TY - JOUR A1 - Adelsberger, Joseph A1 - Bivigou Koumba, Achille Mayelle A1 - Miasnikova, Anna A1 - Busch, Peter A1 - Laschewsky, André A1 - Müller-Buschbaum, Peter A1 - Papadakis, Christine M. T1 - Polystyrene-block-poly (methoxy diethylene glycol acrylate)-block-polystyrene triblock copolymers in aqueous solution-a SANS study of the temperature-induced switching behavior JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - A concentrated solution of a symmetric triblock copolymer with a thermoresponsive poly(methoxy diethylene glycol acrylate) (PMDEGA) middle block and short hydrophobic, fully deuterated polystyrene end blocks is investigated in D2O where it undergoes a lower critical solution temperature-type phase transition at ca. 36 A degrees C. Small-angle neutron scattering (SANS) in a wide temperature range (15-50 A degrees C) is used to characterize the size and inner structure of the micelles as well as the correlation between the micelles and the formation of aggregates by the micelles above the cloud point (CP). A model featuring spherical core-shell micelles, which are correlated by a hard-sphere potential or a sticky hard-sphere potential together with a Guinier form factor describing aggregates formed by the micelles above the CP, fits the SANS curves well in the entire temperature range. The thickness of the thermoresponsive micellar PMDEGA shell as well as the hard-sphere radius increase slightly already below the cloud point. Whereas the thickness of the thermoresponsive micellar shell hardly shrinks when heating through the CP and up to 50 A degrees C, the hard-sphere radius decreases within 3.5 K at the CP. The volume fraction decreases already significantly below the CP, which may be at the origin of the previously observed gel-sol transition far below the CP (Miasnikova et al., Langmuir 28: 4479-4490, 2012). Above the CP, small, and at higher temperatures, large aggregates are formed by the micelles. KW - Hydrogel KW - Thermoresponsive KW - LCST behavior KW - SANS Y1 - 2015 U6 - https://doi.org/10.1007/s00396-015-3535-6 SN - 0303-402X SN - 1435-1536 VL - 293 IS - 5 SP - 1515 EP - 1523 PB - Springer CY - New York ER - TY - THES A1 - Ambrogi, Martina T1 - Application of Poly(Ionic Liquid)s for the synthesis of functional carbons Y1 - 2015 ER - TY - JOUR A1 - Attenberger, Bianca A1 - Moussa, Mehdi El Sayed A1 - Brietzke, Thomas Martin A1 - Vreshch, Volodimir A1 - Holdt, Hans-Jürgen A1 - Lescop, Christophe A1 - Scheer, Manfred T1 - Discrete Polymetallic Arrangements of Ag-I and Cu-I Ions Based on Multiple Bridging Phosphane Ligands and pi-pi Interactions JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - A simple and straightforward approach to new polymetallic Ag-I and Cu-I supramolecules is presented. The reaction of N,P,N,P,N ligand 2 with Ag-I ions affords a trimetallic complex bearing a triangular Ag-3 core; metallophilic interactions are stabilized by ligands that display a multiple bridging coordination mode as 10-electron donors. Heteroleptic polymetallic Ag-I and Cu-I complexes based on ligand 2 and the 1,12-diazaperylene (dape) ligand are obtained by an alternative molecular organization of the polymetallic arrays compared to that in homoleptic complexes of ligand 2. KW - Heterocycles KW - N KW - P ligands KW - Pi interactions KW - Polyaromatic fragments KW - Supramolecular chemistry Y1 - 2015 U6 - https://doi.org/10.1002/ejic.201500445 SN - 1434-1948 SN - 1099-0682 IS - 18 SP - 2934 EP - 2938 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Baier, Heiko T1 - Palladium(II)-Komplexe mit 4,5-Dicyanoimidazol-2-ylidenen BT - Synthese, Charakterisierung und Anwendung in der Mizoroki-Heck- und der Suzuki-Miyaura-Reaktion Y1 - 2015 ER - TY - JOUR A1 - Baier, Heiko A1 - Kelling, Alexandra A1 - Holdt, Hans-Jürgen T1 - PEPPSI-Effect on Suzuki-Miyaura Reactions Using 4,5-Dicyano-1,3-dimesitylimidazol-2-ylidene-Palladium Complexes: A Comparison between trans-Ligands JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - The PEPPSI (Pyridine Enhanced Precatalyst Preparation, Stabilization and Initiation) complexes 12-15 with the structure [PdCl2{(CN)(2)IMes}(3-R-py)] (12: R = H; 13: R = Cl; 14: R = Br; 15: R = CN) bearing the maleonitrile-based N-heterocyclic carbene (NHC) (CN)(2)IMes ({(CN)(2)IMes}: 4,5-dicyano-1,3-dimesitylimidazol-2-ylidene) were prepared. Solid state structures of 14 and 15 were obtained. Complexes 14 and 15 adopt a slightly distorted square-planar coordination geometry in the solid state with the substituted pyridine ligand trans to the NHC. Catalytic activities of precatalysts 12-15 were studied and subsequently compared to complexes [PdCl2{(CN)(2)IMes}(PPh3)] (4) and [PdCl(dmba){(CN)(2)IMes}] (5) recently reported by our group in the Suzuki-Miyaura reaction of various aryl halides and phenylboronic acid. Reactions using previously reported [PdCl2(IMes)(py)] (IMes: 1,3-dimesitylimidazol-2-ylidene) (1) were also carried out and their results contrasted to those involving 12-15, 4 and 5. Differences in initiation rates and the catalytically active species related to the seven complexes in regards to the throw away ligand were investigated. Poisoning experiments with mercury show that palladium nanoparticles are responsible for the catalytic activity. KW - Carbene ligands KW - Palladium KW - Cross-coupling KW - Arenes Y1 - 2015 U6 - https://doi.org/10.1002/ejic.201500010 SN - 1434-1948 SN - 1099-0682 IS - 11 SP - 1950 EP - 1957 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Banerjee, Shiladitya A1 - Stueker, Tony A1 - Saalfrank, Peter T1 - Vibrationally resolved optical spectra of modified diamondoids obtained from time-dependent correlation function methods JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - Optical properties of modified diamondoids have been studied theoretically using vibrationally resolved electronic absorption, emission and resonance Raman spectra. A time-dependent correlation function approach has been used for electronic two-state models, comprising a ground state (g) and a bright, excited state (e), the latter determined from linear-response, time-dependent density functional theory (TD-DFT). The harmonic and Condon approximations were adopted. In most cases origin shifts, frequency alteration and Duschinsky rotation in excited states were considered. For other cases where no excited state geometry optimization and normal mode analysis were possible or desired, a short-time approximation was used. The optical properties and spectra have been computed for (i) a set of recently synthesized sp(2)/sp(3) hybrid species with CQC double-bond connected saturated diamondoid subunits, (ii) functionalized (mostly by thiol or thione groups) diamondoids and (iii) urotropine and other C-substituted diamondoids. The ultimate goal is to tailor optical and electronic features of diamondoids by electronic blending, functionalization and substitution, based on a molecular-level understanding of the ongoing photophysics. Y1 - 2015 U6 - https://doi.org/10.1039/c5cp02615f SN - 1463-9076 SN - 1463-9084 VL - 17 IS - 29 SP - 19656 EP - 19669 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Banerjee, Shiladitya A1 - Stüker, Tony A1 - Saalfrank, Peter T1 - Vibrationally resolved optical spectra of modified diamondoids obtained from time-dependent correlation function methods N2 - Optical properties of modified diamondoids have been studied theoretically using vibrationally resolved electronic absorption, emission and resonance Raman spectra. A time-dependent correlation function approach has been used for electronic two-state models, comprising a ground state (g) and a bright, excited state (e), the latter determined from linear-response, time-dependent density functional theory (TD-DFT). The harmonic and Condon approximations were adopted. In most cases origin shifts, frequency alteration and Duschinsky rotation in excited states were considered. For other cases where no excited state geometry optimization and normal mode analysis were possible or desired, a short-time approximation was used. The optical properties and spectra have been computed for (i) a set of recently synthesized sp2/sp3 hybrid species with C[double bond, length as m-dash]C double-bond connected saturated diamondoid subunits, (ii) functionalized (mostly by thiol or thione groups) diamondoids and (iii) urotropine and other C-substituted diamondoids. The ultimate goal is to tailor optical and electronic features of diamondoids by electronic blending, functionalization and substitution, based on a molecular-level understanding of the ongoing photophysics. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 211 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-86826 ER - TY - JOUR A1 - Banerjee, Shiladitya A1 - Stüker, Tony A1 - Saalfrank, Peter T1 - Vibrationally resolved optical spectra of modified diamondoids obtained from time-dependent correlation function methods JF - Physical chemistry, chemical physics : PCCP ; a journal of European chemical societies N2 - Optical properties of modified diamondoids have been studied theoretically using vibrationally resolved electronic absorption, emission and resonance Raman spectra. A time-dependent correlation function approach has been used for electronic two-state models, comprising a ground state (g) and a bright, excited state (e), the latter determined from linear-response, time-dependent density functional theory (TD-DFT). The harmonic and Condon approximations were adopted. In most cases origin shifts, frequency alteration and Duschinsky rotation in excited states were considered. For other cases where no excited state geometry optimization and normal mode analysis were possible or desired, a short-time approximation was used. The optical properties and spectra have been computed for (i) a set of recently synthesized sp2/sp3 hybrid species with C[double bond, length as m-dash]C double-bond connected saturated diamondoid subunits, (ii) functionalized (mostly by thiol or thione groups) diamondoids and (iii) urotropine and other C-substituted diamondoids. The ultimate goal is to tailor optical and electronic features of diamondoids by electronic blending, functionalization and substitution, based on a molecular-level understanding of the ongoing photophysics. Y1 - 2015 U6 - https://doi.org/10.1039/C5CP02615F SN - 1463-9084 SN - 1463-9076 VL - 17 IS - 29 SP - 19656 EP - 19669 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Bartoloni, Marco A1 - Jin, Xian A1 - Marcaida, Maria José A1 - Banha, Joao A1 - Dibonaventura, Ivan A1 - Bongoni, Swathi A1 - Bartho, Kathrin A1 - Gräbner, Olivia A1 - Sefkow, Michael A1 - Darbre, Tamis A1 - Reymond, Jean-Louis T1 - Bridged bicyclic peptides as potential drug scaffolds BT - synthesis, structure, protein binding and stability JF - Chemical Science N2 - Double cyclization of short linear peptides obtained by solid phase peptide synthesis was used to prepare bridged bicyclic peptides (BBPs) corresponding to the topology of bridged bicyclic alkanes such as norbornane. Diastereomeric norbornapeptides were investigated by 1H-NMR, X-ray crystallography and CD spectroscopy and found to represent rigid globular scaffolds stabilized by intramolecular backbone hydrogen bonds with scaffold geometries determined by the chirality of amino acid residues and sharing structural features of β-turns and α-helices. Proteome profiling by capture compound mass spectrometry (CCMS) led to the discovery of the norbornapeptide 27c binding selectively to calmodulin as an example of a BBP protein binder. This and other BBPs showed high stability towards proteolytic degradation in serum. Y1 - 2015 U6 - https://doi.org/10.1039/C5SC01699A SN - 2041-6520 SN - 2041-6539 VL - 10 IS - 6 SP - 5473 EP - 5490 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Bartoloni, Marco A1 - Jin, Xian A1 - Marcaida, Maria José A1 - Banha, Joao A1 - Dibonaventura, Ivan A1 - Bongoni, Swathi A1 - Bartho, Kathrin A1 - Gräbner, Olivia A1 - Sefkow, Michael A1 - Darbre, Tamis A1 - Reymond, Jean-Louis T1 - Bridged bicyclic peptides as potential drug scaffolds BT - synthesis, structure, protein binding and stability N2 - Double cyclization of short linear peptides obtained by solid phase peptide synthesis was used to prepare bridged bicyclic peptides (BBPs) corresponding to the topology of bridged bicyclic alkanes such as norbornane. Diastereomeric norbornapeptides were investigated by 1H-NMR, X-ray crystallography and CD spectroscopy and found to represent rigid globular scaffolds stabilized by intramolecular backbone hydrogen bonds with scaffold geometries determined by the chirality of amino acid residues and sharing structural features of β-turns and α-helices. Proteome profiling by capture compound mass spectrometry (CCMS) led to the discovery of the norbornapeptide 27c binding selectively to calmodulin as an example of a BBP protein binder. This and other BBPs showed high stability towards proteolytic degradation in serum. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 197 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-81239 ER - TY - JOUR A1 - Bauer, Monika A1 - Hartmann, Lutz A1 - Kleinpeter, Erich A1 - Kuschel, Frank A1 - Pithart, Cornelia A1 - Weissflog, Wolfgang T1 - Chiral Dopants Derived from Ephedrine/Pseudoephedrine: Structure and Medium Effects on the Helical Twisting Power JF - Molecular crystals and liquid crystals N2 - Chiral dopants were obtained by acylation of enantiomerically pure ephedrine and pseudoephedrine with promesogenic carbonyl reagents. The products have been investigated with respect to their chiral transfer ability on nematic host matrices characterized by extreme differences of the dielectric anisotropy. It has been found that the medium dependence of the helicity induction nearly disappears at reduced temperatures. Based on variable temperature H-1 NMR studies on monoacylated homologues, the estimated coalescence temperatures and free activation enthalpies for the hindered rotation around C-N bonds could be correlated with the helical twisting power. Measurements by dielectric spectroscopy reveal the correlation between the molar mass of substituents linked to the chiral building block and the dynamic glass transition of corresponding chiral dopants. Furthermore, the effect of intramolecular and intermolecular hydrogen bonds has been studied by ATR-FTIR spectroscopy. KW - ephedrine/pseudoephedrine KW - Chiral dopants KW - ATR-FTIR KW - molecular structure KW - dielectric spectroscopy KW - H-1 NMR Y1 - 2015 U6 - https://doi.org/10.1080/15421406.2014.949592 SN - 1542-1406 SN - 1563-5287 VL - 608 IS - 1 SP - 14 EP - 24 PB - Routledge, Taylor & Francis Group CY - Abingdon ER - TY - JOUR A1 - Behrens, Karsten A1 - Mondal, Suvendu Selchar A1 - Nöske, Robert A1 - Baburin, Igor A. A1 - Leoni, Stefano A1 - Günter, Christina A1 - Weber, Jens A1 - Holdt, Hans-Jürgen T1 - Microwave-Assisted Synthesis of Defects Metal-Imidazolate-Amide-Imidate Frameworks and Improved CO2 Capture JF - Inorganic chemistry N2 - In this work, we report three isostructural 3D frameworks, named IFP-11 (R = Cl), IFP-12 (R = Br), and IFP-13 (R = Et) (IFP = Imidazolate Framework Potsdam) based on a cobalt(II) center and the chelating linker 2-substituted imidazolate-4-amide-5-imidate. These chelating ligands were generated in situ by partial hydrolysis of 2-substituted 4,5-dicyanoimidazoles under microwave (MW)-assisted conditions in DMF. Structure determination of these IFPs was investigated by IR spectroscopy and a combination of powder X-ray diffraction (PXRD) with structure modeling. The structural models were initially built up from the single-crystal X-ray structure determination of IFP-5 (a cobalt center and 2-methylimidazolate-4-amide-5-imidate linker based framework) and were optimized by using density functional theory calculations. Substitution on position 2 of the linker (R = Cl, Br, and Et) in the isostructural IFP-11, -12, and -13 allowed variation of the potential pore window in 1D hexagonal channels (3.8 to 1.7 angstrom A). The potential of the materials to undergo specific interactions with CO2 was measured by the isosteric heat adsorption. Further, we resynthesized zinc based IFPs, namely IFP-1 = Me), IFP-2 (R = Cl), IFP-3 (R = Br), and IFP-4 (R = Et), and cobalt based IFP-5 under MW-assisted conditions with higher yield. The transition from a nucleation phase to the pure crystalline material of IFP-1 in MW-assisted synthesis depends on reaction time. IFP-1, -3, and -5, which are synthesized by MW-assisted conditions, showed an enhancement of N-2 and CO2, compared to the analogous conventional electrical (CE) heating method based materials due to crystal defects. Y1 - 2015 U6 - https://doi.org/10.1021/acs.inorgchem.5b01952 SN - 0020-1669 SN - 1520-510X VL - 54 IS - 20 SP - 10073 EP - 10080 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Beisebekov, Madiar Maratovich A1 - Serikpayeva, Saniya B. A1 - Zhumagalieva, Shynar Nurlanovna A1 - Beisebekov, Marat Kianovich A1 - Abilov, Zharylkasyn Abduachitovich A1 - Kosmella, Sabine A1 - Koetz, Joachim T1 - Interactions of bentonite clay in composite gels of non-ionic polymers with cationic surfactants and heavy metal ions JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - Chemically cross-linked composite gels based on bentonite clay from Manyrak deposit (Kazakhstan Republic) and nonionic polymers, i.e., poly(hydroxyethylacrylate) and poly(acrylamide), were polymerized in situ after preliminary intercalation of monomers in an aqueous suspension of bentonite clay. By means of cryo-scanning electron microscopy, it was shown that bentonite clay is well incorporated into the gel network structure with pore sizes up to 1.5 mu m. The intercalated bentonite clay can adsorb cationic surfactants as well as heavy metal ions due to electrostatic interactions. Conductometric and surface tension measurements indicate not only the adsorption of surfactants and heavy metals inside the hydrogel, but also the displacement of the critical micellization concentration (CMC) of the surfactants. KW - Bentonite clay KW - Cationic surfactants KW - Heavy metal ions KW - Composite hydrogels Y1 - 2015 U6 - https://doi.org/10.1007/s00396-014-3463-x SN - 0303-402X SN - 1435-1536 VL - 293 IS - 2 SP - 633 EP - 639 PB - Springer CY - New York ER - TY - JOUR A1 - Bodrova, Anna A1 - Chechkin, Aleksei V. A1 - Cherstvy, Andrey G. A1 - Metzler, Ralf T1 - Quantifying non-ergodic dynamics of force-free granular gases JF - Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies N2 - Brownianmotion is ergodic in the Boltzmann–Khinchin sense that long time averages of physical observables such as the mean squared displacement provide the same information as the corresponding ensemble average, even at out-of-equilibrium conditions. This property is the fundamental prerequisite for single particle tracking and its analysis in simple liquids. We study analytically and by event-driven molecular dynamics simulations the dynamics of force-free cooling granular gases and reveal a violation of ergodicity in this Boltzmann– Khinchin sense as well as distinct ageing of the system. Such granular gases comprise materials such as dilute gases of stones, sand, various types of powders, or large molecules, and their mixtures are ubiquitous in Nature and technology, in particular in Space. We treat—depending on the physical-chemical properties of the inter-particle interaction upon their pair collisions—both a constant and a velocity-dependent (viscoelastic) restitution coefficient e. Moreover we compare the granular gas dynamics with an effective single particle stochastic model based on an underdamped Langevin equation with time dependent diffusivity. We find that both models share the same behaviour of the ensemble mean squared displacement (MSD) and the velocity correlations in the limit of weak dissipation. Qualitatively, the reported non-ergodic behaviour is generic for granular gases with any realistic dependence of e on the impact velocity of particles. Y1 - 2015 U6 - https://doi.org/10.1039/C5CP02824H SN - 1463-9084 IS - 17 SP - 21791 EP - 21798 ER - TY - GEN A1 - Bodrova, Anna A1 - Chechkin, Aleksei V. A1 - Cherstvy, Andrey G. A1 - Metzler, Ralf T1 - Quantifying non-ergodic dynamics of force-free granular gases N2 - Brownianmotion is ergodic in the Boltzmann–Khinchin sense that long time averages of physical observables such as the mean squared displacement provide the same information as the corresponding ensemble average, even at out-of-equilibrium conditions. This property is the fundamental prerequisite for single particle tracking and its analysis in simple liquids. We study analytically and by event-driven molecular dynamics simulations the dynamics of force-free cooling granular gases and reveal a violation of ergodicity in this Boltzmann-Khinchin sense as well as distinct ageing of the system. Such granular gases comprise materials such as dilute gases of stones, sand, various types of powders, or large molecules, and their mixtures are ubiquitous in Nature and technology, in particular in Space. We treat—depending on the physical-chemical properties of the inter-particle interaction upon their pair collisions—both a constant and a velocity-dependent (viscoelastic) restitution coefficient e. Moreover we compare the granular gas dynamics with an effective single particle stochastic model based on an underdamped Langevin equation with time dependent diffusivity. We find that both models share the same behaviour of the ensemble mean squared displacement (MSD) and the velocity correlations in the limit of weak dissipation. Qualitatively, the reported non-ergodic behaviour is generic for granular gases with any realistic dependence of e on the impact velocity of particles. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 206 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-85200 ER - TY - JOUR A1 - Boese, Adrian Daniel T1 - Density Functional Theory and Hydrogen Bonds: Are We There Yet? JF - ChemPhysChem : a European journal of chemical physics and physical chemistry N2 - Density functional theory (DFT) has become more successful at introducing dispersion interactions, and can be thus applied to a wide range of systems. Amongst these are systems that contain hydrogen bonds, which are extremely important for the biological regime. Here, the description of hydrogen-bonded interactions by DFT with and without dispersion corrections is investigated. For small complexes, for which electrostatics are the determining factor in the intermolecular interactions, the inclusion of dispersion with most functionals yields large errors. Only for larger systems, in which van der Waals interactions are more important, do dispersion corrections improve the performance of DFT for hydrogen-bonded systems. None of the studied functionals, including double hybrid functionals (with the exception of DSD-PBEP86 without dispersion corrections), are more accurate than MP2 for the investigated species. KW - ab initio calculations KW - basis sets KW - density functional calculations KW - hydrogen bonds KW - intermolecular interactions Y1 - 2015 U6 - https://doi.org/10.1002/cphc.201402786 SN - 1439-4235 SN - 1439-7641 VL - 16 IS - 5 SP - 978 EP - 985 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Boese, Adrian Daniel T1 - Basis set limit coupled-cluster studies of hydrogen-bonded systems JF - Molecular physics N2 - As hydrogen-bonded systems are of utmost importance in especially biological and chemical systems, a new set of highly accurate reference dissociation energies, denoted HB49, is devised. For the molecules in this set, the basis set convergence of post-Hartree-Fock methods, including F12 methods, is investigated. Using combined Moller-Plesset perturbation theory (MP2) and CCSD(T) approaches for energies and MP2 and QCISD(T) for gradients, we achieve CCSD(T) accuracy, which has been determined before to yield an accuracy of 0.2 kJ/mol for a subset of HB49. Both conventional extrapolation techniques and F12 techniques are competitive with each other. By using MP2+Delta CCSD(T), a rather fast basis set convergence is obtained when both basis sets are carefully chosen. KW - coupled-cluster KW - hydrogen bonds KW - ab initio KW - F12 methods Y1 - 2015 U6 - https://doi.org/10.1080/00268976.2014.1001806 SN - 0026-8976 SN - 1362-3028 VL - 113 IS - 13-14 SP - 1618 EP - 1629 PB - Routledge, Taylor & Francis Group CY - Abingdon ER - TY - JOUR A1 - Boese, Adrian Daniel A1 - Boese, Roland T1 - Tetrahydrothiophene and Tetrahydrofuran, Computational and X-ray Studies in the Crystalline Phase JF - Crystal growth & design : integrating the fields of crystal engineering and crystal growth for the synthesis and applications of new materials N2 - Calculations at various levels of theory with different methods and respective evaluations confirm that the twist conformation (C-2) is preferred for tetrahydrothiophene (THT) in the gas phase. In the crystalline phase, achieved by a laser assisted crystallization device, THT has C-1 symmetry (slightly distorted C-2 symmetry) in the chiral space group P2(1)2(1)2(1). This is obviously a packing effect caused by the nonsymmetrical arrangement of neighboring molecules. The distortion from C-2 symmetry costs very little energy as confirmed by computational methods in the gas phase. Only one enantiomer of the chiral THT is found in the cell which requires spontaneous crystallization, which results in a racemic mixture of crystals, or a racemization occurs prior to/during nucleation or in the embryonic state. The racemization happens by a mechanism that can be described as a partial pseudo rotation within a five-membered mono-heterocycle with a C-2-C-S-C-2' transition (C-2 and C-2' are enantiomers) maintaining the heteroatom residing within the symmetry elements. While THT has the molecular symmetry of the gas phase almost also in the crystalline phase, THF has an envelope conformation (CS). This was also established by calculations at various levels of theory which agrees well with the previously experimentally found conformation by electron diffraction. However, in the X-ray crystal structure, previously determined by Luger & Buschmann, THF has C-2 symmetry in the centrosymmetric space group C2/c with the oxygen atom situated on the crystallographic C-2 polar axis, requesting a racemic crystal for the twisted conformers of the enantiomers. No solid-state phase transitions were detected within the experimental ranges for THT and THF. Following the stabilization by molecular clustering, and ending at the crystal lattice, we stepwise increased the number of molecules by calculation of the respective monomers, dimers, trimers, and tetramers for THF and THT. The starting point was taken from the arrangements as found in the respective crystal structures. Both conformational enantiomers are equal in energy. In such cases, a crystal may contain either a racemate of conformers or one of the conformational enantiomers only. The first case is observed in THF, the latter one in THT. It is quite likely that the selection of one enantiomeric conformer of THT from an equilibrium of conformers at the early stage of nucleation (embryonic stage) is responsible for the spontaneous crystallization. In order to check if THF could form a polymorph with the molecular packing of THT and vice versa, we first calculated THF and THT in their respective crystal lattices as determined by X-ray diffraction. Exchanging the compounds in the THT and THF crystal lattices (i.e., replacing O against S and vice versa) results in significantly worse lattice energies indicating that such a polymorph is not a probable option. Y1 - 2015 U6 - https://doi.org/10.1021/cg501228w SN - 1528-7483 SN - 1528-7505 VL - 15 IS - 3 SP - 1073 EP - 1081 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Brietzke, Thomas Martin T1 - Mono- und dinukleare Metallkomplexe mit dem neuen Bis(a,a'-diimin)-Brückenliganden 1,6,7,12-Tetraazaperylen Y1 - 2015 ER - TY - JOUR A1 - Brosnan, Sarah M. A1 - Schlaad, Helmut A1 - Antonietti, Markus T1 - Aqueous Self-Assembly of Purely Hydrophilic Block Copolymers into Giant Vesicles JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - Self-assembly of macromolecules is fundamental to life itself, and historically, these systems have been primitively mimicked by the development of amphiphilic systems, driven by the hydrophobic effect. Herein, we demonstrate that self-assembly of purely hydrophilic systems can be readily achieved with similar ease and success. We have synthesized double hydrophilic block copolymers from polysaccharides and poly(ethylene oxide) or poly(sarcosine) to yield high molar mass diblock copolymers through oxime chemistry. These hydrophilic materials can easily assemble into nanosized (<500nm) and microsized (>5m) polymeric vesicles depending on concentration and diblock composition. Because of the solely hydrophilic nature of these materials, we expect them to be extraordinarily water permeable systems that would be well suited for use as cellular mimics. KW - block copolymers KW - polymersomes KW - polysaccharides KW - self-assembly KW - vesicles Y1 - 2015 U6 - https://doi.org/10.1002/anie.201502100 SN - 1433-7851 SN - 1521-3773 VL - 54 IS - 33 SP - 9715 EP - 9718 PB - Wiley-VCH CY - Weinheim ER - TY - BOOK A1 - Buddrus, Joachim A1 - Schmidt, Bernd T1 - Grundlagen der organischen Chemie Y1 - 2015 SN - 978-3-11-030559-3 PB - de Gruyter CY - Berlin ET - 5., überarb. und aktualisierte Aufl. ER - TY - JOUR A1 - Chandran, Sivasurender A1 - Dold, Stefanie A1 - Buvignier, Amaury A1 - Krannig, Kai-Steffen A1 - Schlaad, Helmut A1 - Reiter, Günter A1 - Reiter, Renate T1 - Tuning Morphologies of Langmuir Polymer Films Through Controlled Relaxations of Non-Equilibrium States JF - Langmuir N2 - Langmuir polymers films (LPFs) frequently form non-equilibrium states which are manifested in a decay of the surface pressure with time when the system is allowed to relax. Monitoring and manipulating the temporal evolution of these relaxations experimentally helps to shed light on the associated molecular reorganization processes. We present a systematic study based on different compression protocols and show how these reorganization processes impact the morphology of LPFs of poly(gamma-benzyl-L-glutamate) (PBLG); visualized by means of atomic force microscopy. Upon continuous compression, a fibrillar morphology was formed with a surface decorated by squeezed-out islands. By contrast, stepwise compression promoted the formation of a fibrillar network with a bimodal distribution of fibril diameters, caused by merging of fibrils. Finally, isobaric compression induced in-plane compaction of the monolayer. We correlate these morphological observations with the kinetics of the corresponding relaxations, described best by a sum of two exponential functions with different time scales representing two molecular processes. We discuss the observed kinetics and the resulting morphologies in the context of nucleation and growth, characteristic for first-order phase transitions. Our results demonstrate that the preparation conditions of LPFs have tremendous impact on ordering of the molecules and hence various macroscopic properties of such films. Y1 - 2015 U6 - https://doi.org/10.1021/acs.langmuir.5b01212 SN - 0743-7463 VL - 31 IS - 23 SP - 6426 EP - 6435 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Chen, Zupeng T1 - Novel strategies to improve (photo)catalytic performance of carbon nitride-based composites Y1 - 2015 ER - TY - JOUR A1 - Codorniu-Hernandez, Edelsys A1 - Hall, Kyle Wm. A1 - Boese, Adrian Daniel A1 - Ziemianowicz, Daniel A1 - Carpendale, Sheelagh A1 - Kusalik, Peter G. T1 - Mechanism of O(P-3) Formation from a Hydroxyl Radical Pair in Aqueous Solution JF - Journal of chemical theory and computation N2 - The reaction mechanism for the rapid formation of a triplet oxygen atom, O(P-3), from a pair of triplet-state hydroxyl radicals in liquid water is explored utilizing extensive Car-Parrinello MD simulations and advanced visualization techniques. The local solvation structures, the evolution of atomic charges, atomic separations, spin densities, electron localization functions, and frontier molecular orbitals, as well as free energy profiles, evidence that the reaction proceeds through a hybrid (hydrogen atom transfer and electron proton transfer) and hemibond-assisted reaction mechanism. A benchmarking study utilizing high-level ab initio calculations to examine the interactions of a hydroxyl radical pair in the gas phase and the influence of a hemibonded water is also provided. The results presented here should serve as a foundation for further experimental and theoretical studies aimed at better understanding the role and potential applications of the triplet oxygen atom as a potent reactive oxygen species. Y1 - 2015 U6 - https://doi.org/10.1021/acs.jctc.5b00783 SN - 1549-9618 SN - 1549-9626 VL - 11 IS - 10 SP - 4740 EP - 4748 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Couturier, Jean-Philippe A1 - Sütterlin, Martin A1 - Laschewsky, André A1 - Hettrich, Cornelia A1 - Wischerhoff, Erik T1 - Responsive Inverse Opal Hydrogels for the Sensing of Macromolecules JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - Dual responsive inverse opal hydrogels were designed as autonomous sensor systems for (bio)macromolecules, exploiting the analyte-induced modulation of the opal's structural color. The systems that are based on oligo(ethylene glycol) macromonomers additionally incorporate comonomers with various recognition units. They combine a coil-to-globule collapse transition of the LCST type with sensitivity of the transition temperature toward molecular recognition processes. This enables the specific detection of macromolecular analytes, such as glycopolymers and proteins, by simple optical methods. While the inverse opal structure assists the effective diffusion even of large analytes into the photonic crystal, the stimulus responsiveness gives rise to strong shifts of the optical Bragg peak of more than 100nm upon analyte binding at a given temperature. The systems' design provides a versatile platform for the development of easy-to-use, fast, and low-cost sensors for pathogens. KW - hydrogels KW - photonic crystals KW - polymers KW - responsive materials KW - sensors Y1 - 2015 U6 - https://doi.org/10.1002/anie.201500674 SN - 1433-7851 SN - 1521-3773 VL - 54 IS - 22 SP - 6641 EP - 6644 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Cramer, Ashley D. A1 - Gambinossi, Filippo A1 - Wischerhoff, Erik A1 - Laschewsky, André A1 - Miller, Reinhard A1 - Ferri, James K. T1 - Flexible thermoresponsive nanomembranes at the aqueous-air interface JF - Chemical communications N2 - A synthetic pathway is described to construct thermoresponsive freestanding nanomembranes at the aqueous-air interface of a pendant drop. Dynamic control of the reaction kinetics allows formation of viscoelastic interfaces supporting anisotropic stresses and mechanical stability, which can be tuned by external stimuli. Y1 - 2015 U6 - https://doi.org/10.1039/c4cc07359b SN - 1359-7345 SN - 1364-548X VL - 51 IS - 5 SP - 877 EP - 880 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Crone, Barbara A1 - Aschner, Michael A. A1 - Schwerdtle, Tanja A1 - Karst, Uwe A1 - Bornhorst, Julia T1 - Elemental bioimaging of Cisplatin in Caenorhabditis elegans by LA-ICP-MS JF - Metallomics N2 - cis-Diamminedichloroplatinum(II) (Cisplatin) is one of the most important and frequently used cytostatic drugs for the treatment of various solid tumors. Herein, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method incorporating a fast and simple sample preparation protocol was developed for the elemental mapping of Cisplatin in the model organism Caenorhabditis elegans (C. elegans). The method allows imaging of the spatially-resolved elemental distribution of platinum in the whole organism with respect to the anatomic structure in L4 stage worms at a lateral resolution of 5 μm. In addition, a dose- and time-dependent Cisplatin uptake was corroborated quantitatively by a total