck, Christian}, title = {Gold and silver nanolenses self-assembled by DNA origami}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-409002}, school = {Universit{\"a}t Potsdam}, pages = {ix, 125}, year = {2017}, abstract = {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.}, language = {en} } @article{HeckPrinzDatheetal.2017, author = {Heck, Christian and Prinz, Julia and Dathe, Andre and Merk, Virginia and Stranik, Ondrej and Fritzsche, Wolfgang and Kneipp, Janina and Bald, Ilko}, title = {Gold Nanolenses Self-Assembled by DNA Origami}, series = {ACS Photonics}, volume = {4}, journal = {ACS Photonics}, publisher = {American Chemical Society}, address = {Washington}, issn = {2330-4022}, doi = {10.1021/acsphotonics.6b00946}, pages = {1123 -- 1130}, year = {2017}, abstract = {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.}, language = {en} } @article{AndrewsFergusonRangaswamyetal.2017, author = {Andrews, N. L. P. and Ferguson, T. and Rangaswamy, A. M. M. and Bernicky, A. R. and Henning, N. and Dudelzak, A. and Reich, Oliver and Barnes, Jack A. and Loock, Hans-Peter}, title = {Hadamard-Transform Fluorescence Excitation-Emission-Matrix Spectroscopy}, series = {Analytical chemistry}, volume = {89}, journal = {Analytical chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {0003-2700}, doi = {10.1021/acs.analchem.7b02400}, pages = {8554 -- 8564}, year = {2017}, abstract = {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.}, language = {en} } @article{vonKlitzingStehlPogrzebaetal.2017, author = {von Klitzing, Regine and Stehl, Dimitrij and Pogrzeba, Tobias and Schoma{\"a}cker, Reinhard and Minullina, Renata and Panchal, Abhishek and Konnova, Svetlana and Fakhrullin, Rawil and Koetz, Joachim and Moehwald, Helmuth and Lvov, Yuri}, title = {Halloysites Stabilized Emulsions for Hydroformylation of Long Chain Olefins}, series = {Advanced materials interfaces}, volume = {4}, journal = {Advanced materials interfaces}, number = {1}, publisher = {Wiley}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.201600435}, pages = {8}, year = {2017}, abstract = {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.}, language = {en} } @article{DippongCarlLenzetal.2017, author = {Dippong, Martin and Carl, Peter and Lenz, Christine and Schenk, J{\"o}rg A. and Hoffmann, Katrin and Schwaar, Timm and Schneider, Rudolf J. and Kuhne, Maren}, title = {Hapten-Specific Single-Cell Selection of Hybridoma Clones by Fluorescence-Activated Cell Sorting for the Generation of Monoclonal Antibodies}, series = {Analytical chemistry}, volume = {89}, journal = {Analytical chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {0003-2700}, doi = {10.1021/acs.analchem.6b04569}, pages = {4007 -- 4012}, year = {2017}, language = {en} } @phdthesis{Braun2017, author = {Braun, Max}, title = {Heterogeneous Catalysis for the Conversion of Fructose to Chemicals and Fuel in a Continuous Flow Process}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-410370}, school = {Universit{\"a}t Potsdam}, pages = {151}, year = {2017}, abstract = {Die Umsetzung von Zucker (Kohlenhydrate) in einem kontinuierlichen Prozess er{\"o}ffnet M{\"o}glichkeiten der Synthese diverser Chemikalien und Treibstoff aus erneuerbaren Ressourcen, welche heute {\"u}berwiegend aus fossilen Quellen stammen. Passend zum Konzept der Bioraffinerie und der „gr{\"u}nen Chemie", liegt der Fokus dieser Arbeit auf der Umsetzung von in Ethanol gel{\"o}ster Fruktose in einem kontinuierlichen Verfahren, mit Hilfe eigens entwickelter heterogener Katalysatoren. Die Dehydratisierung von Fruktose wird mit einem heterogenen S{\"a}urekatalysator realisiert, w{\"a}hrend die Folgeprodukte mittels einer Hydrodesoxygenierung umgesetzt werden. F{\"u}r 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 Molek{\"u}le sind vielversprechende alternative Treibstoffe, bzw. k{\"o}nnen gebr{\"a}uchlichen Treibstoffen beigemischt werden, um deren Einsatz zu reduzieren und schrittweise zu substituieren. Alternativ k{\"o}nnen die Zwischenprodukte der Dehydratisierung, sowie DMF und EL weiter zu Chemikalien umgesetzt werden, welche in der Polymersynthese, als L{\"o}sungsmittel oder als Grundchemikalien eingesetzt werden k{\"o}nnen. Die Entwicklung der jeweiligen Katalysatoren f{\"u}r Dehydratisierungs- und Hydrodesoxygenierungsreaktionen erfolgt auf Basis von karbonisierter Biomasse, sowie Wolframcarbid. Die jeweiligen Reaktivit{\"a}ten 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 zus{\"a}tzlichen Nickel-Nanopartikeln werden f{\"u}r weiterf{\"u}hrende Reaktionen in einem kontinuierlichen Prozess herangezogen und kombiniert. Um den Umsatz von Fruktose zu DMF in einer „zwei Reaktoren Anlage" zu erm{\"o}glichen, wird eine Erweiterung eines kommerziellen Reaktorsystems um einen weiteren Reaktor vorgenommen. Die Verweilzeit in der Reaktoranlage betr{\"a}gt somit ca. 14 Minuten, wobei 11 Minuten auf die erste S{\"a}ule (Dehydratisierung) und 3 Minuten auf die zweite S{\"a}ule (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 Stabilit{\"a}t 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 unver{\"a}ndert in L{\"o}sung. Das zweistufige System wurde schließlich in einem Mischkatalysatorsystem kombiniert, wobei auf aktivierten und sulfonierten Kohlenstoff zur{\"u}ckgegriffen wurde. Dieser zeigte bereits eine Transferhydrodesoxygenierungsaktivit{\"a}t. Diese Beobachtung ist deshalb bemerkenswert, da erst seit kurzem bekannt ist, dass Graphenstrukturen an sich katalytisch aktiv sein k{\"o}nnen. Um diese Aktivit{\"a}t weiter zu steigern, wurde der aktivierte Kohlenstoff mit 10 wt\% Ni@WC gemischt, sodass beide Katalysatoren in einer S{\"a}ule vorliegen. Die urspr{\"u}nglichen 2 \% DMF Ausbeute mit reinem aktivierten Kohlenstoff k{\"o}nnen 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, Dr{\"u}cke von 100 bar und Temperaturen bis zu 500 °C.}, language = {en} } @article{SchwarzeMertensMuelleretal.2017, author = {Schwarze, Thomas and Mertens, Monique and Mueller, Peter and Riemer, Janine and Wessig, Pablo and Holdt, Hans-J{\"u}rgen}, title = {Highly K+-Selective Fluorescent Probes for Lifetime Sensing of K+ in Living Cells}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201704368}, pages = {17186 -- 17190}, year = {2017}, abstract = {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.}, language = {en} } @article{YangDingKochovskietal.2017, author = {Yang, Guang and Ding, Hong-ming and Kochovski, Zdravko and Hu, Rongting and Lu, Yan and Ma, Yu-qiang and Chen, Guosong and Jiang, Ming}, title = {Highly Ordered Self-Assembly of Native Proteins into 1D, 2D, and 3D Structures Modulated by the Tether Length of Assembly-Inducing Ligands}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {56}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201703052}, pages = {10691 -- 10695}, year = {2017}, abstract = {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.}, language = {en} } @article{KleinpeterKoch2017, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Identification of mesomeric substructures by through-space NMR shieldings (TSNMRS). Trimethine cyanine/merocyanine-like or aromatic pi-electron delocalization?}, series = {Tetrahedron}, volume = {73}, journal = {Tetrahedron}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4020}, doi = {10.1016/j.tet.2017.05.062}, pages = {4265 -- 4274}, year = {2017}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of amino-substituted heteraromatic six-membered ring systems such as pyrylium/thiopyrylium analogues have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to quantify and visualize the existing aromaticity of the studied compounds. Due to strong conjugation of six-membered ring pi-electrons and lone pairs of the exo-cyclic amino substituents (restricted rotation about partial C,N double bonds) the interplay of still aromatic and already dominating trimethine cyanine/merocyanine-like substructures can be estimated. (C) 2017 Elsevier Ltd. All rights reserved.}, language = {en} } @article{HaberPohlmeierToetzkeOswaldetal.2017, author = {Haber-Pohlmeier, Sabina and T{\"o}tzke, Christian and Oswald, Sascha and Lehmann, Eberhard and Bl{\"u}mich, Bernhard and Pohlmeier, Andreas}, title = {Imaging of root zone processes using MRI T-1 mapping}, series = {Microporous and mesoporous materials : zeolites, clays, carbons and related materials}, volume = {269}, journal = {Microporous and mesoporous materials : zeolites, clays, carbons and related materials}, publisher = {Elsevier}, address = {Amsterdam}, issn = {1387-1811}, doi = {10.1016/j.micromeso.2017.10.046}, pages = {43 -- 46}, year = {2017}, abstract = {Noninvasive imaging in the root soil compartment is mandatory for improving knowledge about root soil interactions and uptake processes which eventually control crop growth and productivity. Here we propose a method of MRI T-1 relaxation mapping to investigate water uptake patterns, and as second example, in combination with neutron tomography (NT), property changes in the rhizosphere. The first part demonstrates quantification of solute enrichment by advective transport to the roots due to water uptake. This accumulation is counterbalanced by net downward flow and dispersive spreading. One can furthermore discriminate between zones of high accumulation patterns and zones with much less enrichment. This behavior persists over days. The second part presents the novel combination of MRI with neutron tomography to couple static, proton density information of roots and their interface to the surrounding soil with information about the local water dynamics, reflected by NMR relaxation times. The root soil interface of a broad bean plant is characterized by slightly increasing MRI and NT signal intensity but decreasing T-1 relaxation time indicating locally changed soil properties.}, language = {en} } @article{WadeWoodColladoFregosoetal.2017, author = {Wade, Jessica and Wood, Sebastian and Collado-Fregoso, Elisa and Heeney, Martin and Durrant, James and Kim, Ji-Seon}, title = {Impact of Fullerene Intercalation on Structural and Thermal Properties of Organic Photovoltaic Blends}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {121}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.7b05893}, pages = {20976 -- 20985}, year = {2017}, abstract = {The performance of organic photovoltaic blend devices is critically dependent on the polymer:fullerene interface. These interfaces are expected to impact the structural and thermal properties of the polymer with regards to the conjugated backbone planarity and transition temperatures during annealing/cooling processes. Here, we report the impact of fullerene intercalation on structural and thermal properties of poly(2,5-bis(3-tetradecylthiophen-2-yOthieno[3,2-b]thiophene (PBTTT), a highly stable material known to exhibit liquid crystalline behavior. We undertake a detailed systematic study of the extent of intercalation in the PBTTT:fullerene blend, considering the use of four different fullerene derivatives and also varying the loading ratios. Resonant Raman spectroscopy allows morphology in situ during controlled heating and cooling. We find that small fullerene molecules readily intercalate into PBTTT crystallites, resulting in a planarization of the polymer backbone, but high fullerene loading ratios or larger fullerenes result in nonintercalated domains. During cooling from melt, nonintercalated blend films are found to return to their original morphology and reproduce all thermal transitions on cooling with minimal hysteresis. Intercalated blend films show significant hysteresis on cooling due to the crystallized fullerene attempting to reintercalate. The strongest hysteresis is for intercalated blend films with excess fullerene loading ratio, which form a distinct nanoribbon morphology and exhibit a reduced geminate recombination rate. These results reveal that careful consideration should be taken during device fabrication, as postdeposition thermal treatments significantly impact the charge generation and recombination dynamics.}, language = {en} } @article{KellyRolandZhangetal.2017, author = {Kelly, Mary Allison and Roland, Steffen and Zhang, Qianqian and Lee, Youngmin and Kabius, Bernd and Wang, Qing and Gomez, Enrique D. and Neher, Dieter and You, Wei}, title = {Incorporating Fluorine Substitution into Conjugated Polymers for Solar Cells}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {121}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, number = {4}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.6b10993}, pages = {2059 -- 2068}, year = {2017}, abstract = {Fluorinating conjugated polymers is a proven strategy for creating high performance materials in polymer solar cells, yet few studies have investigated the importance of the fluorination method. We compare the performance of three fluorinated systems: a poly(benzodithieno-dithienyltriazole) (PBnDT-XTAZ) random copolymer where 50\% of the acceptor units are difluorinated, PBnDT-mFTAZ where every acceptor unit is monofluorinated, and a 1:1 physical blend of the difluorinated and nonfluorinated polymer. All systems have the same degree of fluorination (50\%) yet via different methods (chemically vs physically, random vs regular). We show that these three systems have equivalent photovoltaic behavior:,similar to 5.2\% efficiency with a short-circuit current (J(sc)) at,similar to 11 mA cm(-2), an open-circuit voltage (v(oc)) at 0.77 V, and a fill factor (FF) of similar to 60\%. Further investigation of these three systems demonstrates that the charge generation, charge extraction, and charge transfer state are essentially identical for the three studied systems. Transmission electron microscopy shows no significant differences in the morphologies. All these data illustrate that it is possible to improve performance not only via regular or random fluorination but also by physical addition via a ternary blend. Thus, our results demonstrate the versatility of incorporating fluorine in the active layer of polymer solar cells to enhance device performance.}, language = {en} } @article{RumschoettelBausKosmellaetal.2017, author = {Rumsch{\"o}ttel, Jens and Baus, Susann and Kosmella, Sabine and Appelhans, Dietmar and Koetz, Joachim}, title = {Incorporation of DNA/PEI polyplexes into gelatin/chitosan hydrogel scaffolds}, series = {Composite interfaces}, volume = {25}, journal = {Composite interfaces}, number = {1}, publisher = {Routledge, Taylor \& Francis Group}, address = {Abingdon}, issn = {1568-5543}, doi = {10.1080/09276440.2017.1302725}, pages = {1 -- 11}, year = {2017}, abstract = {Polyplexes between a double-stranded Salmon DNA and hyperbranched poly(ethyleneimine) (PEI) as well as a maltosylated PEI-Mal were incorporated into a gelatin/chitosan hydrogel scaffold. Calorimetric experiments of the polyplexes show a decrease of the melting temperature in presence of PEI and a peak splitting in presence of PEI-Mal, which can be interpreted to a partial compaction of the DNA strands in presence of PEI-Mal. When the polyplexes are incorporated into a gelatin/chitosan scaffold in the swollen state, the DNA melting peaks at 90 and 93 degrees C, respectively, indicate in both cases the release of the DNA at the surface of the hydrogel scaffold in a more compact form. Specific interactions between the PEI-Mal shell and gelatin are responsible for the tuning of the release properties in presence of the maltose units in the hyperbranched PEI.}, language = {en} } @article{BrunacciWischkeNaolouetal.2017, author = {Brunacci, Nadia and Wischke, Christian and Naolou, Toufik and Neffe, Axel T. and Lendlein, Andreas}, title = {Influence of surfactants on depsipeptide submicron particle formation}, series = {European Journal of Pharmaceutics and Biopharmaceutics}, volume = {116}, journal = {European Journal of Pharmaceutics and Biopharmaceutics}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0939-6411}, doi = {10.1016/j.ejpb.2016.11.011}, pages = {61 -- 65}, year = {2017}, abstract = {Surfactants are required for the formation and stabilization of hydrophobic polymeric particles in aqueous environment. In order to form submicron particles of varying sizes from oligo[3-(S)-sec-butylmorpholine-2,5-dione]diols ((OBMD)-diol), different surfactants were investigated. As new surfactants, four-armed star-shaped oligo(ethylene glycol)s of molecular weights of 5-20 kDa functionalized with desamino-tyrosine (sOEG-DAT) resulted in smaller particles with lower PDI than with desaminotyrosyl tyrosine (sOEG-DATT) in an emulsion/solvent evaporation method. In a second set of experiments, sOEG-DAT of M-n= 10 kDa was compared with the commonly employed emulsifiers polyvinylalcohol (PVA), polyoxyethylene (20) sorbitan monolaurate (Tween 20), and D-alpha-tocopherol polyethylene glycol succinate (VIT E-TPGS) for OBMD particle preparation. sOEG-DAT allowed to systematically change sizes in a range of 300 up to 900 nm with narrow polydispersity, while in the other cases, a lower size range (250-400 nm, PVA; 300 nm, Tween 20) or no effective particle formation was observed. The ability of tailoring particle size in a broad range makes sOEG-DAT of particular interest for the formation of oligodepsipeptide particles, which can further be investigated as drug carriers for controlled delivery. (C) 2016 Elsevier B.V. All rights reserved.}, language = {en} } @misc{EnzenbergLaschewskyBoeffeletal.2017, author = {Enzenberg, Anne and Laschewsky, Andr{\´e} and Boeffel, Christine and Wischerhoff, Erik}, title = {Influence of the near molecular vicinity on the temperature regulated fluorescence response of poly(N-vinylcaprolactam)}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-400634}, pages = {21}, year = {2017}, abstract = {A series of new fluorescent dye bearing monomers, including glycomonomers, based on maleamide and maleic esteramide was synthesized. The dye monomers were incorporated by radical copolymerization into thermo-responsive poly(N-vinyl-caprolactam) that displays a lower critical solution temperature (LCST) in aqueous solution. The effects of the local molecular environment on the polymers' luminescence, in particular on the fluorescence intensity and the extent of solvatochromism, were investigated below as well as above the phase transition. By attaching substituents of varying size and polarity in the close vicinity of the fluorophore, and by varying the spacer groups connecting the dyes to the polymer backbone, we explored the underlying structure-property relationships, in order to establish rules for successful sensor designs, e.g., for molecular thermometers. Most importantly, spacer groups of sufficient length separating the fluorophore from the polymer backbone proved to be crucial for obtaining pronounced temperature regulated fluorescence responses.