reflection X-ray fluorescence spectroscopy (TXRF) method, and the elemental mapping indicated that Cisplatin is located in the intestine and in the head of the worms. Better understanding of the distribution of Cisplatin in this well-established model organism will be instrumental in deciphering Cisplatin toxicity and pharmacokinetics. Since the cytostatic effect of Cisplatin is based on binding the DNA by forming intra- and interstrand crosslinks, the response of poly(ADP-ribose)metabolism enzyme 1 (pme-1) deletion mutants to Cisplatin was also examined. Loss of pme-1, which is the C. elegans ortholog of human poly(ADP-ribose) polymerase 1 (PARP-1) led to disturbed DNA damage response. With respect to survival and brood size, pme-1 deletion mutants were more sensitive to Cisplatin as compared to wildtype worms, while Cisplatin uptake was indistinguishable. Y1 - 2015 U6 - https://doi.org/10.1039/c5mt00096c SN - 1756-591X SN - 1756-5901 VL - 2015 IS - 7 SP - 1189 EP - 1195 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Crone, Barbara A1 - Aschner, Michael A. A1 - Schwerdtle, Tanja A1 - Karst, Uwe A1 - Bornhorst, Julia T1 - Elemental bioimaging of Cisplatin in Caenorhabditis elegans by LA-ICP-MS N2 - cis-Diamminedichloroplatinum(II) (Cisplatin) is one of the most important and frequently used cytostatic drugs for the treatment of various solid tumors. Herein, a laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) method incorporating a fast and simple sample preparation protocol was developed for the elemental mapping of Cisplatin in the model organism Caenorhabditis elegans (C. elegans). The method allows imaging of the spatially-resolved elemental distribution of platinum in the whole organism with respect to the anatomic structure in L4 stage worms at a lateral resolution of 5 μm. In addition, a dose- and time-dependent Cisplatin uptake was corroborated quantitatively by a total reflection X-ray fluorescence spectroscopy (TXRF) method, and the elemental mapping indicated that Cisplatin is located in the intestine and in the head of the worms. Better understanding of the distribution of Cisplatin in this well-established model organism will be instrumental in deciphering Cisplatin toxicity and pharmacokinetics. Since the cytostatic effect of Cisplatin is based on binding the DNA by forming intra- and interstrand crosslinks, the response of poly(ADP-ribose)metabolism enzyme 1 (pme-1) deletion mutants to Cisplatin was also examined. Loss of pme-1, which is the C. elegans ortholog of human poly(ADP-ribose) polymerase 1 (PARP-1) led to disturbed DNA damage response. With respect to survival and brood size, pme-1 deletion mutants were more sensitive to Cisplatin as compared to wildtype worms, while Cisplatin uptake was indistinguishable. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 192 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-80031 SP - 1189 EP - 1195 ER - TY - JOUR A1 - Cui, Qianling A1 - Xia, Bihua A1 - Mitzscherling, Steffen A1 - Masic, Admir A1 - Li, Lidong A1 - Bargheer, Matias A1 - Moehwald, Helmuth T1 - Preparation of gold nanostars and their study in selective catalytic reactions JF - Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects N2 - In this work, gold nanostars (AuNSs) with size around 90 nm were prepared through an easy one-step method. They show excellent catalytic activity and large surface-enhanced Raman scattering (SERS) activity at the same time. Surprisingly, they exhibited different catalytic performance on the reduction of aromatic nitro compounds with different substituents on the para position. To understand such a difference, the SERS spectra were recorded, showing that the molecular orientation of reactants on the gold surface were different. We anticipate that this research will help to understand the relationship of the molecular orientation with the catalytic activity of gold nanoparticles. KW - Nanoparticles KW - Gold KW - Catalytic reaction KW - Surface enhanced Raman scattering (SERS) KW - Molecular orientation Y1 - 2015 U6 - https://doi.org/10.1016/j.colsurfa.2014.10.028 SN - 0927-7757 SN - 1873-4359 VL - 465 SP - 20 EP - 25 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Cywinski, Piotr J. A1 - Olejko, Lydia A1 - Löhmannsröben, Hans-Gerd T1 - A time-resolved luminescent competitive assay to detect L-selectin using aptamers as recognition elements JF - Analytica chimica acta : an international journal devoted to all branches of analytical chemistry N2 - L-selectin is a protein with potential importance for numerous diseases and clinical disorders. In this paper, we present a new aptamer-based luminescent assay developed to detect L-selectin. The sensing system working principle is based on Forster Resonance Energy Transfer (FRET) from a donor terbium complex (TbC) to an acceptor cyanine dye (Cy5). In the present approach, the biotinylated aptamer is combined with Cy5-labelled streptavidin (Cy5-Strep) to yield an aptamer-based acceptor construct (Apta-Cy5-Strep), while L-selectin is conjugated using luminescent TbC. Upon aptamer binding to the TbC-labelled L-selectin (L-selectin-TbC), permanent donor-acceptor proximity is established which allows for radiationless energy transfer to occur. However, when unlabelled L-selectin is added, it competes with the L-selectin-TbC and the FRET signal decreases as the L-selectin concentration increases. FRET from the TbC to Cy5 was observed with time-gated time-resolved luminescence spectroscopy. A significant change in the corrected luminescence signal was observed in the dynamic range of 10 -500 ng/mL L-selectin, the concentration range relevant for accelerated cognitive decline of Alzheimer's disease, with a limit of detection (LOD) equal to 10 ng/mL. The aptasensor-based assay is homogeneous and can be realized within one hour. Therefore, this method has the potential to become an alternative to tedious heterogeneous analytical methods, e.g. based on enzyme-linked immunosorbent assay (ELISA). (C) 2015 Elsevier B.V. All rights reserved. KW - Aptamer KW - FRET KW - L-selectin KW - Luminescence spectroscopy KW - Fluoroassay KW - Lanthanide Y1 - 2015 U6 - https://doi.org/10.1016/j.aca.2015.06.045 SN - 0003-2670 SN - 1873-4324 VL - 887 SP - 209 EP - 215 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - de Carvalho, Sidney J. A1 - Metzler, Ralf A1 - Cherstvy, Andrey G. T1 - Inverted critical adsorption of polyelectrolytes in confinement JF - Soft matter N2 - What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer–surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sc—defining the adsorption–desorption transition—are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sc for the concave interfaces versus the Debye screening length 1/k and the extent of confinement a for these three interfaces for small ka values. For large ka the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/k. We also rationalize how sc(k) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption—the effect often hard to tackle theoretically—putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids. Y1 - 2015 U6 - https://doi.org/10.1039/C5SM00635J SN - 1744-6848 SN - 1744-683X IS - 11 SP - 4430 EP - 4443 PB - Royal Society of Chemistry CY - London ER - TY - GEN A1 - de Carvalho, Sidney J. A1 - Metzler, Ralf A1 - Cherstvy, Andrey G. T1 - Inverted critical adsorption of polyelectrolytes in confinement N2 - What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer–surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density sc—defining the adsorption–desorption transition—are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of sc for the concave interfaces versus the Debye screening length 1/k and the extent of confinement a for these three interfaces for small ka values. For large ka the critical adsorption condition approaches the known planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness a is of the order of 1/k. We also rationalize how sc(k) dependence gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length for critical adsorption—the effect often hard to tackle theoretically—putting an emphasis on polymers inside attractive spherical cavities. The applications of our findings to some biological systems are discussed, for instance the adsorption of nucleic acids onto the inner surfaces of cylindrical and spherical viral capsids. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 214 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-89562 SP - 4430 EP - 4443 ER - TY - JOUR A1 - de Molina, Paula Malo A1 - Ihlefeldt, Franziska Stefanie A1 - Prevost, Sylvain A1 - Herfurth, Christoph A1 - Appavou, Marie-Sousai A1 - Laschewsky, André A1 - Gradzielski, Michael T1 - Phase Behavior of Nonionic Microemulsions with Multi-end-capped Polymers and Its Relation to the Mesoscopic Structure JF - Langmuir N2 - The polymer architecture of telechelic or associative polymers has a large impact on the bridging of self-assembled structures. This Work presents: the phase behavior, small angle neutron scattering (SANS), dynamic light scattering (DLS), and fluorescence correlation spectroscopy (FCS) of a nonionic oil-in-water (O/W) microemulsion with hydrophobically end-capped multiarm polymers With functionalities f = 2, 3, and 4. For high polymer concentrations and large average interdroplet distance relative to the end-to-end distance of the polymer, d/R-ee; the system phase separates into a dense, highly connected droplet network phase, in equilibrium with a dilute phase. The extent of the two-phase region is larger for polymers With similar length but higher f. The Interaction potential between the droplets in the presence of polymer has both a repulsive and an attractive contribution as a result of the counterbalancing effects of the exclusion by polymer chains and bridging between droplets. This study experimentally demonstrates that higher polymer functionalities induce a stronger attractive force between droplets, which is responsible for a more extended phase separation region., and correlate with lower Collective droplet diffusivities and higher amplitude of the second relaxation time in DLS. The viscosity and the droplet self-diffusion obtained from FCS, however, are dominated by the end-capped chain concentration. Y1 - 2015 U6 - https://doi.org/10.1021/acs.langmuir.5b00817 SN - 0743-7463 VL - 31 IS - 18 SP - 5198 EP - 5209 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Dietrich, Paul M. A1 - Streeck, Cornelia A1 - Glamsch, Stephan A1 - Ehlert, Christopher A1 - Lippitz, Andreas A1 - Nutsch, Andreas A1 - Kulak, Nora A1 - Beckhoff, Burkhard A1 - Unger, W. E. S. T1 - Quantification of Silane Molecules on Oxidized Silicon: Are there Options for a Traceable and Absolute Determination? JF - Analytical chemistry N2 - Organosilanes are used routinely to functionalize various support materials for further modifications. Nevertheless, reliable quantitative information about surface functional group densities after layer formation is rarely available. Here, we present the analysis of thin organic nanolayers made from nitrogen containing silane molecules on naturally oxidized silicon wafers with reference-free total reflection X-ray fluorescence (TXR.F) and X-ray photoelectron spectroscopy (XPS). An areic density of 2-4 silane molecules per nm(2) was calculated from the layer's nitrogen mass deposition per area unit obtained by reference-free TXRF. Complementary energy and angle-resolved XPS (ER/AR-XPS) in the Si 2p core-level region was used to analyze the outermost surface region of the organic (silane layer)-inorganic (silicon wafer) interface. Different coexisting silicon species as silicon, native silicon oxide, and silane were identified and quantified. As a result of the presented proof-of-concept, absolute and traceable values for the areic density of silanes containing nitrogen as intrinsic marker are obtained by calibration of the XPS methods with reference-free TXRF. Furthermore, ER/AR-XPS is shown to facilitate the determination of areic densities in (mono)layers made from silanes having no heteroatomic marker other than silicon. After calibration with reference-free TXRF, these areic densities of silane molecules can be determined when using the XPS component intensity of the silane's silicon atom. Y1 - 2015 U6 - https://doi.org/10.1021/acs.analchem.5b02846 SN - 0003-2700 SN - 1520-6882 VL - 87 IS - 19 SP - 10117 EP - 10124 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Ehlert, Christopher A1 - Kröner, Dominik A1 - Saalfrank, Peter T1 - A combined quantum chemical/molecular dynamics study of X-ray photoelectron spectra of polyvinyl alcohol using oligomer models JF - Journal of electron spectroscopy and related phenomena : the international journal on theoretical and experimental aspects of electron spectroscopy N2 - X-ray photoelectron spectroscopy (XPS) is a powerful tool for probing the local chemical environment of atoms near surfaces. When applied to soft matter, such as polymers, XPS spectra are frequently shifted and broadened due to thermal atom motion and by interchain interactions. We present a combined quantum mechanical QM/molecular dynamics (MD) simulation of X-ray photoelectron spectra of polyvinyl alcohol (PVA) using oligomer models in order to account for and quantify these effects on the XPS (C1s) signal. In our study, molecular dynamics at finite temperature were performed with a classical forcefield and by ab initio MD (AIMD) using the Car-Parrinello method. Snapshots along, the trajectories represent possible conformers and/or neighbouring environments, with different C1s ionization potentials for individual C atoms leading to broadened XPS peaks. The latter are determined by Delta-Kohn Sham calculations. We also examine the experimental practice of gauging XPS (C1s) signals of alkylic C-atoms in C-containing polymers to the C1s signal of polyethylene. We find that (i) the experimental XPS (C1s) spectra of PVA (position and width) can be roughly represented by single-strand models, (ii) interchain interactions lead to red-shifts of the XPS peaks by about 0.6 eV, and (iii) AIMD simulations match the findings from classical MD semi-quantitatively. Further, (iv) the gauging procedure of XPS (C1s) signals to the values of PE, introduces errors of about 0.5 eV. (C) 2014 Elsevier B.V. All rights reserved. KW - Simulation of polymer XPS KW - Delta-Kohn Sham method KW - Thermal broadening effects KW - Interchain interactions KW - Classical MD KW - Poly vinyl alcohol Y1 - 2015 U6 - https://doi.org/10.1016/j.elspec.2014.12.007 SN - 0368-2048 SN - 1873-2526 VL - 199 SP - 38 EP - 45 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Eisold, Ursula A1 - Sellrie, Frank A1 - Schenk, Jörg A. A1 - Lenz, Christine A1 - Stöcklein, Walter F. M. A1 - Kumke, Michael Uwe T1 - Bright or dark immune complexes of anti-TAMRA antibodies for adapted fluorescence-based bioanalysis JF - Analytical & bioanalytical chemistry N2 - Fluorescence labels, for example fluorescein or rhodamin derivatives, are widely used in bioanalysis applications including lateral-flow assays, PCR, and fluorescence microscopy. Depending on the layout of the particular application, fluorescence quenching or enhancement may be desired as the detection principle. Especially for multiplexed applications or high-brightness requirements, a tunable fluorescence probe can be beneficial. The alterations in the photophysics of rhodamine derivatives upon binding to two different anti-TAMRA antibodies were investigated by absorption and fluorescence-spectroscopy techniques, especially determining the fluorescence decay time and steady-state and time-resolved fluorescence anisotropy. Two monoclonal anti-TAMRA antibodies were generated by the hybridoma technique. Although surface-plasmon-resonance measurements clearly proved the high affinity of both antibodies towards 5-TAMRA, the observed effects on the fluorescence of rhodamine derivatives were very different. Depending on the anti-TAMRA antibody either a strong fluorescence quenching (G71-DC7) or a distinct fluorescence enhancement (G71-BE11) upon formation of the immune complex was observed. Additional rhodamine derivatives were used to gain further information on the binding interaction. The data reveal that such haptens as 5-TAMRA could generate different paratopes with equal binding affinities but different binding interactions, which provide the opportunity to adapt bioanalysis methods including immunoassays for optimized detection principles for the same hapten depending on the specific requirements. KW - mAb KW - Fluorescence KW - Anisotropy KW - Exciplex KW - Energy-transfer probe Y1 - 2015 U6 - https://doi.org/10.1007/s00216-015-8538-0 SN - 1618-2642 SN - 1618-2650 VL - 407 IS - 12 SP - 3313 EP - 3323 PB - Springer CY - Heidelberg ER - TY - THES A1 - Enzenberg, Anne T1 - Neue fluoreszierende Copolymere für sensitive Detektionssysteme in Wasser T1 - New fluorescent copolymers for sensitive detection systems in water N2 - Ziel dieser Arbeit war die Synthese und Charakterisierung von neuartigen fluoreszierenden Copolymeren zur Analytdetektion in wässrigen Systemen. Das Detektionssystem sollte ein einfaches Schalten der Fluoreszenz bei Analytbindung „Aus“ bzw. Verdrängung „An“ ermöglichen. Dafür wurde die Synthese eines funktionalisierten Monomers so geplant, dass sich Fluorophor und Analyt innerhalb derselben Monomereinheit in direkter Nachbarschaft zueinander befinden. So sollten bei Erkennung des Analyten durch eine mit einem Fluoreszenzlöscher funktionalisierte Erkennungsstruktur Fluorophor und Löscher in einen vorgegebenen Abstand zueinander gezwungen und die Fluoreszenz des Fluorophors effizient gelöscht werden. Bei anschließender Verdrängung der Erkennungseinheit durch einen stärker bindenden Analyten sollte die Fluoreszenz wieder „angeschaltet“ werden. Eine weitere Zielstellung für das Detektionssystem war eine hohe Löslichkeit und Fluoreszenzintensität in Wasser. Da die Anwendung solcher Sensoren besonders in der Medizin und Biologie, z.B. für Schnellerkennungstest von Pathogenen, von