}, language = {en} } @article{MondalDeyAttallahetal.2017, author = {Mondal, Suvendu Sekhar and Dey, Subarna and Attallah, Ahmed G. and Krause-Rehberg, Reinhard and Janiak, Christoph and Holdt, Hans-J{\"u}rgen}, title = {Insights into the pores of microwave-assisted metal-imidazolate frameworks showing enhanced gas sorption}, series = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, volume = {46}, journal = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-9226}, doi = {10.1039/c7dt00350a}, pages = {4824 -- 4833}, year = {2017}, abstract = {Microwave heating (MW)-assisted synthesis has been widely applied as an alternative method for the chemical synthesis of organic and inorganic materials. In this work, we report MW-assisted synthesis of three isostructural 3D frameworks with a flexible linker arm of the chelating linker 2-substituted imidazolate- 4-amide-5-imidate, named IFP-7-MW (M = Zn, R = OMe), IFP-8-MW (M = Co; R = OMe) and IFP-10-MW (M = Co; R = OEt) (IFP = Imidazolate Framework Potsdam). These chelating ligands were generated in situ by partial hydrolysis of 2-substituted 4,5-dicyanoimidazoles under MW-and also conventional electrical heating (CE)-assisted conditions in DMF. The structure of these materials was determined by IR spectroscopy and powder X-ray diffraction (PXRD) and the identity of the materials synthesized under CE-conditions was established. Materials obtained from MW-heating show many fold enhancement of CO2 and H-2 uptake capacities, compared to the analogous CE-heating method based materials. To understand the inner pore-sizes of IFP structures and variations of gas sorptions, we performed positron annihilation lifetime spectroscopy (PALS), which shows that MW-assisted materials have smaller pore sizes than materials synthesized under CE-conditions. The "kinetically controlled" MW-synthesized material has an inherent ability to trap extra linkers, thereby reducing the pore sizes of CE-materials to ultra/micropores. These ultramicropores are responsible for high gas sorption.}, language = {en} } @article{BauchKlaperLinker2017, author = {Bauch, Marcel and Klaper, Matthias and Linker, Torsten}, title = {Intermediates in the cleavage of endoperoxides}, series = {Journal of physical organic chemistry}, volume = {30}, journal = {Journal of physical organic chemistry}, publisher = {Wiley}, address = {Hoboken}, issn = {0894-3230}, doi = {10.1002/poc.3607}, pages = {6}, year = {2017}, abstract = {The decomposition of anthracene endoperoxides has been investigated under various conditions. Thermolyses proceed via radical intermediates and afford anthracenes and rearrangement products, depending on the substitution pattern. Interestingly, not only the O-O but also the C-O bond can be cleaved homolytically. Under basic conditions fragmentations take place, affording anthraquinone, and reactive oxygen species. This mechanism explains the often observed decomposition of endoperoxides during work-up. Finally, an acid-catalyzed cleavage has been observed under release of hydrogen peroxide. The results should be interesting for the mechanistic understanding of peroxide decomposition and the endoperoxides might serve as mild sources of reactive oxygen species for future applications. Copyright (C) 2016 John Wiley \& Sons, Ltd.}, language = {en} } @article{ArminDurrantShoaee2017, author = {Armin, Ardalan and Durrant, James R. and Shoaee, Safa}, title = {Interplay Between Triplet-, Singlet-Charge Transfer States and Free Charge Carriers Defining Bimolecular Recombination Rate Constant of Organic Solar Cells}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {121}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.7b04825}, pages = {13969 -- 13976}, year = {2017}, abstract = {Despite the myriad of organic donor:acceptor materials, only few systems have emerged in the life of organic solar cells to, exhibit considerable reduced bimolecular recombination, with respect to the random encounter rate given by the Langevin equation. Monte Carlo simulations have revealed that the rate constant of the formation of electron-hole bound states depends on the random encounter of opposite charges and is nearly given by the Langevin equation for the domain sizes relevant to efficient bulk heterojunction systems. Recently, three studies :suggested that charge transfer states dissociating much faster than their decay rate to the ground state, can result in reduced bimolecular recombination by lowering the recombination rate to the ground state as a loss pathway. A separate study identified another loss pathway and suggested that forbidden back electron transfer from triplet charge transfer states to triplet excitons is a key to achieving reduced recombination. Herein we further explain the reduced bimolecular recombination by investigating the limitations of these two proposals. By solving kinetic rate equations for a BHJ system with realistic rates, we show that both of these previously presented conditions must only be held at the same time fora system to exhibit non-Langevin behavior. We demonstrate that suppression of both of the parallel loss channels of singlet and triplet states can be achieved through increasing the dissociation rate of the charge transfer states; a crucial requirement to achieve a high charge carrier extraction efficiency.}, language = {en} } @phdthesis{Firkala2017, author = {Firkala, Tam{\´a}s}, title = {Investigation of nanoparticle-molecule interactions and pharmaceutical model formulations by means of surface enhanced raman spectroscopy}, school = {Universit{\"a}t Potsdam}, pages = {118}, year = {2017}, language = {en} } @misc{ZehbeKolloscheLardongetal.2017, author = {Zehbe, Kerstin and Kollosche, Matthias and Lardong, Sebastian and Kelling, Alexandra and Schilde, Uwe and Taubert, Andreas}, title = {Ionogels based on poly(methyl methacrylate) and metal-containing ionic liquids}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-400607}, pages = {16}, year = {2017}, abstract = {Ionogels (IGs) based on poly(methyl methacrylate) (PMMA) and the metal-containing ionic liquids (ILs) bis-1-butyl-3-methlimidazolium tetrachloridocuprate(II), tetrachloride cobaltate(II), and tetrachlorido manganate(II) have been synthesized and their mechanical and electrical properties have been correlated with their microstructure. Unlike many previous examples, the current IGs show a decreasing stability in stress-strain experiments on increasing IL fractions. The conductivities of the current IGs are lower than those observed in similar examples in the literature. Both effects are caused by a two-phase structure with micrometer-sized IL-rich domains homogeneously dispersed an IL-deficient continuous PMMA phase. This study demonstrates that the IL-polymer miscibility and the morphology of the IGs are key parameters to control the (macroscopic) properties of IGs.}, language = {en} } @article{DeyouMarcoHeydenreichetal.2017, author = {Deyou, Tsegaye and Marco, Makungu and Heydenreich, Matthias and Pan, Fangfang and Gruhonjic, Amra and Fitzpatrick, Paul A. and Koch, Andreas and Derese, Solomon and Pelletier, Jerry and Rissanen, Kari and Yenesew, Abiy and Erdelyi, Mate}, title = {Isoflavones and Rotenoids from the Leaves of Millettia oblata ssp teitensis}, series = {Journal of natural products}, volume = {80}, journal = {Journal of natural products}, publisher = {American Chemical Society}, address = {Washington}, issn = {0163-3864}, doi = {10.1021/acs.jnatprod.7b00255}, pages = {2060 -- 2066}, year = {2017}, abstract = {A new isoflavone, 8-prenylmilldrone (1), and four new rotenoids, oblarotenoids A-D (2-5), along with nine known compounds (6-14), were isolated from the CH2Cl2/CH3OH (1:1) extract of the leaves of Millettia oblata ssp. teitensis by chromatographic separation. The purified compounds were identified by NMR spectroscopic and mass spectrometric analyses, whereas the absolute configurations of the rotenoids were established on the basis of chiroptical data and in some cases by single-crystal X-ray crystallography. Maximaisoflavone J (11) and oblarotenoid C (4) showed weak activity against the human breast cancer cell line MDA-MB-231 with IC50 values of 33.3 and 93.8 mu M, respectively.