Interesse ist, ist die Kompatibilität mit wässrigen Medien essentiell. Die funktionalisierten Monomere wurden frei radikalisch mit N Vinyl-pyrrolidon bzw. N Vinyl¬caprolactam zu wasserlöslichen, fluoreszierenden Copolymeren umgesetzt. In den N-Vinyl¬pyrrolidon-Polymeren (PNVP) wurde RhodaminB, in den thermoresponsiven N Vinyl¬caprolactam-Polymeren (PNVCL) ein Naphthalsäureimid als Fluorophor verwendet. Während Rhodamine eine hohe Fluoreszenzintensität, gute Quantenausbeuten und hohen Extinktionskoeffizienten in Wasser zeigen, sind Naphthalsäure¬imide umgebungssensitive Chromophore, die bei Änderung ihrer Lösungsmittelumgebung, wie z.B. beim Kollaps eines thermoresponsiven Polymers in Wasser, ihre Fluoreszenzintensität und Quantenausbeute drastisch ändern können. Der Vorteil der hier verwendeten Strategie der Monomersynthese liegt darin, dass bei jeder spezifischen Analytdetektion durch eine Erkennungseinheit die Fluoreszenz effizient gelöscht bzw. bei Verdrängung durch einen stärker bindenden Analyten wieder „angeschaltet“ wird. Dieses Prinzip wird bereits vielfach in der Biologie in sogenannten „Molecular Beacons“ ausgenutzt, wobei ein Fluorophor und ein Löscher durch spezifische DNA Basenpaarung in einen vorgegebenen Abstand zueinander gezwungen werden und so ein „Schalten“ der Fluoreszenz ermöglichen. Aufgrund der vorgegebenen Struktur der DNA Basensequenzen ist es jedoch nicht direkt auf andere Erkennungsreaktionen übertragbar. Daher wurde ein Modellsystem entwickelt, welches die Möglichkeit bietet Analyt, Erkennungseinheit und Signalgeber variabel, je nach Anforderungen des Systems, auszutauschen. So soll es möglich sein, den Sensor a priori für jede Erkennungs¬reaktion zu verwenden. Als Modell Bindungs¬paare wurden ß Cyclodextrin/Adamantan und Con¬cana¬valinA/Mannose ausgewählt. Adamantan bzw. Mannose wurde als Analyt zusammen mit dem Fluorophor in das Polymer eingebunden. ß Cyclo¬dextrin (ß CD) bzw. ConcanavalinA (ConA) wurde als Erkennungsstruktur an einem Fluoreszenzlöscher immobilisiert. Polymer-basierte Fluoreszenzsensoren sind in der Fachliteratur gut dokumentiert. In der Regel sind Signalgeber und Analyt jedoch statistisch im Polymer verteilt, da sie sich entweder in unterschiedlichen Monomereinheiten befinden oder die Funktionalisierung durch eine polymeranaloge Umsetzung erfolgt. Der gewählte Ansatz Fluorophor und Analyt innerhalb derselben Monomereinheit einzubinden, soll bei jeder Erkennungsreaktion des Analyten zu einer Änderung der Signalintensität des Fluorophors führen. Eine hohe Signalintensität bei Analytdetektion ist wünschenswert, insbesondere für Erkennungsreaktionen, die mit möglichst geringem apparativem Aufwand, am besten mit dem bloßen Auge zu verfolgen sein sollen. Des Weiteren ist es möglich den Fluorophorgehalt im Polymer genau einzustellen und so Selbstlöschung zu vermeiden. Die synthetisierten Polymere haben einen Fluorophorgehalt von 0,01 mol% bis 0,5 mol%. Für die RhodaminB haltigen Polymere zeigte sich, dass ein Fluorophorgehalt unterhalb 0,1 mol% im Polymer die höchsten Ausbeuten, Molmassen und Quantenausbeuten liefert. Für die Naphthalsäureimid haltigen Polymere hingegen wurden auch für einen Fluorophorgehalt von bis zu 1 mol% hohe Ausbeuten und Molmassen erreicht. Die Naphthalsäureimid haltigen Polymere haben jedoch in wässriger Lösungsmittelumgebung nur geringe Quantenausbeuten. Als Fluoreszenzlöscher wurden Goldnanopartikel synthetisiert, die mit den entsprechenden Erkennungsstrukturen (ß-CD oder ConA) für den verwendeten Analyten funktionalisiert wurden. Goldnanopartikel als Löscher bieten den Vorteil, dass ihre Dispergierbarkeit in einem Lösemittel durch Funktionalisierung ihrer Hülle gezielt gesteuert werden kann. Durch die hohe Affinität von Goldnanopartikeln zu Thiolen und Aminen konnten sie mit Hilfe einfacher Syntheseschritte mit Thio ß CD Derivaten bzw. ConA funktionalisiert werden. In der hier vorgelegten Arbeit sollte ein Modellsystem für einen solches fluoreszenz-basiertes Detektionssystem in Wasser entwickelt werden. Nachfolgend werden die zu erfüllenden strukturellen Voraussetzungen für die Synthese eines solchen Sensors nochmals zusammengefasst: 1. Verwendung eines Fluorophors, der eine hohe Signalintensität zeigt. 2. Analyt bzw. Erkennungseinheit soll sich im Abstand von wenigen Nanometern zum Signalgeber befinden, um bei jeder Detektionsreaktion die Signalintensität des Signalgebers beeinflussen zu können. 3. Die Detektionseinheit benötigt eine funktionelle Gruppe zur Immobilisierung. Immobilisierung kann z.B. durch Einbindung in ein Polymer erfolgen. 4. Der Fluorophor soll bei Änderung seiner lokalen Umgebung, durch Binden eines Löschers oder Änderung seiner Lösemittelumgebung seine Fluoreszenzeigenschaften drastisch ändern. 5. Die Reaktion sollte schnell und mit möglichst geringem apparativem Aufwand, am besten mit bloßem Auge zu verfolgen sein. Für das ß-CD/Adamantan Modellsystem wurde ein Fluoreszenz Aus/An Sensor entwickelt, der bei Binden ß CD funktionalisierter Goldnanopartikel an das polymergebundene Adamantan die Fluoreszenz des RhodaminB Fluorophors effizient löscht und bei Verdrängung der Goldnanopartikel wieder zurück gewinnt. Dies konnte auch mit bloßem Auge verfolgt werden. Für die Naphthalsäureimid Monomere, die mit NVCL copolymerisiert wurden, wurde abhängig von der lokalen Umgebung des Fluorophors eine unterschiedliche Verstärkung der Fluoreszenzintensität bei Überschreiten des Trübungspunktes des Polymers gefunden. Dabei zeigte sich, dass die Einführung eines Abstandshalters zwischen Polymerrückgrat und Fluorophor zu einer großen Fluoreszenz¬verstärkung führt, während sich ohne Abstandshalter die Fluoreszenzintensität bei Über¬schreiten des Trübungspunktes kaum ändert. N2 - Novel fluorescent copolymers for analyte detection in aqueous media have been synthesized and characterized. The detection system is designed to switch fluorescence between an “Off” state for analyte binding and an “On” state for analyte displacement. A functional monomer was synthesized in which fluorophore and analyte are placed close to each other within the same monomer unit. If the fluorescence quencher labeled recognition unit detects an analyte, fluorophore and quencher are forced in a very short distance to each other and fluorescence is quenched efficiently. The recognition unit is afterwards replaced through a stronger binding analyte and fluorescence should be “turned on” again. Another requirement for the detection system was high solubility and fluorescence intensity in water. Water compatibility is essential for implementation of such sensor systems especially in medicine and biology, e.g. for fast testing systems of pathogens. The synthesized monomers have been copolymerized in a free radical polymerization with N vinyl¬pyrrolidone or N vinylcaprolactame to give fluorescent, water soluble copolymers. For the N vinyl-pyrrolidone polymers (PNVP) a rhodamineB fluorophore was used whereas for the thermoresponsive N vinyl-caprolactame polymers (PNVCL) a naphthalimide fluorophore was used in the comonomer. While rhodamines are well known for their high fluorescence intensity, quantum yield and extinction coefficient in water, naphthalimides are known to be environment sensitive fluorophores who can change their fluorescence intensity drastically depending on their local solvent vicinity. Such a functional monomer design should give the advantage of efficient fluorescence quenching during analyte binding and fluorescence enhancement when the recognition unit is afterwards displaced. This principle is often used in systems like molecular beacons. Fluorophore and quencher are forced in a given distance through specific DNA base pairing and fluorescence can be switched. Because of the given DNA base sequence this detection system cannot be directly implemented to other recognition reactions. Here a model system was developed which gives the possibility to vary analyte, recognition unit and fluorophore. This way it should be possible to adopt the sensor a priori to every recognition reaction. ß-cyclodextrin/adamantane and concana¬valinA/mannose were chosen as model binding pairs. Adamantane or mannose and the fluorophore are attached to the polymer backbone. The ß cyclodextrin (ß-CD) or concanavalinA (ConA) recognition unit is immobilized on a fluorescence quencher. Polymer based fluorescence sensors are well known in literature. Usually fluorophore and analyte are statistically spread in the polymer because they are independently incorporated via different monomer units or functionalization is done polymer analog. To place fluorophore and analyte in the same monomer unit should have the benefit that every recognition event also leads to a change of signal intensity of the fluorophore. High signal intensity is crucial especially for recog¬nition reactions which should be tracked with only simple equipment or even with the naked eye. Even more it is possible to adjust the fluorophore content in the polymer. The synthesized polymers have a fluorophore content between 0.01 mol% and 0.5 mol%. For the rhodamineB containing polymers a fluorophore content below 0.1 mol% gives the highest yields, molecular weight and quantum yields. The polymers which contain naphthalimide as fluorophore give high yields and molecular weight up to 1 mol% of fluorophore content in the polymer but the quantum yields are in general low in aqueous media. Gold nano¬particles (Au NP) are synthesized as fluorescence quencher and functionalized with the recognition units (ß-CD or ConA) for analyte detection. Gold nanoparticles as fluorescence quencher have the advantage that their dispersibility in a solvent can be controlled by the choice of ligand used for the stabilization of the particles. Because of their high affinity to thiols and amines it was possible to synthesize thio-ß-CD and ConA functionalized gold nanoparticles in only a few synthetic steps.   Here a model system for fluorescent detection in water is presented. The structural requirements that have to be fulfilled for the synthesis of such a detection system are summarized: 1. The fluorophore needs to have high signal intensity. 2. Analyte or recognition unit have to be only a few nanometer apart from the signaling unit so every recognition reaction leads to a change of signal intensity. 3. The detection unit needs a functional group for immobilization. Immobilization can be done for example in a polymer matrix. 4. The fluorophore should change its fluorescence properties drastically through change of its local environment for example when binding a fluorescence quencher. 5. Reaction should be fast and detection should be possible with only little equipment or even with the naked eye It was possible to synthesis a fluorescence Off/On sensor for a ß-CD/adamantane model system. Fluorescence of the rhodamineB fluorophore is quenched during binding of ß-CD-Au-NPs and efficiently enhanced when the ß-CD-Au-NPs are displaced through a better binding analyte which can be even followed by the naked eye (Scheme 1). For the naphthalimide containing thermoresponsive N-vinylcaprolactame polymers a dependence of the fluorescence enhancement at polymer collapse is found depending on the local vicinity of the fluorophore. Introducing a spacer between fluorophore and polymer backbone leads to a high fluorescence enhancement while polymers without a spacer show almost no fluorescence enhancement during the collapse. KW - Fluoreszenzsensor KW - fluorescence sensor KW - thermoresponsiv KW - thermoresponsive KW - ß-Cyclodextrin KW - ß-cyclodextrine KW - Rhodamin B KW - rhodamine b KW - Naphthalimid KW - naphthalimide KW - Solvatochromie KW - solvatochrome KW - N-Vinylpyrrolidon KW - N-vinylpyrrolidone KW - N-Vinylcaprolactam KW - N-vinylcaprolactame Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-82325 ER - TY - JOUR A1 - Fandrich, Artur A1 - Buller, Jens A1 - Schäfer, Daniel A1 - Wischerhoff, Erik A1 - Laschewsky, André A1 - Lisdat, Fred T1 - Electrochemical characterization of a responsive macromolecular interface on gold JF - Physica status solidi : A, Applications and materials science N2 - This study reports on the investigation of a thermoresponsive polymer as a thin film on electrodes and the influence of coupling a peptide and an antibody to the film. The utilized polymer from the class of poly(oligoethylene glycol)-methacrylate polymers (poly(OEGMA)) with carboxy functions containing side chains was synthesized and properly characterized in aqueous solutions. The dependence of the cloud point on the pH of the surrounding media is discussed. The responsive polymer was immobilized on gold electrodes as shown by electrochemical, quartz crystal microbalance (QCM), and atomic force microscopy (AFM) techniques. The temperature dependent behavior of the polymer covalently grafted to gold substrates is investigated using cyclic voltammetry (CV) in ferro-/ferricyanide solution. Significant changes in the slope of the temperature-dependence of the voltammetric peak current and the peak separation values clearly indicate the thermally induced conformational change on the surface. Finally, a biorecognition reaction between a short FLAG peptide (N-Asp-Tyr-Lys-Asp-Asp-Asp-Asp-Lys-C) covalently immobilized on the polymer interface and the corresponding IgG antibody was performed. The study shows that the responsiveness of the electrode is retained after peptide coupling and antibody binding, although the response is diminished. KW - biorecognition reactions KW - cyclic voltammetry KW - electrodes KW - gold KW - interfaces KW - responsive polymers Y1 - 2015 U6 - https://doi.org/10.1002/pssa.201431698 SN - 1862-6300 SN - 1862-6319 VL - 212 IS - 6 SP - 1359 EP - 1367 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Federico, Stefania A1 - Pierce, Benjamin F. A1 - Piluso, Susanna A1 - Wischke, Christian A1 - Lendlein, Andreas A1 - Neffe, Axel T. T1 - Design of Decorin-Based Peptides That Bind to CollagenI and their Potential as Adhesion Moieties in Biomaterials JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - Mimicking the binding epitopes of protein-protein interactions by using small peptides is important for generating modular biomimetic systems. A strategy is described for the design of such bioactive peptides without accessible structural data for the targeted interaction, and the effect of incorporating such adhesion peptides in complex biomaterial systems is demonstrated. The highly repetitive structure of decorin was analyzed to identify peptides that are representative of the inner and outer surface, and it was shown that only peptides based on the inner surface of decorin bind to collagen. The peptide with the highest binding affinity for collagenI, LHERHLNNN, served to slow down the diffusion of a conjugated dye in a collagen gel, while its dimer could physically crosslink collagen, thereby enhancing the elastic modulus of the gel by one order of magnitude. These results show the potential of the identified peptides for the design of biomaterials for applications in regenerative medicine. KW - biomaterials KW - collagen KW - gels KW - peptides KW - protein-protein interactions Y1 - 2015 U6 - https://doi.org/10.1002/anie.201505227 SN - 1433-7851 SN - 1521-3773 VL - 54 IS - 37 SP - 10980 EP - 10984 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Feldbusch, Elvira T1 - Geochemische Charakterisierung eines Formationsfluids im Unteren Perm T1 - Geochemical characterization of a formation fluid of Lower Permian reservoir BT - Herkunft, betriebsbedingte Prozesse und Rolle organischer Verbindungen im geothermischen Kreislauf BT - origin, operational processes and role of organic compounds in the geothermal cycle N2 - Diese Arbeit befasst sich mit der ganzheitlichen Betrachtung der Fluideigenschaften eines unterpermischen Reservoirs am Geothermie Forschungsstandort Groß Schönebeck (GrSk) bei Reservoirbedingungen und im Betrieb der Geothermieanlage. Die Untersuchungen zur Fluidherkunft ergeben, dass es sich um ein konnates Wasser meteorischen Ursprungs ohne den Einfluss der darüberliegenden Zechsteinwässer handelt. Die Ionen und Isotopenverhältnisse im Formationswasser gelöster Komponenten in GrSk belegen einen gemeinsamen Genesepfad mit Wässern anderer Rotliegend-Reservoire des Nordostdeutschen Beckens (NEGB). Die Isotopenverhältnisse von ⁸⁷Sr/⁸⁶Sr ≈ 0,7158 und von δ³⁴SV CDT ≈ 4,1 ‰ des Sulfats weisen auf die Anreicherung des Fluids mit schweren Isotopen durch die Fluid Gestein-Wechselwirkung mit Vulkaniten und Rotliegend Sandsteinen des Unteren Perms hin. Das im Formationswasser bei Reservoirbedingungen gelöste Gas (Gas/Wasser ≤ 2 bei STP) enthält Stickstoff (δ¹⁵NAir ≈ 0,6 ‰) und thermogenes Methan (δ¹³CV-PDB ≈ - 18 ‰) aus organischen Karbonablagerungen (Kerogen Typ - III Kohlen) hoher Reife. Die Isotopenverhältnisse der Edelgase belegen eine krustale Herkunft des Gasgemisches. Die berechnete Verweilzeit τ (⁴He) der Gase im Reservoir liegt zwischen 275 und 317 Ma und überschreitet damit bei gegebener Konzentration von Mutternukliden im Reservoirgestein das allgemein angenommene Zeitalter der Sedimentgruppe. Das lässt sich durch eine Zuwanderung von Gasen aus älteren Sedimentfolgen erklären. Die Veränderungen der physikochemischen Fluidparameter während des Anlagenbetriebs sind hauptsächlich temperaturbedingt. Bei stabilen Produktionsbedingungen und einer Temperatur von ca. 100 °C stabilisieren sich auch die Fluideigenschaften. Bei In situ Bedingungen übertage beträgt die Dichte ρ = 1,1325 ± 0,0002 g ∙ mL⁻¹, das Redoxpotential Eh = -105,5 ± 1,3 mV und der pH = 6,61 ± 0,002. Die relative Zusammensetzung der Gasphase bei stabilen Produktionsbedingungen zeigt dagegen eine geringe Erhöhung des Stickstoffanteils sowie des Anteils der Kohlenwasserstoffe (Ethan, Propan, usw.) und Abnahme des relativen Methananteils im Laufe des Betriebs. Die quantitative Untersuchung der sekundären mineralischen Ausfällungen im Fluid mittels sequentieller Extraktion zeigte, dass Schwermetalle als eine Hauptkomponente der Fluidfestphase größtenteils in Verbindung mit