}, language = {en} } @article{SchulzeKoetz2017, author = {Schulze, Nicole and Koetz, Joachim}, title = {Kinetically controlled growth of gold nanotriangles in a vesicular template phase by adding a strongly alternating polyampholyte}, series = {Journal of dispersion science and technology}, volume = {38}, journal = {Journal of dispersion science and technology}, number = {8}, publisher = {Taylor \& Francis}, address = {Philadelphia}, issn = {0193-2691}, doi = {10.1080/01932691.2016.1220318}, pages = {1073 -- 1078}, year = {2017}, abstract = {This paper is focused on the temperature-dependent synthesis of gold nanotriangles in a vesicular template phase, containing phosphatidylcholine and AOT, by adding the strongly alternating polyampholyte PalPhBisCarb. UV-vis absorption spectra in combination with TEM micrographs show that flat gold nanoplatelets are formed predominantly in the presence of the polyampholyte at 45°C. The formation of triangular and hexagonal nanoplatelets can be directly influenced by the kinetic approach, i.e., by varying the polyampholyte dosage rate at 45°C. Corresponding zeta potential measurements indicate that a temperature-dependent adsorption of the polyampholyte on the {111} faces will induce the symmetry breaking effect, which is responsible for the kinetically controlled hindered vertical and preferred lateral growth of the nanoplatelets.}, language = {en} } @article{OnalSassHurpinetal.2017, author = {Onal, Emel and Sass, Stephan and Hurpin, Jeanne and Ertekin, Kadriye and Topal, Sevinc Zehra and Kumke, Michael Uwe and Hirel, Catherine}, title = {Lifetime-Based Oxygen Sensing Properties of palladium(II) and platinum(II) meso-tetrakis(4-phenylethynyl)phenylporphyrin}, series = {Journal of fluorescence}, volume = {27}, journal = {Journal of fluorescence}, publisher = {Springer}, address = {New York}, issn = {1053-0509}, doi = {10.1007/s10895-016-2022-x}, pages = {861 -- 868}, year = {2017}, abstract = {High oxygen permeable [poly(TMSP)] nanofibers incorporating porphyrin macrocycle as luminescence indicators were prepared by electrospinning technique. The porphyrins involves were modified by i) introducing phenylacetylide substituents on the para position of the phenyl moieties and ii) varying the metal centers [Pt(II) or Pd(II)] of the meso-tetrakisphenylporphyrins. A set of nanofibers; (Pt-TPP)NF, (Pd-TPP)NF, (Pt-TPA)NF and (Pd-TPA)NF were obtained to study their structure-activity relationship toward oxygen. The lifetime-based technique was privileged to take advantage of their long-lived phosphorescent properties. A two-fold enhancement was observed for (Pt-TPA)NF and (Pd-TPA)NF compared to (Pt-TPP)NF and (Pd-TPP)NF demonstrating the positive effect of the phenylacetylide moieties on the lifetime. Also, Silver nanoparticles were included in nanofibers to investigate their influence on lifetime-based oxygen sensitivity, showing that the presence of AgNPs only affects (Pd-TPA)NF.}, language = {en} } @phdthesis{Graglia2017, author = {Graglia, Micaela}, title = {Lignin valorization}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-104863}, school = {Universit{\"a}t Potsdam}, pages = {133}, year = {2017}, abstract = {The topic of this project is the use of lignin as alternative source of aromatic building blocks and oligomers to fossil feedstocks. Lignin is known as the most abundant aromatic polymer in nature and is isolated from the lignocellulosic component of plants by different possible extraction treatments. Both the biomass source and the extraction method affect the structure of the isolated lignin, therefore influencing its further application. Lignin was extracted from beech wood by two different hydrothermal alkaline treatments, which use NaOH and Ba(OH)2 as base and by an acid-catalyzed organosolv process. Moreover, lignin was isolated from bamboo, beech wood and coconut by soda treatment of the biomasses. A comparison of the structural features of such isolated lignins was performed through the use of a wide range of analytical methods. Alkaline lignins resulted in a better candidate as carbon precursor and macromonomers for the synthesis of polymer than organosolv lignin. In fact, alkaline lignins showed higher residual mass after carbonization and higher content of the reactive hydroxy functionalities. In contrast, the lignin source turned out to slightly affect the lignin hydroxyl content. One of the most common lignin modifications is its deconstruction to obtain aromatic molecules, which can be used as starting materials for the synthesis of fine chemicals. Lignin deconstruction leads to a complex mixture of aromatic molecules. A gas chromatographic analytical method was developed to characterize the mixture of products obtained by lignin deconstruction via heterogeneous catalytic hydrogenolysis. The analytical protocol allowed the quantification of three main groups of molecules by means of calibration curves, internal standard and a preliminary silylation step of the sample. The analytical method was used to study the influence of the hydrogenolysis catalyst, temperature and system (flow and batch reactor) on the yield and selectivity of the aromatic compounds. Lignin extracted from beech wood by a hydrothermal process using Ba(OH)2 as base, was functionalized by aromatic nitration in order to add nitrogen functionalities. The final goal was the synthesis of a nitrogen doped carbon. Nitrated lignin was reduced to the amino form in order to compare the influence of different nitrogen functionalities on the porosity of the final carbon. The carbons were obtained by ionothermal treatment of the precursors in the presence of the eutectic salt mixture KCl/ZnCl2 Such synthesized carbons showed micro-, macro- and mesoporosity and were tested for their electrocatalytic activity towards the oxygen reduction reaction. Mesoporous carbon derived from nitro lignin displayed the highest electrocatalytic activity. Lignins isolated from coconut, beech wood and bamboo were used as macromonomers for the synthesis of biobased polyesters. A condensation reaction was performed between lignin and a hyper branched poly(ester-amine), previously obtained by condensation of triethanolamine and adipic acid. The influence of the lignin source and content on the thermochemical and mechanical properties of the final material was investigated. The prepolymer showed adhesive properties towards aluminum and its shear strength was therefore measured. The gluing properties of such synthesized glues turned out to be independent from the lignin source but affected by the amount of lignin in the final material. This work shows that, although still at a laboratory scale, the valorization of lignin can overcome the critical issues of lignin´s structure variability and complexity.}, language = {en} } @misc{HuZhaoZhangetal.2017, author = {Hu, Shuangyan and Zhao, Junpeng and Zhang, Guangzhao and Schlaad, Helmut}, title = {Macromolecular architectures through organocatalysis}, series = {Progress in Polymer Science}, volume = {74}, journal = {Progress in Polymer Science}, publisher = {Elsevier}, address = {Oxford}, issn = {0079-6700}, doi = {10.1016/j.progpolymsci.2017.07.002}, pages = {34 -- 77}, year = {2017}, abstract = {In virtue of the rising demand for metal-free polymeric materials, organocatalytic polymerization has emerged and blossomed unprecedentedly in the past 15 years into an appealing research area and a powerful arsenal for polymer synthesis. In addition to the inherent merits as being metal-free, small molecule organocatalysts have also provided opportunities to develop alternative and, in many cases, more expedient synthetic approaches toward macromolecular architectures, that play a crucial role in shaping the properties of the obtained polymers. A majority of preliminary studies exploring for new catalysts, catalytic mechanisms and optimized polymerization conditions are extended to application of the catalytic systems on rational design and controlled synthesis of various macromolecular architectures. Such endeavors are described in this review, categorized by the architectural elements including chain structure (types, sequence and composition of monomeric units constituting the polymer chains), topological structure (the fashion different polymer chains are covalently attached to each other within the macromolecule) and functionality (position and amount of functional groups that endow the entire macromolecule with specific chemical, physico-chemical or biological properties). (C) 2017 Published by Elsevier B.V.