organischen Molekülen vorliegen. Experimente zum Einfluss organischer Verbindungen unterschiedlicher Substanzklassen auf eine Mobilisierung der Schwermetalle aus dem Reservoirgestein ergaben, dass die Verbindungen wie Fettsäuren und PAK (polyzyklische aromatische Kohlenwasserstoffe) die Freisetzung von Kupfer, Nickel, Chrom und Blei verhindern bzw. zu derer Immobilisierung beitragen. Im Gegensatz dazu wird die Mobilität von Zink in Anwesenheit von diesen Verbindungen erhöht. Niedermolekulare Monocarbonsäuren und stickstoffhaltige Heteroaromaten tragen, mit Ausnahme von Blei, zur Freisetzung bzw. Mobilisierung von Schwermetallen aus dem Reservoirgestein bei. Die gewonnenen Erkenntnisse dieser Arbeit bestätigen das Risiko massiver Ausfällungen auf der kalten Seite der Geothermieanlage bei Inbetriebnahme des Kraftwerks, wenn keine an den Fluidchemismus angepassten Präventionsmethoden eingesetzt werden. Die Isotopenzusammensetzung der Fluidkomponenten sowie geringfügige Schwankungen der Gaszusammensetzung im kontinuierlichen Anlagenbetrieb lässt eine Kommunikation des unterpermischen Reservoirs mit dem darunter liegenden Oberkarbon vermuten, was eine nachträgliche Veränderung der Fluidzusammensetzung beim Dauerbetrieb der Anlage bedeuten kann. N2 - This work represents a holistic study of the properties of fluid from the Lower Permian reservoirs of the geothermal research site Gross Schönebeck at reservoir and at wellhead conditions during fluid circulation. Investigations of the fluid origin show that the formation water represents a connate water of meteoric origin without any evidence of influences from overlying Zechstein. The tracers of formation water as well as the isotopic signatures of relevant components reveal a common genesis path with waters of other Rotliegend reservoirs of the Northeast German Basin (NEGB). The isotope ratios of ⁸⁷Sr/⁸⁶Sr ≈ 0,7158 and sulphate δ³⁴SV-CDT ≈ 4,1 ‰ indicate strong water rock interaction with Lower Permian Rotliegend sandstones and volcanic rocks, resulting in an enrichment with 87Sr and 34S. The fluid dissolves about gas/water ≤ 2 (at STP) of formation gas at reservoir conditions. Major components are nitrogen (δ¹⁵NAir ≈ 0,6 ‰) and methane (δ¹³CV PDB ≈ - 18 ‰) of thermogenic origin from carboniferous organic matter with kerogen Type III coals of high maturity. The noble gases represent a gas mixture of crustal origin with a residence time τ (⁴He) in the reservoir of 275 - 317 Ma. This value exceeds commonly accepted age and parent radionuclide content of the stratigraphic group. This indicates migration of gases from older sediment layers. The changes of physico-chemical fluid properties above ground during plant operation are primarily temperature-affected. At steady operating conditions with a stable temperature of ~ 100 °C fluid properties stabilise with an in-situ density ρ = 1,1325 ± 0,0002 g ∙ mL⁻¹, redox potential Eh = -105,5 ± 1,3 mV and pH = 6,61 ± 0,002. The composition of formation gas at steady operating conditions shows a slight increase of nitrogen content and lower concentrated hydrocarbons (ethane, propane, etc.). Methane content decreases during fluid production, which could be an indicator for gas migration from different reservoir sections. A quantitative examination of secondary mineral precipitations in the fluid by means of sequential extractions indicates that heavy metals are largely bonded on the organic matter. Experiments on the impact different classes of organic components on the mobilisation of heavy metals from the reservoir rock demonstrated that the most heavy metals (Cu, Pb, Cr and Ni) can hardly be mobilized by fatty acids and polycyclic aromatic hydrocarbons or can be precipitated from the fluid. Zinc showed the opposite behaviour with these organic compounds. Organic components such as monocarboxylic acids and nitrogen heterocycles contribute to removing of heavy metals from the reservoir rock, with exception of lead. The findings of this work confirm the risk of considerable precipitation on the cold side of the geothermal plant during commissioning of the power station unless prevention methods adapted for the fluid chemistry are applied. The isotopic composition of fluid components as well as a minor fluctuation of gas composition during continuous plant operation indicates a potential communication of the Lower Permian reservoir with the underlying Upper Carboniferous formation. This may lead to a subsequent change of the fluid composition during a long-term operation of the plant in GrSk. KW - Groß Schönebeck KW - Rotliegend KW - Formationsfluid KW - Schwermetalle KW - Herkunft KW - geothermal KW - origin KW - formation fluid KW - heavy metals KW - onsite monitoring Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-87402 ER - TY - THES A1 - Fettkenhauer, Christian T1 - Ionothermale Synthese funktioneller Kohlenstoffnitrid basierter Materialien T1 - Ionothermal synthesis of functional carbon nitride based materials N2 - Die Doktorarbeit behandelt die Synthese Kohlenstoffnitrid basierter Materialien in eutektischen Mischungen bivalenter Metallchloride. Der Fokus liegt dabei auf ZnCl2-, SnCl2- und CoCl2-haltigen eutektischen Mischungen, in denen die Kondensation gebräuchlicher organischer Precursoren durchgeführt wird. Im Rahmen dessen wird untersucht wie durch die Reaktionsführung in Salzschmelzen unterschiedlicher Lewis-Acidität, neben der Molekülstruktur andere charakteristische Eigenschaften, wie Morphologie, Kristallinität und spezifische Oberflächen, der Materialien kontrolliert werden können. Darüber hinaus werden die optischen Eigenschaften der Materialien erörtert und in diesem Zusammenhang die Eignung als Photokatalysatoren für den oxidativen Abbau organischer Farbstoffe und für die photokatalytische Wasserreduktion bzw. –oxidation untersucht. Zusätzlich wird gezeigt, wie im System LiCl/KCl in einem einstufigen Prozess edelmetallfreie Kohlenstoffnitrid Komposite zur photokatalytischen Wasserreduktion hergestellt werden können. N2 - The thesis deals with the synthesis of carbon nitride based materials in eutectic mixtures of bivalent metal chlorides. The focus is on ZnCl2, SnCl2 and CoCl2 containing eutectic mixtures in which the condensation reaction of classical organic precursors is carried out. In this context, it is investigated how to control molecular structure and other materials properties, like morphology, crystallinity and specific surface areas by using salt melts of different Lewis acidity. Moreover optical properties of the materials are discussed and in this connection their suitability as photocatalysts for dye degradation and photocatalytic water reduction and oxidation is investigated. Additionally it is demonstrated how to produce noble metal free carbon nitride composites in LiCl/KCl melt for photocatalytic water reduction. KW - Kohlenstoffnitride KW - ionothermal KW - Komposite KW - Photokatalyse KW - Wasserstoff KW - carbon nitride KW - ionothermal KW - composites KW - photocatalysis KW - hydrogen Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-78087 ER - TY - JOUR A1 - Floss, Gereon A1 - Saalfrank, Peter T1 - The Photoinduced E -> Z Isomerization of Bisazobenzenes: A Surface Hopping Molecular Dynamics Study JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - The photoinduced E -> Z isomerization of azobenzene is a prototypical example of molecular switching. On the way toward rigid molecular rods such as those for opto-mechanical applications, multiazobenzene structures have been suggested in which several switching units are linked together within the same molecule (Bleger et al., J. Phys. Chem. B 2011, 115, 9930-9940). Large differences in the switching efficiency of multiazobenzenes have been observed, depending on whether the switching units are electronically decoupled or not. In this paper we study, on a time-resolved molecular level, the E -> Z isomerization of the simplest multiazobenzene, bisazobenzene (BAB). Two isomers (ortho- and para-BAB), differing only in the connectivity of two azo groups on a shared phenyl ring will be considered.To do so, nonadiabatic semiclassical dynamics after photo-excitation of the isomers are studied by employing an "on-the-fly", fewest switches surface hopping approach. States and couplings are calculated by Configuration Interaction (CI) based on a semiempirical (AM1) Hamiltonian (Persico and co-workers, Chem. Eur. J. 2004, 10, 2327-2341). In the case of para-BAB, computed quantum yields for photoswitching are drastically reduced compared to pristine azobenzene, due to electronic coupling of both switching units. A reason for this (apart from altered absorption spectra and reduced photochromicity) is the drastically reduced lifetimes of electronically excited states which are transiently populated. In contrast for meta-connected species, electronic subsystems are largely decoupled, and computed quantum yields are slightly higher than that for pristine azobenzene because of new isomerization channels. In this case we can also distinguish between single- and double-switch events and we find a cooperative effect: The isomerization of a single azo group is facilitated if the other azo group is already in the Z-configuration. Y1 - 2015 U6 - https://doi.org/10.1021/acs.jpca.5b02933 SN - 1089-5639 VL - 119 IS - 20 SP - 5026 EP - 5037 PB - American Chemical Society CY - Washington ER - TY - CHAP A1 - Frombach, Janna A1 - Rancan, Fiorenza A1 - Fleige, Emanuel A1 - Haag, Rainer A1 - Schumacher, Frank A1 - Kleuser, Burkhard A1 - Yamamoto, Kenji A1 - Rühl, Eckart A1 - Blume-Peytavi, Ulrike A1 - Vogt, Annika T1 - Skin penetration and dexamethasone release from polymer nanoparticles in ex vivo human skin T2 - The journal of investigative dermatology Y1 - 2015 SN - 0022-202X SN - 1523-1747 VL - 135 SP - S52 EP - S52 PB - Nature Publ. Group CY - New York ER - TY - JOUR A1 - Gallandi, Lukas A1 - Körzdörfer, Thomas T1 - Long-Range Corrected DFT Meets GW: Vibrationally Resolved Photoelectron Spectra from First Principles JF - Journal of chemical theory and computation N2 - We propose an entirely nonempirical and computationally efficient scheme to calculate highly reliable vibrationally resolved photoelectron spectra for molecules from first principles. To this end, we combine nonempirically tuned long-range corrected hybrid functionals with non-self-consistent many-body perturbation theory in the G(0)W(0) approximation and a Franck-Condon multimode analysis based on DFT-calculated frequencies. The vibrational analysis allows for a direct comparison of the GW-calculated spectra to gas-phase ultraviolet photoelectron measurements of neutral and anionic molecules, respectively. Direct comparison of the calculated peak maxima with experiment yields mean absolute errors below 0.1 eV for ionization potentials, electron affinities, and fundamental gaps, clearly outperforming commonly used G(0)W(0) approaches at similar numerical costs. Y1 - 2015 U6 - https://doi.org/10.1021/acs.jctc.5b00820 SN - 1549-9618 SN - 1549-9626 VL - 11 IS - 11 SP - 5391 EP - 5400 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Gambinossi, Filippo A1 - Sefcik, Lauren S. A1 - Wischerhoff, Erik A1 - Laschewsky, André A1 - Ferri, James K. T1 - Engineering Adhesion to Thermoresponsive Substrates: Effect of Polymer Composition on Liquid-Liquid-Solid Wetting JF - ACS applied materials & interfaces N2 - Adhesion control in liquidliquidsolid systems represents a challenge for applications ranging from self-cleaning to biocompatibility of engineered materials. By using responsive polymer chemistry and molecular self-assembly, adhesion at solid/liquid interfaces can be achieved and modulated by external stimuli. Here, we utilize thermosensitive polymeric materials based on random copolymers of di(ethylene glycol) methyl ether methacrylate (x = MEO(2)MA) and oligo(ethylene glycol) methyl ether methacrylate (y = OEGMA), that is, P(MEO(2)MA(x)-co-OEGMA(y)), to investigate the role of hydrophobicity on the phenomenon of adhesion. The copolymer ratio (x/y) dictates macromolecular changes enabling control of the hydrophilic-to-lipophilic balance (HBL) of the polymer brushes through external triggers such as ionic strength and temperature. We discuss the HBL of the thermobrushes in terms of the surface energy of the substrate by measuring the contact angle at waterdecaneP(MEO(2)MA(x)-co-OEGMA(y)) brush contact line as a function of polymer composition and temperature. Solid supported polyelectrolyte layers grafted with P(MEO(2)MA(x)-co-OEGMA(y)) display a transition in the wettability that is related to the lower critical solution temperature of the polymer brushes. Using experimental observation of the hydrophilic to hydrophobic transition by the contact angle, we extract the underlying energetics associated with liquidliquidsolid adhesion as a function of the copolymer ratio. The change in cellular attachment on P(MEO(2)MA(x)-co-OEGMA(y)) substrates of variable (x/y) composition demonstrates the subtle role of compositional tuning on the ability to control liquidliquidsolid adhesion in biological applications. KW - water/decane contact angle KW - thermoresponsive substrates KW - di(ethylene glycol) methy ether methacrylate KW - oligo(ethylene glycol) methyl ether methacrylate KW - hydrophilic-to-lipophilic balance KW - programmable adhesion Y1 - 2015 U6 - https://doi.org/10.1021/am507418m SN - 1944-8244 VL - 7 IS - 4 SP - 2518 EP - 2528 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Gorobtsov, Oleg Yu. A1 - Lorenz, Ulf A1 - Kabachnik, Nicolai M. A1 - Vartanyants, Ivan A. T1 - Theoretical study of electronic damage in single-particle imaging experiments at x-ray free-electron lasers for pulse durations from 0.1 to 10 fs JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - X-ray free-electron lasers (XFELs) may allow us to employ the single-particle imaging (SPI) method to determine the structure of macromolecules that do not form stable crystals. Ultrashort pulses of 10 fs and less allow us to outrun complete disintegration by Coulomb explosion and minimize radiation damage due to nuclear motion, but electronic damage is still present. The major contribution to the electronic damage comes from the plasma generated in the sample that is strongly dependent on the amount of Auger ionization. Since the Auger process has a characteristic time scale on the order of femtoseconds, one may expect that its contribution will be significantly reduced for attosecond pulses. Here we study the effect of electronic damage on the SPI at pulse durations from 0.1 to 10 fs and in a large range of XFEL fluences to determine optimal conditions for imaging of biological samples. We analyzed the contribution of different electronic excitation processes and found that at fluences higher than 1013-1015 photons/mu m(2) (depending on the photon energy and pulse duration) the diffracted signal saturates and does not increase further. A significant gain in the signal is obtained by reducing the pulse duration from 10 to 1 fs. Pulses below a duration of 1 fs do not give a significant gain in the scattering signal in comparison with 1-fs pulses. We also study the limits imposed on SPI by Compton scattering. Y1 - 2015 U6 - https://doi.org/10.1103/PhysRevE.91.062712 SN - 1539-3755 SN - 1550-2376 VL - 91 IS - 6 PB - American Physical Society CY - College Park ER - TY - THES A1 - Grygiel, Konrad T1 - Poly(ionic liquid) stabilizers and new synthetic approaches T1 - Polyionische Flüssigkeiten als Stabilisatoren und neue Synthesewege N2 - The main focus of the present thesis was to investigate the stabilization ability of poly(ionic liquid)s (PILs) in several examples as well as develop novel chemical structures and synthetic routes of PILs. The performed research can be specifically divided into three parts that include synthesis and application of hybrid material composed of PIL and cellulose nanofibers (CNFs), thiazolium-containing PILs, and main-chain imidazolium-type PILs. In the first chapter, a vinylimidazolium-type IL was polymerized in water in the presence of CNFs resulting in the in situ electrostatic grafting of polymeric chains onto the surface of CNFs. The synthesized hybrid material merged advantages of its two components, that is, superior mechanical strength of CNFs and anion dependent solution properties of PILs. In contrast to unmodified CNFs, the hybrid could be stabilized and processed in organic solvents enabling its application as reinforcing agent for porous polyelectrolyte membranes. In the second part, PILs and ionic polymers containing two types of thiazolium repeating units were synthesized. Such polymers displayed counterion dependent thermal stability and solubility in organic solvents of various dielectric constants. This new class of PILs was tested as stabilizers and phase transfer agents for carbon nanotubes in aqueous and organic media, and as binder materials to disperse electroactive powders and carbon additives in solid electrode in lithium-ion batteries. The incorporation of S and N atoms into the polymeric structures make such PILs also potential precursors for S, N - co-doped carbons. In the last chapter, reactants originating from biomass were successfully harnessed to synthesize main-chain imidazolium-type PILs. An imidazolium-type diester IL obtained via a modified Debus-Radziszewski reaction underwent transesterification with diol in a polycondensation reaction. This yielded a polyester-type PIL which CO2 sorption properties were investigated. In the next step, the modified Debus-Radziszewski reaction was further applied to synthesize main-chain PILs according to a convenient, one-step protocol, using water as a green solvent and simple organic molecules as reagents. Depending on the structure of the employed diamine, the synthesized PILs after anion exchange showed superior thermal stability with unusually high carbonization yields. Overall, the outcome of these studies will actively contribute to the current research on PILs by introducing novel PIL chemical structures, improved synthetic routes, and new