}, language = {en} } @article{GhaisariWinklhoferStrauchetal.2017, author = {Ghaisari, Sara and Winklhofer, Michael and Strauch, Peter and Klumpp, Stefan and Faivre, Damien}, title = {Magnetosome Organization in Magnetotactic Bacteria Unraveled by Ferromagnetic Resonance Spectroscopy}, series = {Biophysical journal}, volume = {113}, journal = {Biophysical journal}, publisher = {Cell Press}, address = {Cambridge}, issn = {0006-3495}, doi = {10.1016/j.bpj.2017.06.031}, pages = {637 -- 644}, year = {2017}, abstract = {Magnetotactic bacteria form assemblies of magnetic nanoparticles called magnetosomes. These magnetosomes are typically arranged in chains, but other forms of assemblies such as clusters can be observed in some species and genetic mutants. As such, the bacteria have developed as a model for the understanding of how organization of particles can influence the magnetic properties. Here, we use ferromagnetic resonance spectroscopy to measure the magnetic anisotropies in different strains of Magnetosprillum gtyphiswaldense MSR-1, a bacterial species that is amendable to genetic mutations. We combine our experimental results with a model describing the spectra. The model includes chain imperfections and misalignments following a Fisher distribution function, in addition to the intrinsic magnetic properties of the magnetosomes. Therefore, by applying the model to analyze the ferromagnetic resonance data, the distribution of orientations in the bulk sample can be retrieved in addition to the average magnetosome arrangement. In this way, we quantitatively characterize the magnetosome arrangement in both wild-type cells and Delta mamJ mutants, which exhibit differing magnetosome organization.}, language = {en} } @article{KarpitschkaLiebigRiegler2017, author = {Karpitschka, Stefan and Liebig, Ferenc and Riegler, Hans}, title = {Marangoni Contraction of Evaporating Sessile Droplets of Binary Mixtures}, series = {Langmuir}, volume = {33}, journal = {Langmuir}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.7b00740}, pages = {4682 -- 4687}, year = {2017}, abstract = {The Marangoni contraction of sessile drops of a binary mixture of a volatile and a nonvolatile liquid has been investigated experimentally and theoretically. The origin of the contraction is the locally inhomogeneous evaporation rate of sessile drops. This leads to surface tension gradients and thus to a Marangoni flow. Simulations show that the interplay of Marangoni flow, capillary flow, diffusive transport, and evaporative losses can establish a quasistationary drop profile with an apparent nonzero contact angle even if both liquid components individually wet the substrate completely. Experiments with different solvents, initial mass fractions, and gaseous environments reveal a previously unknown universal power-law relation between the apparent contact angle and the relative undersaturation of the ambient atmosphere: theta(app) similar to (RHeq - RH)(1/3). This experimentally observed power law is in quantitative agreement with simulation results. The exponent can also be inferred from a scaling analysis of the hydrodynamic-evaporative evolution equations of a binary mixture of liquids with different volatilities.}, language = {en} } @article{SprengerErbanSeddigetal.2017, author = {Sprenger, Heike and Erban, Alexander and Seddig, Sylvia and Rudack, Katharina and Thalhammer, Anja and Le, Mai Q. and Walther, Dirk and Zuther, Ellen and Koehl, Karin I. and Kopka, Joachim and Hincha, Dirk K.}, title = {Metabolite and transcript markers for the prediction of potato drought tolerance}, series = {Plant Biotechnology Journal}, volume = {16}, journal = {Plant Biotechnology Journal}, number = {4}, publisher = {Wiley}, address = {Hoboken}, issn = {1467-7644}, doi = {10.1111/pbi.12840}, pages = {939 -- 950}, year = {2017}, abstract = {Potato (Solanum tuberosum L.) is one of the most important food crops worldwide. Current potato varieties are highly susceptible to drought stress. In view of global climate change, selection of cultivars with improved drought tolerance and high yield potential is of paramount importance. Drought tolerance breeding of potato is currently based on direct selection according to yield and phenotypic traits and requires multiple trials under drought conditions. Marker-assisted selection (MAS) is cheaper, faster and reduces classification errors caused by noncontrolled environmental effects. We analysed 31 potato cultivars grown under optimal and reduced water supply in six independent field trials. Drought tolerance was determined as tuber starch yield. Leaf samples from young plants were screened for preselected transcript and nontargeted metabolite abundance using qRT-PCR and GC-MS profiling, respectively. Transcript marker candidates were selected from a published RNA-Seq data set. A Random Forest machine learning approach extracted metabolite and transcript markers for drought tolerance prediction with low error rates of 6\% and 9\%, respectively. Moreover, by combining transcript and metabolite markers, the prediction error was reduced to 4.3\%. Feature selection from Random Forest models allowed model minimization, yielding a minimal combination of only 20 metabolite and transcript markers that were successfully tested for their reproducibility in 16 independent agronomic field trials. We demonstrate that a minimum combination of transcript and metabolite markers sampled at early cultivation stages predicts potato yield stability under drought largely independent of seasonal and regional agronomic conditions.}, language = {en} } @article{BehrendtSchlaad2017, author = {Behrendt, Felix Nicolas and Schlaad, Helmut}, title = {Metathesis polymerization of cystine-based macrocycles}, series = {Polymer Chemistry}, volume = {8}, journal = {Polymer Chemistry}, number = {2}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1759-9954}, doi = {10.1039/c6py01864e}, pages = {366 -- 369}, year = {2017}, abstract = {Macrocycles based on L-cystine were synthesized by ring-closing metathesis (RCM) and subsequently polymerized by entropy-driven ring-opening metathesis polymerization (ED-ROMP). Monomer conversion reached similar to 80\% in equilibrium and the produced poly (ester-amine-disulfide-alkene)s exhibited apparent molar masses (M-w(app)) of up to 80 kDa and dispersities (D) of similar to 2. The polymers can be further functionalized with acid anhydrides and degraded by reductive cleavage of the main-chain disulfide.}, language = {en} } @article{MichalikOnichimowskaBeitzPanneetal.2017, author = {Michalik-Onichimowska, Aleksandra and Beitz, Toralf and Panne, Ulrich and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Riedel, Jens}, title = {Microsecond mid-infrared laser pulses for atmospheric pressure laser ablation/ionization of liquid samples}, series = {Sensors and actuators : B, Chemical}, volume = {238}, journal = {Sensors and actuators : B, Chemical}, publisher = {Elsevier}, address = {Lausanne}, issn = {0925-4005}, doi = {10.1016/j.snb.2016.06.155}, pages = {298 -- 305}, year = {2017}, abstract = {In many laser based ionization techniques with a subsequent drift time separation, the laser pulse generating the ions is considered as the start time to. Therefore, an accurate temporal definition of this event is crucial for the resolution of the experiments. In this contribution, the laser induced plume dynamics of liquids evaporating into atmospheric pressure are visualized for two distinctively different laser pulse widths, Delta t = 6 nanoseconds and Delta tau = 280 microseconds. For ns-pulses the expansion of the generated vapour against atmospheric pressure is found to lead to turbulences inside the gas phase. This results in spatial and temporal broadening of the nascent clouds. A more equilibrated expansion, without artificial smearing of the temporal resolution can, in contrast, be observed to follow mu s-pulse excitation. This leads to the counterintuitive finding that longer laser pulses results in an increased temporal vapour formation definition. To examine if this fume expansion also eventually results in a better definition of ion formation, the nascent vapour plumes were expanded into a linear drift tube ion mobility spectrometer (IMS). This time resolved detection of ion formation corroborates the temporal broadening caused by collisional impeding of the supersonic expansion at atmospheric pressure and the overall better defined ion formation by evaporation with long laser pulses. A direct comparison of the observed results strongly suggests the coexistence of two individual ion formation mechanisms that can be specifically addressed by the use of appropriate laser sources.}, language = {en} } @article{SchmidtRiemer2017, author = {Schmidt, Bernd and Riemer, Martin}, title = {Microwave-Promoted Pd-Catalyzed Synthesis of Dibenzofurans from Ortho-Arylphenols}, series = {Journal of Heterocyclic Chemistry}, volume = {54}, journal = {Journal of Heterocyclic Chemistry}, number = {2}, publisher = {Wiley}, address = {Hoboken}, issn = {0022-152X}, doi = {10.1002/jhet.2704}, pages = {1287 -- 1297}, year = {2017}, abstract = {ortho-Aryl phenols, synthesized via protecting group free Suzuki-Miyaura coupling of ortho-halophenols and arene boronic acids, undergo a cyclization to dibenzofurans via oxidative C-H activation. The reaction proceeds under microwave irradiation in short reaction times using catalytic amounts of Pd(OAc)(2) without additional ligands.