examples of stabilized materials. The synthesis of main-chain imidazolium-type PILs by a modified Debus-Radziszewski reaction is of a special interest for the future work on porous ionic liquid networks as well as colloidal PIL nanoparticles. N2 - Im Mittelpunkt der vorliegenden Arbeit stand die Entwicklung neuer polymerer ionischen Flüssigkeiten (PILs) mittels neuer Synthesewege als auch auf diesen PILs basierenden Kompositmaterialien. Die hergestellten Materialien wurden folgend hinsichtlich ihrer Tauglichkeit als Stabilisatoren, Phasentransferreagenzien, „binder“ oder CO2-Absorber untersucht. Die Untersuchungen lassen sich in drei Teile untergliedern und beinhalten Herstellung und Anwendungsuntersuchungen von Hybridmaterialien basierend auf PILs und Cellulosefasern im Nanometerbereich (CNF), von PILs mit Thiazoliumgruppen und schließlich PILs welche teilweise oder vollständig aus Biomaterialien hergestellt wurden mit Imidazoliumgruppen in der Hauptkette. In Gegenwart von CNF wurde eine vinylimidazoliumbasierte ionische Flüssigkeit (IL) in Wasser polymerisiert. Dies führte in situ zu einem elektrostatischen angraften der Ketten auf der Oberfläche der CNFs. Diese Kompositmaterialien vereinigen die Vorteile beider Komponenten, die außerordentliche mechanische Stabilität der CNFs und die vielseitigen mittels Gegenionen einstellbaren Lösungseigenschaften der PIL. Beispielsweise können diese Hybridmaterialien im Gegensatz zu den unmodifizierten CNFs in organischen Lösungsmitteln und somit zur Verstärkung für poröse Polyelektrolytmembranen eingesetzt werden. Im zweiten Teil wurden PILs und ioniosche Polymere synthetisiert mit Thiazoliumkationen in den Monomerbausteinen. Diese Polymere zeigten eine vom Gegenion abhängige thermische Stabilität und Löslichkeit in Lösungsmitteln verschiedenster Dielektrizitätskonstanten. Diese neue Klasse der PILs bzw. ionischen Polymere wurde hinsichtlich der Nutzbarkeit als Vorläufer für Stickstoff- und Schwefel-codotierte Kohlenstoffsysteme, Stabilisator sowie Phasentransferreagenz für „carbon nanotubes“ in wässrigem und organischen Lösungsmitteln und „binder“ für Elektrodenmaterialien in Lithiumionenbatterien. Im letzten Teil wurden aus Biomaterialien die Ausgangsstoffe für PILs mit imidazoliumbasierter Hauptkette gewonnen. Hierzu wurde der imidazoliumbasierende Diester mittels abgewandelter Debus-Radziszewski-Reaktion gewonnen und eine Umesterung mittels eines ebenfalls aus Biomaterialien stammenden Diols vorgenommen. Die erhaltene polyesterbasierte PIL wurde folgend hinsichtlich ihres CO2 – Absorbtionspotentials untersucht. Die geänderte Debus-Radziszewski-Reaktion wurde folgend für eine PIL-Einstufensynthese mit Wasser als grünem Lösungsmittel und einfachen hauptsächlich aus Biomasse gewonnen Reagenzien herangezogen. Abhängig von den eingesetzten Diaminen und Gegenionen konnten für die hergestellten PILs hervorragende thermische Stabilitäten oder beträchtliche Karbonisierungsausbeuten erreicht werden, welche für PILs zu den höchsten publizierten Werten in der Literatur zählen. Die vorgelegten Studien stellen einen wichtigen Beitrag auf dem Gebiet der PIL-Forschung dar mit neuen PIL-Strukturen, verbesserten Synthesewegen und neuen Stabilisierungsmöglichkeiten. Die Synthese der Hauptkettenimidazolium-PIL mittels angepasster Debus-Radziszewski-Reaktion ist eine vielversprechende Methode sowohl für die Herstellung poröser IL-Netzwerke als auch kolloidaler PIL-Nanopartikel. KW - ionic polymers KW - polymerised ionic liquids KW - ionic liquids KW - Debus-Radziszewski polymerization KW - thiazolium KW - ionische Flüssigkeit KW - Thiazol-Salze KW - ionischen Polymere KW - elektroaktive Polymere Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-80367 ER - TY - JOUR A1 - Guha, S. A1 - Warsinke, A. A1 - Tientcheu, Ch. M. A1 - Schmalz, K. A1 - Meliani, C. A1 - Wenger, Ch. T1 - Label free sensing of creatinine using a 6 GHz CMOS near-field dielectric immunosensor JF - The analyst : the analytical journal of the Royal Society of Chemistry N2 - In this work we present a CMOS high frequency direct immunosensor operating at 6 GHz (C-band) for label free determination of creatinine. The sensor is fabricated in standard 0.13 μm SiGe:C BiCMOS process. The report also demonstrates the ability to immobilize creatinine molecules on a Si3N4 passivation layer of the standard BiCMOS/CMOS process, therefore, evading any further need of cumbersome post processing of the fabricated sensor chip. The sensor is based on capacitive detection of the amount of non-creatinine bound antibodies binding to an immobilized creatinine layer on the passivated sensor. The chip bound antibody amount in turn corresponds indirectly to the creatinine concentration used in the incubation phase. The determination of creatinine in the concentration range of 0.88–880 μM is successfully demonstrated in this work. A sensitivity of 35 MHz/10 fold increase in creatinine concentration (during incubation) at the centre frequency of 6 GHz is gained by the immunosensor. The results are compared with a standard optical measurement technique and the dynamic range and sensitivity is of the order of the established optical indication technique. The C-band immunosensor chip comprising an area of 0.3 mm2 reduces the sensing area considerably, therefore, requiring a sample volume as low as 2 μl. The small analyte sample volume and label free approach also reduce the experimental costs in addition to the low fabrication costs offered by the batch fabrication technique of CMOS/BiCMOS process. Y1 - 2015 U6 - https://doi.org/10.1039/c4an02194k SN - 0003-2654 SN - 1364-5528 VL - 9 IS - 140 SP - 3019 EP - 3027 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Guha, S. A1 - Warsinke, A. A1 - Tientcheu, Ch. M. A1 - Schmalz, K. A1 - Meliani, C. A1 - Wenger, Ch. T1 - Label free sensing of creatinine using a 6 GHz CMOS near-field dielectric immunosensor N2 - In this work we present a CMOS high frequency direct immunosensor operating at 6 GHz (C-band) for label free determination of creatinine. The sensor is fabricated in standard 0.13 μm SiGe:C BiCMOS process. The report also demonstrates the ability to immobilize creatinine molecules on a Si3N4 passivation layer of the standard BiCMOS/CMOS process, therefore, evading any further need of cumbersome post processing of the fabricated sensor chip. The sensor is based on capacitive detection of the amount of non-creatinine bound antibodies binding to an immobilized creatinine layer on the passivated sensor. The chip bound antibody amount in turn corresponds indirectly to the creatinine concentration used in the incubation phase. The determination of creatinine in the concentration range of 0.88–880 μM is successfully demonstrated in this work. A sensitivity of 35 MHz/10 fold increase in creatinine concentration (during incubation) at the centre frequency of 6 GHz is gained by the immunosensor. The results are compared with a standard optical measurement technique and the dynamic range and sensitivity is of the order of the established optical indication technique. The C-band immunosensor chip comprising an area of 0.3 mm2 reduces the sensing area considerably, therefore, requiring a sample volume as low as 2 μl. The small analyte sample volume and label free approach also reduce the experimental costs in addition to the low fabrication costs offered by the batch fabrication technique of CMOS/BiCMOS process. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 195 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-81177 ER - TY - JOUR A1 - Guiet, Amandine A1 - Goebel, Caren A1 - Klingan, Katharina A1 - Lublow, Michael A1 - Reier, Tobias A1 - Vainio, Ulla A1 - Kraehnert, Ralph A1 - Schlaad, Helmut A1 - Strasser, Peter A1 - Zaharieva, Ivelina A1 - Dau, Holger A1 - Driess, Matthias A1 - Polte, Joerg A1 - Fischer, Anna T1 - Hydrophobic Nanoreactor Soft-Templating: A Supramolecular Approach to Yolk@Shell Materials JF - Advanced functional materials N2 - Due to their unique morphology-related properties, yolk@shell materials are promising materials for catalysis, drug delivery, energy conversion, and storage. Despite their proven potential, large-scale applications are however limited due to demanding synthesis protocols. Overcoming these limitations, a simple soft-templated approach for the one-pot synthesis of yolk@shell nanocomposites and in particular of multicore metal nanoparticle@metal oxide nanostructures (M-NP@MOx) is introduced. The approach here, as demonstrated for Au-NP@ITOTR (ITOTR standing for tin-rich ITO), relies on polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) inverse micelles as two compartment nanoreactor templates. While the hydrophilic P4VP core incorporates the hydrophilic metal precursor, the hydrophobic PS corona takes up the hydrophobic metal oxide precursor. As a result, interfacial reactions between the precursors can take place, leading to the formation of yolk@shell structures in solution. Once calcined these micelles yield Au-NP@ITOTR nanostructures, composed of multiple 6 nm sized Au NPs strongly anchored onto the inner surface of porous 35 nm sized ITOTR hollow spheres. Although of multicore nature, only limited sintering of the metal nanoparticles is observed at high temperatures (700 degrees C). In addition, the as-synthesized yolk@shell structures exhibit high and stable activity toward CO electrooxidation, thus demonstrating the applicability of our approach for the design of functional yolk@shell nanocatalysts. KW - inverse micelles KW - nanoreactor KW - polystyrene-block-poly(4-vinylpyridine) KW - soft-templating KW - tin-rich ITO KW - yolk@shell materials Y1 - 2015 U6 - https://doi.org/10.1002/adfm.201502388 SN - 1616-301X SN - 1616-3028 VL - 25 IS - 39 SP - 6228 EP - 6240 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Hahn, Simone A1 - Träger, Juliane A1 - Holdt, Hans-Jürgen T1 - Solid-Phase extraction of Pt(IV) with Dialkyl-(hexane-1,6-diyl) phosphate modified merrifield resins from aqueous chloride media in column operations JF - Separation and purification technology N2 - A series of three dialkyl phosphate resins with a Merrifield resin support was used to extract platinum from acidic media. In column operations total capacities of 85-130 mg/g were gained. The presence of palladium and rhodium results in the order: Pt(IV) > Pd(II) >> Rh(III). From a leach liquor gained from spent automotive catalysts metals forming anionic chloro complexes are co-extracted only to a small extent. However, in order to separate and enrich platinum a selective back-extraction can be done with a sodium thiocyanate solution. A second elution step with acidic thiourea leads to a mixed solution of palladium and rhodium. KW - platinum KW - column operation mode KW - phosphate KW - solid-phase extraction Y1 - 2015 U6 - https://doi.org/10.1080/01496395.2014.968264 SN - 0149-6395 SN - 1520-5754 VL - 50 IS - 2 SP - 191 EP - 206 PB - Taylor & Francis Group CY - Philadelphia ER - TY - JOUR A1 - Haralampiev, Ivan A1 - Mertens, Monique A1 - Schwarzer, Roland A1 - Herrmann, Andreas A1 - Volkmer, Rudolf A1 - Wessig, Pablo A1 - Mueller, Peter T1 - Recruitment of SH-Containing peptides to lipid and biological membranes through the use of a palmitic acid functionalized with a Maleimide Group JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - This study presents a novel and easily applicable approach to recruit sulfhydryl-containing biomolecules to membranes by using a palmitic acid which is functionalized with a maleimide group. Notably, this strategy can also be employed with preformed (biological) membranes. The applicability of the assay is demonstrated by characterizing the binding of a Rhodamine-labeled peptide to lipid and cellular membranes using methods of fluorescence spectroscopy, lifetime measurement, and microscopy. Our approach offers new possibilities for preparing biologically active liposomes and manipulating living cells. KW - liposomes KW - maleimide KW - membranes KW - palmitic acid KW - palmitoylation KW - peptides Y1 - 2015 U6 - https://doi.org/10.1002/anie.201408089 SN - 1433-7851 SN - 1521-3773 VL - 54 IS - 1 SP - 323 EP - 326 PB - Wiley-VCH CY - Weinheim ER - TY - CHAP A1 - Haralampiev, Ivan A1 - Mertens, Monique A1 - Schwarzer, Roland A1 - Herrmann, Andreas A1 - Volkmer, Rudolf A1 - Wessig, Pablo A1 - Müller, Peter T1 - A palmitic acid functionalized with a maleimide group is used to recruit SH-containing peptides to lipid and biological membranes T2 - The FEBS journal Y1 - 2015 SN - 1742-464X SN - 1742-4658 VL - 282 SP - 204 EP - 204 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Hass, Roland A1 - Munzke, Dorit A1 - Ruiz, Salome Vargas A1 - Tippmann, Johannes A1 - Reich, Oliver T1 - Optical monitoring of chemical processes in turbid biogenic liquid dispersions by Photon Density Wave spectroscopy JF - Analytical & bioanalytical chemistry N2 - In turbid biogenic liquid material, like blood or milk, quantitative optical analysis is often strongly hindered by multiple light scattering resulting from cells, particles, or droplets. Here, optical attenuation is caused by losses due to absorption as well as scattering of light. Fiber-based Photon Density Wave (PDW) spectroscopy is a very promising method for the precise measurement of the optical properties of such materials. They are expressed as absorption and reduced scattering coefficients (mu (a) and mu (s)', respectively) and are linked to the chemical composition and physical properties of the sample. As a process analytical technology, PDW spectroscopy can sense chemical and/or physical processes within such turbid biogenic liquids, providing new scientific insight and process understanding. Here, for the first time, several bioprocesses are analyzed by PDW spectroscopy and the resulting optical coefficients are discussed with respect to established mechanistic models of the chosen processes. As model systems, enzymatic casein coagulation in milk, temperature-induced starch hydrolysis in beer mash, and oxy- as well as deoxygenation of human donor blood were investigated by PDW spectroscopy. The findings indicate that also for very complex biomaterials (i.e., not well-defined model materials like monodisperse polymer dispersions), obtained optical coefficients allow for the assessment of a structure/process relationship and thus for a new analytical access to biogenic liquid material. This is of special relevance as PDW spectroscopy data are obtained without any dilution or calibration, as often found in conventional spectroscopic approaches. KW - Photon Density Wave spectroscopy KW - Enzymatic milk coagulation KW - Beer mashing KW - Human donor blood KW - Process analytical technology KW - Light scattering Y1 - 2015 U6 - https://doi.org/10.1007/s00216-015-8513-9 SN - 1618-2642 SN - 1618-2650 VL - 407 IS - 10 SP - 2791 EP - 2802 PB - Springer CY - Heidelberg ER - TY - JOUR A1 - Hentrich, Doreen A1 - Junginger, Mathias A1 - Bruns, Michael A1 - Boerner, Hans G. A1 - Brandt, Jessica A1 - Brezesinski, Gerald A1 - Taubert, Andreas T1 - Interface-controlled calcium phosphate mineralization: effect of oligo(aspartic acid)-rich interfaces JF - CrystEngComm N2 - The phase behavior of an amphiphilic block copolymer based on a poly(aspartic acid) hydrophilic block and a poly(n-butyl acrylate) hydrophobic block was investigated at the air-water and air-buffer interface. The polymer forms stable monomolecular films on both subphases. At low pH, the isotherms exhibit a plateau. Compression-expansion experiments and infrared reflection absorption spectroscopy suggest that the plateau is likely due to the formation of polymer bi- or multilayers. At high pH the films remain intact upon compression and no multilayer formation is observed. Furthermore, the mineralization of calcium phosphate beneath the monolayer was studied at different pH. The pH of the subphase and thus the polymer charge strongly affects the phase behavior of the film and the mineral formation. After 4 h of mineralization at low pH, atomic force microscopy shows smooth mineral films with a low roughness. With increasing pH the mineral films become inhomogeneous and the roughness increases. Transmission electron microscopy confirms this: at low pH a few small but uniform particles form whereas particles grown at higher pH are larger and highly agglomerated. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirm the formation of calcium phosphate. The levels of mineralization are higher in samples grown at high pH. Y1 - 2015 U6 - https://doi.org/10.1039/c4ce02274b SN - 1466-8033 VL - 17 IS - 36 SP - 6901 EP - 6913 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Hentrich, Doreen A1 - Junginger, Mathias A1 - Bruns, Michael A1 - Börner, Hans Gerhard A1 - Brandt, Jessica A1 - Brezesinski, Gerald A1 - Taubert, Andreas T1 - Interface-controlled calcium phosphate mineralization BT - effect of oligo(aspartic acid)-rich interfaces JF - CrystEngComm N2 - The phase behavior of an amphiphilic block copolymer based on a poly(aspartic acid) hydrophilic block and a poly(n-butyl acrylate) hydrophobic block was investigated at the air–water and air–buffer interface. The polymer forms stable monomolecular films on both subphases. At low pH, the isotherms exhibit a plateau. Compression–expansion experiments and infrared reflection absorption spectroscopy suggest that the plateau is likely due to the formation of polymer bi- or multilayers. At high pH the films remain intact upon compression and no multilayer formation is observed. Furthermore, the mineralization of calcium phosphate beneath the monolayer was studied at different pH. The pH of the subphase and thus the polymer charge strongly affects the phase behavior of the film and the mineral formation. After 4 h of mineralization at low pH, atomic force microscopy shows smooth mineral films with a low roughness. With increasing pH the mineral films become inhomogeneous and the roughness increases. Transmission electron microscopy confirms this: at low pH a few small but uniform particles form whereas particles grown at higher pH are larger and highly agglomerated. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirm the formation of calcium phosphate. The levels of mineralization are higher in samples grown at high pH. Y1 - 2015 U6 - https://doi.org/10.1039/C4CE02274B SN - 1466-8033 IS - 17 SP - 6901 EP - 6913 PB - Royal Society of Chemistry CY - London ER - TY - GEN A1 - Hentrich, Doreen A1 - Junginger, Mathias A1 - Bruns, Michael A1 - Börner, Hans Gerhard A1 - Brandt, Jessica A1 - Brezesinski, Gerald A1 - Taubert, Andreas T1 - Interface-controlled calcium phosphate mineralization BT - effect of oligo(aspartic acid)-rich interfaces N2 - The phase behavior of an amphiphilic block copolymer based on a poly(aspartic acid) hydrophilic block and a poly(n-butyl acrylate) hydrophobic block was investigated at the air–water and air–buffer interface. The polymer forms stable monomolecular films on both subphases. At low pH, the isotherms exhibit a plateau. Compression–expansion experiments and infrared reflection absorption spectroscopy suggest that the plateau is likely due to the formation of polymer bi- or multilayers. At high pH the films remain intact upon compression and no multilayer formation is observed. Furthermore, the mineralization of calcium phosphate beneath the monolayer was studied at different pH. The pH of the subphase and thus the polymer charge strongly affects the phase behavior of the film and the mineral formation. After 4 h of mineralization at low pH, atomic force microscopy shows smooth mineral films with a low roughness. With increasing pH the mineral films become inhomogeneous and the roughness increases. Transmission electron microscopy confirms this: at low pH a few small but uniform particles form whereas particles grown at higher pH are larger and highly agglomerated. Energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy confirm the formation of calcium phosphate. The levels of mineralization are higher in samples grown at high pH. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 213 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-89540 SP - 6901 EP - 6913 ER - TY - GEN A1 - Hildebrand, Viet A1 - Laschewsky, André A1 - Wischerhoff, Erik T1 - Modulating the solubility of zwitterionic poly((3- methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties N2 - Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition–fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D2O than in H2O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass. Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 309 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-103040 SP - 731 EP - 740 ER - TY - JOUR A1 - Irungu, Beatrice N. A1 - Adipo, Nicholas A1 - Orwa, Jennifer A. A1 - Kimani, Francis A1 - Heydenreich, Matthias A1 - Midiwo, Jacob O. A1 - Bjoremark, Per Martin A1 - Hakansson, Mikael A1 - Yenesew, Abiy A1 - Erdelyi, Mate T1 - Antiplasmodial and cytotoxic activities of the constituents of Turraea robusta and Turraea nilotica JF - Journal of ethnopharmacology : an interdisciplinary journal devoted to bioscientific research on indigenous drugs N2 - Ethnopharmacological relevance: Turraea robusta and Turraea nilotica are African medicinal plants used for the treatment of a wide variety of diseases, including malaria. The genus Turraea is rich in limonoids and other triterpenoids known to possess various biological activities. Materials and methods: From the stem bark of T. robusta six compounds, and from various parts of T nilotica eleven compounds were isolated by the use of a combination of chromatographic techniques. The structures of the isolated compounds were elucidated using NMR and MS, whilst the relative configuration of one of the isolated compounds, toonapubesin F, was established by X-ray crystallography. The antiplasmodial activities of the crude extracts and the isolated constituents against the D6 and W2 strains of Plasmodium falciparum were determined using the semiautomated micro dilution technique that measures the ability of the extracts to inhibit the incorporation of (G-H-3, where G is guanine) hypoxanthine into the malaria parasite. The cytotoxicity of the crude extracts and their isolated constituents was evaluated against the mammalian cell lines African monkey kidney (vero), mouse breast cancer (4T1) and human larynx carcinoma (HEp2). Results: The extracts showed good to moderate antiplasmodial activities, where the extract of the stem bark of T. robusta was also cytotoxic against the 4T1 and the HEp2 cells (IC50 < 10 mu g/ml). The compounds isolated from these extracts were characterized as limonoids, protolimonoids and phytosterol glucosides. These compounds showed good to moderate activities with the most active one being azadironolide, IC50 2.4 +/- 0.03 mu M and 1.1 +/- 0.01 mu M against the D6 and W2 strains of Plasmodium falciparum, respectively; all other compounds possessed IC50 14.4-40.5 mu M. None of the compounds showed significant cytotoxicity against vero cells, yet four of them were toxic against the 4T1 and HEp2 cancer cell lines with piscidinol A having IC50 8.0 +/- 0.03 and 8.4 +/- 0.01 mu M against the 4T1 and HEp2 cells, respectively. Diacetylation of piscidinol A resulted in reduced cytotoxicity. Conclusion: From the medicinal plants T. robusta and T. nilotica, twelve compounds were isolated and characterized; two of the isolated compounds, namely 11-epi-toonacilin and azadironolide showed good antiplasmodial activity with the highest selectivity indices. (C) 2015 The Authors. Published by Elsevier Ireland Ltd. KW - Turraea robusta KW - Turraea nilotica KW - Antiplasmodial activity KW - Cytotoxicity KW - Limonoid KW - Toonapubesins F KW - Toonacilin KW - Azadironolide Y1 - 2015 U6 - https://doi.org/10.1016/j.jep.2015.08.039 SN - 0378-8741 VL - 174 SP - 419 EP - 425 PB - Elsevier CY - Clare ER - TY - THES A1 - Jahn, Karolina T1 - Multiparameter-Detektion von biologisch relevanten Analyten mittels moderner Verfahren der Fluoreszenzmikroskopie Y1 - 2015 ER - TY - JOUR A1 - Jahn, Karolina A1 - Buschmann, Volker A1 - Hille, Carsten T1 - Simultaneous Fluorescence and Phosphorescence Lifetime Imaging Microscopy in Living Cells JF - Scientific reports N2 - In living cells, there are always a plethora of processes taking place at the same time. Their precise regulation is the basis of cellular functions, since small failures can lead to severe dysfunctions. For a comprehensive understanding of intracellular homeostasis, simultaneous multiparameter detection is a versatile tool for revealing the spatial and temporal interactions of intracellular parameters. Here, a recently developed time-correlated single-photon counting (TCSPC) board was evaluated for simultaneous fluorescence and phosphorescence lifetime imaging microscopy (FLIM/PLIM). Therefore, the metabolic activity in insect salivary glands was investigated by recording ns-decaying intrinsic cellular fluorescence, mainly related to oxidized flavin adenine dinucleotide (FAD) and the mu s-decaying phosphorescence of the oxygen-sensitive ruthenium-complex Kr341. Due to dopamine stimulation, the metabolic activity of salivary glands increased, causing a higher pericellular oxygen consumption and a resulting increase in Kr341 phosphorescence decay time. Furthermore, FAD fluorescence decay time decreased, presumably due to protein binding, thus inducing a quenching of FAD fluorescence decay time. Through application of the metabolic drugs antimycin and FCCP, the recorded signals could be assigned to a mitochondrial origin. The dopamine-induced changes could be observed in sequential FLIM and PLIM recordings, as well as in simultaneous FLIM/PLIM recordings using an intermediate TCSPC timing resolution. Y1 - 2015 U6 - https://doi.org/10.1038/srep14334 SN - 2045-2322 VL - 5 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Jahn, Karolina A1 - Buschmann, Volker A1 - Hille, Carsten T1 - Simultaneous Fluorescence and Phosphorescence Lifetime Imaging Microscopy in Living Cells JF - Scientific Reports N2 - In living cells, there are always a plethora of processes taking place at the same time. Their precise regulation is the basis of cellular functions, since small failures can lead to severe dysfunctions. For a comprehensive understanding of intracellular homeostasis, simultaneous multiparameter detection is a versatile tool for revealing the spatial and temporal interactions of intracellular parameters. Here, a recently developed time-correlated single-photon counting (TCSPC) board was evaluated for simultaneous fluorescence and phosphorescence lifetime imaging microscopy (FLIM/PLIM). Therefore, the metabolic activity in insect salivary glands was investigated by recording ns-decaying intrinsic cellular fluorescence, mainly related to oxidized flavin adenine dinucleotide (FAD) and the μs-decaying phosphorescence of the oxygen-sensitive ruthenium-complex Kr341. Due to dopamine stimulation, the metabolic activity of salivary glands increased, causing a higher pericellular oxygen consumption and a resulting increase in Kr341 phosphorescence decay time. Furthermore, FAD fluorescence decay time decreased, presumably due to protein binding, thus inducing a quenching of FAD fluorescence decay time. Through application of the metabolic drugs antimycin and FCCP, the recorded signals could be assigned to a mitochondrial origin. The dopamine-induced changes could be observed in sequential FLIM and PLIM recordings, as well as in simultaneous FLIM/PLIM recordings using an intermediate TCSPC timing resolution. KW - Confocal microscopy KW - Fluorescence imaging KW - Fluorescence spectroscopy KW - Fluorescent probes Y1 - 2015 U6 - https://doi.org/10.1038/srep14334 SN - 2045-2322 IS - 5 PB - Nature Publishing Group CY - London ER - TY - GEN A1 - Jahn, Karolina A1 - Buschmann, Volker A1 - Hille, Carsten T1 - Simultaneous Fluorescence and Phosphorescence Lifetime Imaging Microscopy in Living Cells N2 - In living cells, there are always a plethora of processes taking place at the same time. Their precise regulation is the basis of cellular functions, since small failures can lead to severe dysfunctions. For a comprehensive understanding of intracellular homeostasis, simultaneous multiparameter detection is a versatile tool for revealing the spatial and temporal interactions of intracellular parameters. Here, a recently developed time-correlated single-photon counting (TCSPC) board was evaluated for simultaneous fluorescence and phosphorescence lifetime imaging microscopy (FLIM/PLIM). Therefore, the metabolic activity in insect salivary glands was investigated by recording ns-decaying intrinsic cellular fluorescence, mainly related to oxidized flavin adenine dinucleotide (FAD) and the μs-decaying phosphorescence of the oxygen-sensitive ruthenium-complex Kr341. Due to dopamine stimulation, the metabolic activity of salivary glands increased, causing a higher pericellular oxygen consumption and a resulting increase in Kr341 phosphorescence decay time. Furthermore, FAD fluorescence decay time decreased, presumably due to protein binding, thus inducing a quenching of FAD fluorescence decay time. Through application of the metabolic drugs antimycin and FCCP, the recorded signals could be assigned to a mitochondrial origin. The dopamine-induced changes could be observed in sequential FLIM and PLIM recordings, as well as in simultaneous FLIM/PLIM recordings using an intermediate TCSPC timing resolution. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 202 KW - Confocal microscopy KW - Fluorescence imaging KW - Fluorescence spectroscopy KW - Fluorescent probes Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-82156 ER - TY - THES A1 - Jehannin, Marie T1 - About the role of physico-chemical properties and hydrodynamics on the progress of a precipitation reaction T1 - Über die Rolle physikalisch-chemischer Eigenschaften und Hydrodynamiken auf den Fortschritt einer Fällungsreaktion BT - the case of cerium oxalate particles produced during coalescence of drops BT - Ceroxalat-Partikel, entstanden während der Koaleszenz von Tropfen N2 - The size and morphology control of precipitated solid particles is a major economic issue for numerous industries. For instance, it is interesting for the nuclear industry, concerning the recovery of radioactive species from used nuclear fuel. The precipitates features, which are a key parameter from the post-precipitate processing, depend on the process local mixing conditions. So far, the relationship between precipitation features and hydrodynamic conditions have not been investigated. In this study, a new experimental configuration consisting of coalescing drops is set to investigate the link between reactive crystallization and hydrodynamics. Two configurations of aqueous drops are examined. The first one corresponds to high contact angle drops (>90°) in oil, as a model system for flowing drops, the second one correspond to sessile drops in air with low contact angle (<25°). In both cases, one reactive is dissolved in each drop, namely oxalic acid and cerium nitrate. When both drops get into contact, they may coalesce; the dissolved species mix and react to produce insoluble cerium oxalate. The precipitates features and effect on hydrodynamics are investigated depending on the solvent. In the case of sessile drops in air, the surface tension difference between the drops generates a gradient which induces a Marangoni flow from the low surface tension drop over the high surface tension drop. By setting the surface tension difference between the two drops and thus the Marangoni flow, the hydrodynamics conditions during the drop coalescence could be modified. Diols/water mixtures are used as solvent, in order to fix the surface tension difference between the liquids of both drops regardless from the reactant concentration. More precisely, the used diols, 1,2-propanediol and 1,3-propanediol, are isomer with identical density and close viscosity. By keeping the water volume fraction constant and playing with the 1,2-propanediol and 1,3-propanediol volume fractions of the solvents, the mixtures surface tensions differ up to 10 mN/m for identical/constant reactant concentration, density and viscosity. 3 precipitation behaviors were identified for the coalescence of water/diols/recatants drops depending on the oxalic excess. The corresponding precipitates patterns are visualized by optical microscopy and the precipitates are characterized by confocal microscopy SEM, XRD and SAXS measurements. In the intermediate oxalic excess regime, formation of periodic patterns can be observed. These patterns consist in alternating cerium oxalate precipitates with distinct morphologies, namely needles and “microflowers”. Such periodic fringes can be explained by a feedback mechanism between convection, reaction and the diffusion. N2 - Die Kontrolle der Morphologie und Größe fester durch Fällung erzeugter Partikel ist eine wichtige Herausforderung in Industrie und Forschung. Insbesondere gilt dies für die Wiederaufbereitung verbrauchter Brennstäber in der Atomindustrie. Die Eigenschaften der Ausfällungen hängen von den Mischbedingungen der Flüssigkeiten in den Prozessen ab. Dennoch sind die Beziehungen zwischen den physischen Charakteristiken der erzeugten Partikeln und den hydrodynamischen Bedingungen ungewiss. In dieser Arbeit werden Zwei-Tropfen-Koalezenz-Experiment genutzt, um die Verbindungen zwischen Hydrodynamik und Fällungsreaktion besser zu verstehen. Zwei Konfigurationen von ruhenden wässrigen Tropfen wurden untersucht: Zum einen Tropfen mit hohem Kontaktwinkel (> 90°) in Öl und zum anderen Tropfen mit kleinem Kontaktwinkel (< 25°) in Luft. In beiden Fällen wurde Oxalsäure und Ceriumnitrat jeweils in einem Tropfen gelöst. Wenn beide Tropfen einander in Kontakt treten, können sie sich vereinigen. Dabei mischen sich die Reagenzien und erzeugen Ceriumoxalat. In Abhängigkeit von Lösungsmitteln werden die Eigenschaften der Fällung sowie ihr Einfluss auf die Hydrodynamik untersucht. In Experimenten Tropfen in Luft ist es außerdem möglich, mittels Wasser/Diol-Mischungen den Oberflächenspannungsgradienten zwischen beiden Tropfenflüssigkeiten zu ändern. Damit ist es möglich den resultierenden Marangoni-Fluss zu kontrollieren. So werden die hydrodynamischen Bedingungen unabhängig von dem Oxalsäureüberschuss verwirklicht. In diesem Fall werden drei Fällungsverhalten abhängig er Oxalsäure-Konzentration beobachtet. Das Zwischenverhalten zeigt überraschende periodische Strukturen, welche verschiedenen Morphologien bilden, nämlich Nägeln und „Microflower“. Die Strukturen wurden über Optische Mikroskopie Identifiziert und charakterisiert mit Hilfe von Konfokaler Mikroskopie, SEM, XRD und SAXS. Die Entstehung solcher Strukturen könnte durch eine Konvektion- Diffusion- Reaktion-Rückkopplung erklärt werden. N2 - Réussir à contrôler la morphologie et la taille de particules solides obtenues par précipitation est un enjeu industriel majeur. C’est notamment le cas dans l’industrie nucléaire pour le recyclage du combustible usé. Les caractéristiques des précipités sont liées aux conditions de mélange des phases liquides dans les procédés. Les corrélations entre les paramètres physiques des particules obtenues et les conditions hydrodynamiques n’ont pas été examinées jusqu’à présent. Dans cette étude, des systèmes expérimentaux originaux, basés sur la coalescence de deux gouttes, sont utilisés afin de mieux comprendre les liens entre hydrodynamique et réaction de précipitation. Deux configurations de gouttes aqueuses ont été investiguées, la première consiste en deux goutes posées à fort angle de contact (>90°) dans l’huile, il s’agit d’un système modèle pour les gouttes en émulsion, la second configuration correspond à deux gouttes posées à faible angle de contact (>25°) dans l’air. Dans chaque cas, une espèce réactive est dissoute dans chaque goutte, à savoir de l’acide oxalique ou du nitrate de cérium dans la seconde. Lorsque les deux gouttes se touchent, elles peuvent éventuellement coalescer, alors les espèces chimiques se mélangent et réagissent pour