}, language = {en} } @article{ShainyanBelyakovSigolaevetal.2017, author = {Shainyan, Bagrat A. and Belyakov, Alexander V. and Sigolaev, Yurii F. and Khramov, Alexander N. and Kleinpeter, Erich}, title = {Molecular Structure and Conformational Analysis of 1-Phenyl-1-X-1-Silacyclohexanes (X = F, Cl) by Electron Diffraction, Low-Temperature NMR, and Quantum Chemical Calculations}, series = {The journal of organic chemistry}, volume = {82}, journal = {The journal of organic chemistry}, number = {1}, publisher = {American Chemical Society}, address = {Washington}, issn = {0022-3263}, doi = {10.1021/acs.joc.6b02538}, pages = {461 -- 470}, year = {2017}, abstract = {The molecular structure and conformational preferences of 1-phenyl-1-X-1-silacyclohexanes C5H10Si(Ph,X) (X = F (3), Cl (4)) were studied by gas-phase electron diffraction, low-temperature NMR spectroscopy, and high-level quantum chemical calculations. In the gas phase only three (3) and two (4) stable conformers differing in the axial or equatorial location of the phenyl group and the angle of rotation about the Si-C-ph bond (axi and axo denote the Ph group lying in or out of the X-Si-C-ph plane) contribute to the equilibrium. In 3 the ratio Ph-eq:Ph-axo:Ph-axi is 40(12):55(24):5 and 64:20:16 by experiment and theory, respectively. In 4 the ratio Ph-eq:Ph-axo is 79(15):21(15) and 71:29 by experiment and theory (M06-2X calculations), respectively. The gas-phase electron diffraction parameters are in good agreement with those obtained from theory at the M06-2X/aug-ccPVTZ and MP2/aug-cc-pVTZ levels. Unlike the case for M06-2X, MP2 calculations indicate that 3-Ph-eq conformer lies 0.5 kcal/mol higher than the 3-Ph-axo, conformer. As follows from QTAIM analysis, the phenyl group is more stable when it is located in the axial position but produces destabilization of the silacyclohexane ring: By low temperature NMR spectroscopy the six-membered ring interconversion could be frozen, at 103 K and the present conformational equilibria of 3 and 4 could be determined. The ratio of the conformers is 3-Ph-eq:3-Ph-ax = (75-77):(23-25) and 4-Ph-eq:4-Ph-ax = 82:18.}, language = {en} } @article{ThirumalaikumarDevkarMehterovetal.2017, author = {Thirumalaikumar, Venkatesh P. and Devkar, Vikas and Mehterov, Nikolay and Ali, Shawkat and Ozgur, Rengin and Turkan, Ismail and M{\"u}ller-R{\"o}ber, Bernd and Balazadeh, Salma}, title = {NAC transcription factor JUNGBRUNNEN1 enhances drought tolerance in tomato}, series = {Plant Biotechnology Journal}, volume = {16}, journal = {Plant Biotechnology Journal}, number = {2}, publisher = {Wiley}, address = {Hoboken}, issn = {1467-7644}, doi = {10.1111/pbi.12776}, pages = {354 -- 366}, year = {2017}, abstract = {Water deficit (drought stress) massively restricts plant growth and the yield of crops; reducing the deleterious effects of drought is therefore of high agricultural relevance. Drought triggers diverse cellular processes including the inhibition of photosynthesis, the accumulation of cell-damaging reactive oxygen species and gene expression reprogramming, besides others. Transcription factors (TF) are central regulators of transcriptional reprogramming and expression of many TF genes is affected by drought, including members of the NAC family. Here, we identify the NAC factor JUNGBRUNNEN1 (JUB1) as a regulator of drought tolerance in tomato (Solanum lycopersicum). Expression of tomato JUB1 (SlJUB1) is enhanced by various abiotic stresses, including drought. Inhibiting SlJUB1 by virus-induced gene silencing drastically lowers drought tolerance concomitant with an increase in ion leakage, an elevation of hydrogen peroxide (H2O2) levels and a decrease in the expression of various drought-responsive genes. In contrast, overexpression of AtJUB1 from Arabidopsis thaliana increases drought tolerance in tomato, alongside with a higher relative leaf water content during drought and reduced H2O2 levels. AtJUB1 was previously shown to stimulate expression of DREB2A, a TF involved in drought responses, and of the DELLA genes GAI and RGL1. We show here that SlJUB1 similarly controls the expression of the tomato orthologs SlDREB1, SlDREB2 and SlDELLA. Furthermore, AtJUB1 directly binds to the promoters of SlDREB1, SlDREB2 and SlDELLA in tomato. Our study highlights JUB1 as a transcriptional regulator of drought tolerance and suggests considerable conservation of the abiotic stress-related gene regulatory networks controlled by this NAC factor between Arabidopsis and tomato.}, language = {en} } @article{CharanGlebeAnandetal.2017, author = {Charan, Himanshu and Glebe, Ulrich and Anand, Deepak and Kinzel, Julia and Zhu, Leilei and Bocola, Marco and Garakani, Tayebeh Mirzaei and Schwaneberg, Ulrich and B{\"o}ker, Alexander}, title = {Nano-thin walled micro-compartments from transmembrane protein-polymer conjugates}, series = {Soft matter}, volume = {13}, journal = {Soft matter}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1744-683X}, doi = {10.1039/c6sm02520j}, pages = {2866 -- 2875}, year = {2017}, abstract = {The high interfacial activity of protein-polymer conjugates has inspired their use as stabilizers for Pickering emulsions, resulting in many interesting applications such as synthesis of templated micro-compartments and protocells or vehicles for drug and gene delivery. In this study we report, for the first time, the stabilization of Pickering emulsions with conjugates of a genetically modified transmembrane protein, ferric hydroxamate uptake protein component A (FhuA). The lysine residues of FhuA with open pore (FhuA Delta CVFtev) were modified to attach an initiator and consequently controlled radical polymerization (CRP) carried out via the grafting-from technique. The resulting conjugates of FhuA Delta CVFtev with poly(N-isopropylacrylamide) (PNIPAAm) and poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA), the so-called building blocks based on transmembrane proteins (BBTP), have been shown to engender larger structures. The properties such as pH-responsivity, temperature-responsivity and interfacial activity of the BBTP were analyzed using UV-Vis spectrophotometry and pendant drop tensiometry. The BBTP were then utilized for the synthesis of highly stable Pickering emulsions, which could remain non-coalesced for well over a month. A new UV-crosslinkable monomer was synthesized and copolymerized with NIPAAm from the protein. The emulsion droplets, upon crosslinking of polymer chains, yielded micro-compartments. Fluorescence microscopy proved that these compartments are of micrometer scale, while cryo-scanning electron microscopy and scanning force microscopy analysis yielded a thickness in the range of 11.1 +/- 0.6 to 38.0 +/- 18.2 nm for the stabilizing layer of the conjugates. Such micro-compartments would prove to be beneficial in drug delivery applications, owing to the possibility of using the channel of the transmembrane protein as a gate and the smart polymer chains as trigger switches to tune the behavior of the capsules.}, language = {en} } @misc{NaolouRuehlLendlein2017, author = {Naolou, Toufik and R{\"u}hl, Eckart and Lendlein, Andreas}, title = {Nanocarriers}, series = {European Journal of Pharmaceutics and Biopharmaceutics}, volume = {116}, journal = {European Journal of Pharmaceutics and Biopharmaceutics}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0939-6411}, doi = {10.1016/j.ejpb.2017.03.004}, pages = {1 -- 3}, year = {2017}, language = {en} } @article{KleinpeterHeydenreichKochetal.2017, author = {Kleinpeter, Erich and Heydenreich, Matthias and Koch, Andreas and Krtitschka, Angela and Kr{\"u}ger, Tobias and Linker, Torsten}, title = {NMR spectroscopic conformational analysis of 4-methylene-cyclohexyl pivalateThe effect of sp(2) hybridization}, series = {Magnetic resonance in chemistry}, volume = {55}, journal = {Magnetic resonance in chemistry}, publisher = {Wiley}, address = {Hoboken}, issn = {0749-1581}, doi = {10.1002/mrc.4630}, pages = {1073 -- 1078}, year = {2017}, abstract = {The conformational equilibrium of the axial/equatorial conformers of 4-methylene-cyclohexyl pivalate is studied by dynamic NMR spectroscopy in a methylene chloride/freon mixture. At 153K, the ring interconversion gets slow on the nuclear magnetic resonance timescale, the conformational equilibrium (-G degrees) can be examined, and the barrier to ring interconversion (G(\#)) can be determined. The structural influence of sp(2) hybridization on both G degrees and G(\#) of the cyclohexyl moiety can be quantified.}, language = {en} } @article{FarhanRudolphNoecheletal.2017, author = {Farhan, Muhammad and Rudolph, Tobias and N{\"o}chel, Ulrich and Yan, Wan and Kratz, Karl and Lendlein, Andreas}, title = {Noncontinuously Responding Polymeric Actuators}, series = {ACS applied materials \& interfaces}, volume = {9}, journal = {ACS applied materials \& interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.7b11316}, pages = {33559 -- 33564}, year = {2017}, abstract = {Reversible movements of current polymeric actuators stem from the continuous response to signals from a controlling unit, and subsequently cannot be interrupted without stopping or eliminating the input trigger. Here, we present actuators based on cross-linked blends of two crystallizable polymers capable of pausing their movements in a defined manner upon continuous cyclic heating and cooling. This noncontinuous actuation can be adjusted by varying the applied heating and cooling rates. The feasibility of these devices for technological applications was shown in a 140 cycle experiment of free-standing noncontinuous shape shifts, as well as by various demonstrators.}, language = {en} } @article{UnuabonahKolawoleAgunbiadeetal.2017, author = {Unuabonah, Emmanuel Iyayi and Kolawole, Matthew O. and Agunbiade, Foluso O. and Omorogie, Martins O. and Koko, Daniel T. and Ugwuja, Chidinma G. and Ugege, Leonard E. and Oyejide, Nicholas E. and G{\"u}nter, Christina and Taubert, Andreas}, title = {Novel metal-doped bacteriostatic hybrid clay composites for point-of-use disinfection of water}, series = {Journal of Environmental Chemical Engineering}, volume = {5}, journal = {Journal of Environmental Chemical Engineering}, publisher = {Elsevier}, address = {Oxford}, issn = {2213-3437}, doi = {10.1016/j.jece.2017.04.017}, pages = {2128 -- 2141}, year = {2017}, abstract = {This study reports the facile microwave-assisted thermal preparation of novel metal-doped hybrid clay composite adsorbents consisting of Kaolinite clay, Carica papaya seeds and/or plantain peels (Musa paradisiaca) and ZnCl2. Fourier Transformed IR spectroscopy, X-ray diffraction, Scanning Electron Microscopy and Brunauer-Emmett-Teller (BET) analysis are employed to characterize these composite adsorbents. The physicochemical analysis of these composites suggests that they act as bacteriostatic rather than bacteriacidal agents. This bacterostactic action is induced by the ZnO phase in the composites whose amount correlates with the efficacy of the composite. The composite prepared with papaya seeds (PS-HYCA) provides the best disinfection efficacy (when compared with composite prepared with Musa paradisiaca peels-PP-HYCA) against gram-negative enteric bacteria with a breakthrough time of 400 and 700 min for the removal of 1.5 x10(6) cfu/mL S. typhi and V. cholerae from water respectively. At 10(3) cfu/mL of each bacterium in solution, 2 g of both composite adsorbents kept the levels the bacteria in effluent solutions at zero for up to 24 h. Steam regeneration of 2 g of bacteria-loaded Carica papaya prepared composite adsorbent shows a loss of ca. 31\% of its capacity even after the 3rd regeneration cycle of 25 h of service time. The composite adsorbent prepared with Carica papaya seeds will be useful for developing simple point-of-use water treatment systems for water disinfection application. This composite adsorbent is comparatively of good performance and shows relatively long hydraulic contact times and is expected to minimize energy intensive traditional treatment processes.}, language = {en} } @article{WolfHolzmeierWagneretal.2017, author = {Wolf, Thomas J. A. and Holzmeier, Fabian and Wagner, Isabella and Berrah, Nora and Bostedt, Christoph and Bozek, John and Bucksbaum, Phil and Coffee, Ryan and Cryan, James and Farrell, Joe and Feifel, Raimund and Martinez, Todd J. and McFarland, Brian and Mucke, Melanie and Nandi, Saikat and Tarantelli, Francesco and Fischer, Ingo and G{\"u}hr, Markus}, title = {Observing Femtosecond Fragmentation Using Ultrafast X-ray-Induced Auger Spectra}, series = {Applied sciences}, volume = {7}, journal = {Applied sciences}, number = {7}, publisher = {MDPI}, address = {Basel}, issn = {2076-3417}, doi = {10.3390/app7070681}, pages = {11}, year = {2017}, abstract = {Molecules often fragment after photoionization in the gas phase. Usually, this process can only be investigated spectroscopically as long as there exists electron correlation between the photofragments. Important parameters, like their kinetic energy after separation, cannot be investigated. We are reporting on a femtosecond time-resolved Auger electron spectroscopy study concerning the photofragmentation dynamics of thymine. We observe the appearance of clearly distinguishable signatures from thymines neutral photofragment isocyanic acid. Furthermore, we observe a time-dependent shift of its spectrum, which we can attribute to the influence of the charged fragment on the Auger electron. This allows us to map our time-dependent dataset onto the fragmentation coordinate. The time dependence of the shift supports efficient transformation of the excess energy gained from photoionization into kinetic energy of the fragments. Our method is broadly applicable to the investigation of photofragmentation processes.}, language = {en} } @article{GuelzowHoernerStrauchetal.2017, author = {Guelzow, Jana and Hoerner, Gerald and Strauch, Peter and Stritt, Anika and Irran, Elisabeth and Grohmann, Andreas}, title = {Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201605868}, pages = {7009 -- 7023}, year = {2017}, abstract = {Deprotonation of ligand-appended alkoxyl groups in mononuclear copper(II) complexes of N,O ligands L-1 and L-2, gave dinuclear complexes sharing symmetrical Cu2O2 cores. Molecular structures of these mono-and binuclear complexes have been characterized by XRD, and their electronic structures by UV/Vis, H-1 NMR, EPR and DFT; moreover, catalytic performance as models of catechol oxidase was studied. The binuclear complexes with anti-ferromagnetically coupled copper(II) centers are moderately active in quinone formation from 3,5-di-tert-butyl-catechol under the estab-lished conditions of oxygen saturation, but are strongly activated when additional dioxygen is administered during catalytic turnover. This unforeseen and unprecedented effect is attributed to increased maximum reaction rates v(max), whereas the substrate affinity KM remains unaffected. Oxygen administration is capable of (partially) removing limitations to turnover caused by product inhibition. Because product inhibition is generally accepted to be a major limitation of catechol oxidase models, we think that our observations will be applicable more widely.}, language = {en} } @article{YouBehlLoewenbergetal.2017, author = {You, Zewang and Behl, Marc and L{\"o}wenberg, Candy and Lendlein, Andreas}, title = {pH-sensitivity and conformation change of the n-terminal methacrylated peptide VK20}, series = {MRS advances : a journal of the Materials Research Society (MRS)}, volume = {2}, journal = {MRS advances : a journal of the Materials Research Society (MRS)}, publisher = {Cambridge University Press}, address = {Cambridge}, issn = {2059-8521}, doi = {10.1557/adv.2017.491}, pages = {2571 -- 2579}, year = {2017}, abstract = {N-terminal methacrylation of peptide MAXI, which is capable of conformational changes variation of the pH, results in a peptide, named VK20. Increasing the reactivity of this terminal group enables further coupling reactions or chemical modifications of the peptidc. However, this end group functionalization may influence the ability of confonnational changes of VK20; as well as its properties. In this paper; the influence of pH on the transition between random coil and beta-sheet conformation of VK20; including the transition kinetics, were investigated. At pH values of 9 and higher, the kinetics beta-sheet formation increased tor VK(2 0, compared to MAXI. The self-assembly into beta-sheets recognized by the formation of a physically crosslinked gel was furthermore indicated by a significant increase of G. An increase in pH (from 9 to 9.5) led to a faster gelation of the peptide VK20. Simultaneously, G was increased from 460 +/- 70 Pa (at pH 9) to 1520 +/- 180 Pa (at pH 9.5). At the nanoscale, the gel showed a highly interconnected fibrillar/network structure with uniform fibril widths of approximately 3.4 +/- 0.5 nm (N=30). The recovery of the peptide conformation back to random coil resulted in the dissolution of the gel; whereby the kinetics of the recovery depended on the pH. Conclusively, the ability of MAXI to undergo confommtional changes was not affected by N-terminal methacrylation whereas the kinetics of pH-sensitive beta-sheet formations has been increased.}, language = {en} } @misc{HassSandmannReich2017, author = {Hass, Roland and Sandmann, Michael and Reich, Oliver}, title = {Photonic sensing in highly concentrated biotechnical processes by photon density wave spectroscopy}, series = {Proceedings SPIE 10323, 25th International Conference on Optical Fiber Sensors}, volume = {10323}, journal = {Proceedings SPIE 10323, 25th International Conference on Optical Fiber Sensors}, publisher = {IEEE}, address = {New York}, isbn = {978-1-5090-4850-2}, issn = {0277-786X}, doi = {10.1117/12.2263617}, pages = {4}, year = {2017}, abstract = {Photon Density Wave (PDW) spectroscopy is introduced as a new approach for photonic sensing in highly concentrated biotechnical processes. It independently quantifies the absorption and reduced scattering coefficient calibration-free and as a function of time, thus describing the optical properties in the vis/NIR range of the biomaterial during their processing. As examples of industrial relevance, enzymatic milk coagulation, beer mashing, and algae cultivation in photo bioreactors are discussed.}, language = {en} } @article{BauchKrtitschkaLinker2017, author = {Bauch, Marcel and Krtitschka, Angela and Linker, Torsten}, title = {Photooxygenation of oxygen-substituted naphthalenes}, series = {Journal of physical organic chemistry}, volume = {30}, journal = {Journal of physical organic chemistry}, publisher = {Wiley}, address = {Hoboken}, issn = {0894-3230}, doi = {10.1002/poc.3734}, pages = {6803 -- 6813}, year = {2017}, abstract = {The reaction of oxygen-substituted naphthalenes with singlet oxygen (O-1(2)) has been investigated, and labile endoperoxides have been isolated and characterized at -78 degrees C for the first time. Low-temperature kinetics by UV spectroscopy revealed that alkoxy and silyloxy substituents remarkably increase the rate of photooxygenations compared to 1,4-dimethylnaphthalene, whereas acyloxy-substituted acenes are inert towards O-1(2). The reactivities nicely correlate with HOMO energies and free activation energies, which we determined by density functional theory calculations. The lability of the isolated endoperoxides is due to their very fast back reaction to the corresponding naphthalenes even at -20 degrees C under release of O-1(2), making them to superior sources of this reactive species under very mild conditions. Finally, a carbohydrate-substituted naphthalene has been synthesized, which reacts reversibly with O-1(2) and might be applied for enantioselective oxidations in future work.}, language = {en} } @article{MalyarTitovLomadzeetal.2017, author = {Malyar, Ivan V. and Titov, Evgenii and Lomadze, Nino and Saalfrank, Peter and Santer, Svetlana}, title = {Photoswitching of azobenzene-containing self-assembled monolayers as a tool for control over silicon surface electronic properties}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {146}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4978225}, pages = {8}, year = {2017}, abstract = {We report on photoinduced remote control of work function and surface potential of a silicon surface modified with a photosensitive self-assembled monolayer consisting of chemisorbed azobenzene molecules (4-nitroazobenzene). Itwas found that the attachment of the organic monolayer increases the work function by hundreds of meV due to the increase in the electron affinity of silicon substrates. The change in the work function on UV light illumination is more pronounced for the azobenzene jacketed silicon substrate (ca. 250 meV) in comparison to 50 meV for the unmodified surface. Moreover, the photoisomerization of azobenzene results in complex kinetics of thework function change: immediate decrease due to light-driven processes in the silicon surface followed by slower recovery to the initial state due to azobenzene isomerization. This behavior could be of interest for electronic devices where the reaction on irradiation should be more pronounced at small time scales but the overall surface potential should stay constant over time independent of the irradiation conditions. Published by AIP Publishing.}, language = {en} } @article{WangNaolouMaetal.2017, author = {Wang, Weiwei and Naolou, Toufik and Ma, Nan and Deng, Zijun and Xu, Xun and Mansfeld, Ulrich and Wischke, Christian and Gossen, Manfred and Neffe, Axel T. and Lendlein, Andreas}, title = {Polydepsipeptide Block-Stabilized Polyplexes for Efficient Transfection of Primary Human Cells}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {18}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/acs.biomac.7b01034}, pages = {3819 -- 3833}, year = {2017}, abstract = {The rational design of a polyplex gene carrier aims to balance maximal effectiveness of nucleic acid transfection into cells with minimal adverse effects. Depsipeptide blocks with an M (n) similar to 5 kDa exhibiting strong physical interactions were conjugated with PEI moieties (2.5 or 10 kDa) to di- and triblock copolymers. Upon nanoparticle formation and complexation with DNA, the resulting polyplexes (sizes typically 60-150 nm) showed remarkable stability compared to PEI-only or lipoplex and facilitated efficient gene delivery. Intracellular trafficking was visualized by observing fluorescence-labeled pDNA and highlighted the effective cytoplasmic uptake of polyplexes and release of DNA to the perinuclear space. Specifically, a triblock copolymer with a middle depsipeptide block and two 10 kDa PEI swallowtail structures mediated the highest levels of transgenic VEGF secretion in mesenchymal stem cells with low cytotoxicity. These nanocarriers form the basis for a delivery platform technology, especially for gene transfer to primary human cells.}, language = {en} } @article{ZhangWillaSunetal.2017, author = {Zhang, Weiyi and Willa, Christoph and Sun, Jian-Ke and Guterman, Ryan and Taubert, Andreas and Yuan, Jiayin}, title = {Polytriazolium poly(ionic liquid) bearing triiodide anions: Synthesis, basic properties and electrochemical behaviors}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {124}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2017.07.059}, pages = {246 -- 251}, year = {2017}, abstract = {4-Methyl-1-vinyl-1,2,4-triazolium triiodide ionic liquid and its polymer poly(4-methyl-1-vinyl-1,2,4-triazolium) triiodide were prepared for the first time from their iodide precursors via the reaction of iodide (I-) with elemental iodine (I-2). The change from iodide to triiodide (I-3(-)) was found to introduce particular variations in the physical properties of these two compounds, including lower melting point/glass transition temperature and altered solubility. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, and their electrochemical properties examined in solution and in the solid-state. Compared with their iodide analogues, the triiodide salts exhibited lower electrical impedance and higher current in the cyclic voltammetry. We found that poly(4-methyl-1,2,4-triazolium triiodide) was proven to be a promising solid polymer electrolyte candidate. (C) 2017 Elsevier Ltd. All rights reserved.}, language = {en} } @article{BalderasValadezAntunezOliveMendezetal.2017, author = {Balderas-Valadez, Ruth Fabiola and Antunez, E. E. and Olive-Mendez, Sion Federico and Pacholski, Claudia and Campos-Alvarez, Jose and Bokhimi, Xim and Agarwal, V.}, title = {Porous silicon pillar and bilayer structure as a nucleation center for the formation of aligned vanadium pentoxide nanorods}, series = {Ceramics International}, volume = {43}, journal = {Ceramics International}, publisher = {Elsevier}, address = {Oxford}, issn = {0272-8842}, doi = {10.1016/j.ceramint.2017.03.114}, pages = {8023 -- 8030}, year = {2017}, abstract = {Porous silicon single layer (PSM), bilayer (PSB) and pillar (PSP) structures have been evaluated as nucleation centers for vanadium pentoxide (V2O5) crystals. Deposition of vanadium precursor over different substrates (drop casting technique), followed by annealing treatment under Ar-H-2 (5\% H-2) atmosphere, induced crystallization of vanadium oxide. With respect to c-Si/SiO2 substrate, V2O5 nanorods with relatively large aspect ratio were formed over and within PSP structures. On the other hand, pores in PSM and PSB were found to be filled with relatively smaller crystals. Additionally, PSB provided a nucleation substrate capable to align the nanocrystals in a preferential orientation, while V2O5 crystals grown on PSP were found to be randomly aligned around the nanoporous pillar microstructure. Nanorods and nanocrystals were identified as V2O5 by temperature-controlled XRD measurements and evidence of their crystalline nature was observed via transmission electron microscopy. A careful analysis of electronic microscopy images allows the identification of the facets composing the ends of the crystals and its corresponding surface free energy has been evaluated employing the Wulff theorem. Such high surface area composite structures have potential applications as cathode material in Lithium-ion batteries.}, language = {en} } @article{MeiJaftaLauermannetal.2017, author = {Mei, Shilin and Jafta, Charl J. and Lauermann, Iver and Ran, Qidi and Kaergell, Martin and Ballauff, Matthias and Lu, Yan}, title = {Porous Ti4O7 Particles with Interconnected-Pore Structure as a High-Efficiency Polysulfide Mediator for Lithium-Sulfur Batteries}, series = {Advanced functional materials}, volume = {27}, journal = {Advanced functional materials}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.201701176}, pages = {10}, year = {2017}, abstract = {Multifunctional Ti4O7 particles with interconnected-pore structure are designed and synthesized using porous poly(styrene-b-2-vinylpyridine) particles as a template. The particles can work efficiently as a sulfur-host material for lithium-sulfur batteries. Specifically, the well-defined porous Ti4O7 particles exhibit interconnected pores in the interior and have a high-surface area of 592 m(2) g(-1); this shows the advantage of mesopores for encapsulating of sulfur and provides a polar surface for chemical binding with polysulfides to suppress their dissolution. Moreover, in order to improve the conductivity of the electrode, a thin layer of carbon is coated on the Ti4O7 surface without destroying its porous structure. The porous Ti4O7 and carbon-coated Ti4O7 particles show significantly improved electrochemical performances as cathode materials for Li-S batteries as compared with those of TiO2 particles.}, language = {en} }