produire un précipité d’oxalate de cérium. Les caractéristiques de ce précipité et ses effets sur l’hydrodynamique sont examinés en fonction du solvant utilisé. De plus, dans le cas des gouttes posées sur une surface de silice dans l’air, une différence de tension de surface entre deux gouttes crée un gradient qui génère un flux de Marangoni dirigé de la goutte de faible tension de surface au-dessus de la goutte de forte tension de surface. En jouant sur la différence de tension de surface entre les deux gouttes, et ainsi sur le flux de Marangoni, il est possible de modifier les conditions hydrodynamiques lors de la coalescence des gouttes. Des mélanges eau/diols ont été utilisés comme solvant afin de pouvoir modifier la différence de tension de surface entre les liquides des deux gouttes indépendamment de leur concentration en réactif. Les diols utilisés, le 1,2-propanediol et le 1,3-propanediol sont des isomères, ils sont la même densité, des viscosités semblables mais des tensions de surface différentes. En fixant la fraction volumique d’eau dans le solvant, et en jouant sur les fractions volumiques de chaque diols, il est possible de contrôler la tension de surface des mélanges sur une gamme de 10 mN/m pour une concentration en réactifs donnée, et en conservant la densité et viscosité des solvants. Trois régimes de précipitation ont été identifiés dans le cas de la coalescence de gouttes d’eau/diols/réactifs en fonction de l’excès oxalique. Les motifs de précipitation en découlant ont été imagés par microscopie optique et les différents précipités ont été caractérisés à l’aide de microscopie confocale, MEB, DRX et SAXS. Le régime intermédiaire présente des motifs périodiques surprenants. Ces motifs correspondent à des domaines nettement délimités d’oxalate de cérium de différentes morphologies, à savoir des aiguilles et des « microflowers ». L’obtention de tels motifs peut s’expliquer par un mécanisme de rétroaction entre convection, réaction et diffusion. KW - Marangoni flow KW - coalescence KW - periodic pattern KW - oxalic precipitation KW - drop KW - Marangoni-Fluss KW - Koaleszenz KW - Tropfen KW - Fällungsreaktion KW - periodisches Muster KW - Oxalat-Fällung KW - flux de Marangoni KW - coalescence KW - gouttes KW - précipitation KW - motif périodique KW - précipitation oxalique Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-88364 ER - TY - JOUR A1 - Kastl, Johanna A1 - Braun, Joachim A1 - Prestel, Andreas A1 - Möller, Heiko Michael A1 - Huhn, Thomas A1 - Mayer, Thomas U. T1 - Mad2 Inhibitor-1 (M2I-1): A Small Molecule Protein-Protein Interaction Inhibitor Targeting the Mitotic Spindle Assembly Checkpoint JF - ACS chemical biology N2 - The genetic integrity of each organism depends on the faithful segregation of its genome during mitosis. To meet this challenge, a cellular surveillance mechanism, termed the spindle assembly checkpoint (SAC), evolved that monitors the correct attachment of chromosomes and blocks progression through mitosis if corrections are needed. While the central role of the SAC for genome integrity is well established, its functional dissection has been hampered by the limited availability of appropriate small molecule inhibitors. Using a fluorescence polarization-based screen, we identify Mad2 inhibitor-1 (M2I-1), the first small molecule inhibitor targeting the binding of Mad2 to Cdc20, an essential protein-protein interaction (PPI) within the SAC. Based on computational and biochemical analyses, we propose that M2I-1 disturbs conformational dynamics of Mad2 critical for complex formation with Cdc20. Cellular studies revealed that M2I-1 weakens the SAC response, indicating that the compound might be active in cells. Thus, our study identifies the SAC specific complex formation between Mad2 and Cdc20 as a protein-protein interaction that can be targeted by small molecules. Y1 - 2015 U6 - https://doi.org/10.1021/acschembio.5b00121 SN - 1554-8929 SN - 1554-8937 VL - 10 IS - 7 SP - 1661 EP - 1666 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kathrein, Christine C. A1 - Bai, Wubin A1 - Currivan-Incorvia, Jean Anne A1 - Liontos, George A1 - Ntetsikas, Konstantinos A1 - Avgeropoulos, Apostolos A1 - Böker, Alexander A1 - Tsarkova, Larisa A1 - Ross, Caroline A. T1 - Combining Graphoepitaxy and Electric Fields toward Uniaxial Alignment of Solvent-Annealed Polystyrene-b-Poly(dimethylsiloxane) Block Copolymers JF - Chemistry of materials : a publication of the American Chemical Society N2 - We report a combined directing effect of the simultaneously applied graphoepitaxy and electric field on the self-assembly of cylinder forming polystyrene-b-poly(dimethylsiloxane) block copolymer in thin films. A correlation length of up to 20 mu m of uniaxial ordered striped patterns is an order of magnitude greater than that produced by either graphoepitaxy or electric field alignment alone and is achieved at reduced annealing times. The angle between the electric field direction and the topographic guides as well as the dimensions of the trenches affected both the quality of the ordering and the direction of the orientation of cylindrical domains: parallel or perpendicular to the topographic features. We quantified the interplay between the electric field and the geometry of the topographic structures by constructing the phase diagram of microdomain orientation. This combined approach allows the fabrication of highly ordered block copolymer structures using macroscopically prepatterned photolithographic substrates. Y1 - 2015 U6 - https://doi.org/10.1021/acs.chemmater.5b03354 SN - 0897-4756 SN - 1520-5002 VL - 27 IS - 19 SP - 6890 EP - 6898 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kedracki, Dawid A1 - Filippov, Sergey K. A1 - Gour, Nidhi A1 - Schlaad, Helmut A1 - Nardin, Corinne T1 - Formation of DNA-Copolymer Fibrils Through an Amyloid-Like Nucleation Polymerization Mechanism JF - Macromolecular rapid communications N2 - Conjugation of a hydrophobic poly(2-oxazoline) bearing tertiary amide groups along its backbone with a short single stranded nucleotide sequence results in an amphiphilic comb/graft copolymer, which organizes in fibrils upon direct dissolution in water. Supported by circular dichroism, atomic force microscopy, transmission electron microscopy, and scattering data, fibrils are formed through inter- and intramolecular hydrogen bonding between hydrogen accepting amide groups along the polymer backbone and hydrogen donating nucleic acid grafts leading to the formation of hollow tubes. KW - DNA copolymers KW - fibers KW - hydrogen bonding KW - nucleation polymerization KW - self-assembly Y1 - 2015 U6 - https://doi.org/10.1002/marc.201400728 SN - 1022-1336 SN - 1521-3927 VL - 36 IS - 8 SP - 768 EP - 773 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kirchhecker, Sarah A1 - Tröger-Müller, Steffen A1 - Bake, Sebastian A1 - Antonietti, Markus A1 - Taubert, Andreas A1 - Esposito, Davide T1 - Renewable pyridinium ionic liquids from the continuous hydrothermal decarboxylation of furfural-amino acid derived pyridinium zwitterions JF - Green chemistry : an international journal and green chemistry resource N2 - Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counter-ions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling. Y1 - 2015 U6 - https://doi.org/10.1039/c5gc00913h SN - 1463-9262 SN - 1463-9270 VL - 17 IS - 8 SP - 4151 EP - 4156 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kirchhecker, Sarah A1 - Tröger-Müller, Steffen A1 - Bake, Sebastian A1 - Antonietti, Markus A1 - Taubert, Andreas A1 - Esposito, Davido T1 - Renewable pyridinium ionic liquids from the continuous hydrothermal decarboxylation of furfural-amino acid derived pyridinium zwitterions JF - Green chemistry N2 - Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counterions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling. Y1 - 2015 U6 - https://doi.org/10.1039/c5gc00913h SN - 1463-9262 SN - 1463-9270 VL - 8 IS - 17 SP - 4151 EP - 4156 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Kirchhecker, Sarah A1 - Tröger-Müller, Steffen A1 - Bake, Sebastian A1 - Antonietti, Markus A1 - Taubert, Andreas A1 - Esposito, Davido T1 - Renewable pyridinium ionic liquids from the continuous hydrothermal decarboxylation of furfural-amino acid derived pyridinium zwitterions N2 - Fully renewable pyridinium ionic liquids were synthesised via the hydrothermal decarboxylation of pyridinium zwitterions derived from furfural and amino acids in flow. The functionality of the resulting ionic liquid (IL) can be tuned by choice of different amino acids as well as different natural carboxylic acids as the counterions. A representative member of this new class of ionic liquids was successfully used for the synthesis of ionogels and as a solvent for the Heck coupling. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 198 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-81390 ER - TY - JOUR A1 - Klaper, M. A1 - Wessig, Pablo A1 - Linker, Torsten T1 - Base catalysed decomposition of anthracene endoperoxide JF - Chemical communications : ChemComm N2 - Catalytic amounts of a weak base are sufficient to induce the decomposition of anthracene endoperoxides to anthraquinone. The mechanism has been elucidated by isolation of intermediates in combination with DFT calculations. The whole process is suitable for the convenient generation of hydrogen peroxide under very mild conditions. Y1 - 2015 U6 - https://doi.org/10.1039/C5CC08606J SN - 1364-548X IS - 52 SP - 1210 EP - 1213 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Klaper, M. A1 - Wessig, Pablo A1 - Linker, Torsten T1 - Base catalysed decomposition of anthracene endoperoxide N2 - Catalytic amounts of a weak base are sufficient to induce the decomposition of anthracene endoperoxides to anthraquinone. The mechanism has been elucidated by isolation of intermediates in combination with DFT calculations. The whole process is suitable for the convenient generation of hydrogen peroxide under very mild conditions. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 219 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-89676 SP - 1210 EP - 1213 ER - TY - JOUR A1 - Klaper, Matthias A1 - Linker, Torsten T1 - New Singlet Oxygen Donors Based on Naphthalenes: Synthesis, Physical Chemical Data, and Improved Stability JF - Chemistry - a European journal N2 - Singlet oxygen donors are of current interest for medical applications, but suffer from a short half-life leading to low singlet oxygen yields and problems with storage. We have synthesized more than 25new singlet oxygen donors based on differently substituted naphthalenes in only a few steps. The influence of functional groups on the reaction rate of the photooxygenations, thermolysis, half-life, and singlet oxygen yield has been thoroughly studied. We determined various thermodynamic data and compared them with density functional calculations. Interestingly, remarkable stabilities of functional groups during the photooxygenations and stabilizing effects for some endoperoxides during the thermolysis have been found. Furthermore, we give evidence for a partly concerted and partly stepwise thermolysis mechanism leading to singlet and triplet oxygen, respectively. Our results might be interesting for dark oxygenations and future applications in medicine. KW - density functional calculations KW - oxygenation KW - peroxides KW - photodynamic therapy KW - singlet oxygen Y1 - 2015 U6 - https://doi.org/10.1002/chem.201500146 SN - 0947-6539 SN - 1521-3765 VL - 21 IS - 23 SP - 8569 EP - 8577 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Klaper, Matthias A1 - Linker, Torsten T1 - Intramolecular Transfer of Singlet Oxygen JF - Journal of the American Chemical Society N2 - The intramolecular transfer of energy (FRET) and electrons (Dexter) are of great interest for the scientific community and are well-understood. In contrast, the intramolecular transfer of singlet oxygen (O-1(2)), a reactive and short-lived oxygen species, has until now been unknown. This process would be very interesting because O-1(2) plays an important role in photodynamic therapy (PDT). Herein, we present the first successful intramolecular transfer of O-1(2) from a donor to acceptor. Also, we found a dependence of conformation and temperature comparable with those of FRET. We provide several pieces of evidence for the intramolecular character of this transfer, including competition experiments. Our studies should be interesting not only from the theoretical and mechanistic point of view but also for the design of new O-1(2) donors and applications in PDT. Y1 - 2015 U6 - https://doi.org/10.1021/jacs.5b07848 SN - 0002-7863 VL - 137 IS - 43 SP - 13744 EP - 13747 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Klauß, André A1 - Koenig, Marcelle A1 - Hille, Carsten T1 - Upgrade of a Scanning Confocal Microscope to a Single-Beam Path STED Microscope JF - PLoS one N2 - By overcoming the diffraction limit in light microscopy, super-resolution techniques, such as stimulated emission depletion (STED) microscopy, are experiencing an increasing impact on life sciences. High costs and technically demanding setups, however, may still hinder a wider distribution of this innovation in biomedical research laboratories. As far-field microscopy is the most widely employed microscopy modality in the life sciences, upgrading already existing systems seems to be an attractive option for achieving diffraction-unlimited fluorescence microscopy in a cost-effective manner. Here, we demonstrate the successful upgrade of a commercial time-resolved confocal fluorescence microscope to an easy-to-align STED microscope in the single-beam path layout, previously proposed as "easy-STED", achieving lateral resolution 600 °C a back transfer to the α-phase was observed. Complementarily, the luminescence upconversion properties of the annealed UCNP materials were characterized in steady state and time resolved luminescence measurements. Distinct differences in the upconversion luminescence intensity, the spectral intensity distribution and the luminescence decay kinetics were found for the cubic and hexagonal lattice phases, respectively, corroborating the results of the standard analytical techniques used. In laser power dependent measurements of the upconversion luminescence intensity it was found that the green (G1, G2) and red (R) emission of Er3+ showed different effects of Tan on the number of required photons reflecting the differences in the population routes of different energy levels involved. Furthermore, the intensity ratio of Gfull/R is highly effected by the laser power only when the β-phase is present, whereas the G1/G2 intensity ratio is only slightly effected regardless of the crystal phase. Moreover, based on different upconversion luminescence kinetics characteristics of the cubic and hexagonal phase time-resolved area normalized emission spectra (TRANES) proved to be a very sensitive tool to monitor the phase transition between cubic and hexagonal phases. Based on the TRANES analysis it was possible to resolve the lattice phase transition in more detail for 200 °C < Tan < 300 °C, which was not possible with the standard techniques. Y1 - 2015 U6 - https://doi.org/10.1039/C5TC02218E SN - 2050-7526 SN - 2050-7534 IS - 3 SP - 11228 EP - 11238 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Klier, Dennis Tobias A1 - Kumke, Michael Uwe T1 - Analysing the effect of the crystal structure on upconversion luminescence in Yb3+,Er3+-co-doped NaYF4 nanomaterials N2 - NaYF4:Yb:Er nanoparticles (UCNP) were synthesized under mild experimental conditions to obtain a pure cubic lattice. Upon annealing at different temperatures up to Tan = 700 °C phase transitions to the hexagonal phase and back to the cubic phase were induced. The UCNP materials obtained for different Tan were characterized with respect to the lattice phase using standard XRD and Raman spectroscopy as well as steady state and time resolved upconversion luminescence. The standard techniques showed that for the annealing temperature range 300 °C < Tan < 600 °C the hexagonal lattice phase was dominant. For Tan < 300 °C hardly any change in the lattice phase could be deduced, whereas for Tan > 600 °C a back transfer to the α-phase was observed. Complementarily, the luminescence upconversion properties of the annealed UCNP materials were characterized in steady state and time resolved luminescence measurements. Distinct differences in the upconversion luminescence intensity, the spectral intensity distribution and the luminescence decay kinetics were found for the cubic and hexagonal lattice phases, respectively, corroborating the results of the standard analytical techniques used. In laser power dependent measurements of the upconversion luminescence intensity it was found that the green (G1, G2) and red (R) emission of Er3+ showed different effects of Tan on the number of required photons reflecting the differences in the population routes of different energy levels involved. Furthermore, the intensity ratio of Gfull/R is highly effected by the laser power only when the β-phase is present, whereas the G1/G2 intensity ratio is only slightly effected regardless of the crystal phase. Moreover, based on different upconversion luminescence kinetics characteristics of the cubic and hexagonal phase time-resolved area normalized emission spectra (TRANES) proved to be a very sensitive tool to monitor the phase transition between cubic and hexagonal phases. Based on the TRANES analysis it was possible to resolve the lattice phase transition in more detail for 200 °C < Tan < 300 °C, which was not possible with the standard techniques. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 217 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-89630 SP - 11228 EP - 11238 ER - TY - JOUR A1 - Klier, Dennis Tobias A1 - Kumke, Michael Uwe T1 - Analysing the effect of the crystal structure on upconversion luminescence in Yb3+, Er3+-co-doped NaYF4 nanomaterials JF - Journal of materials chemistry : C, Materials for optical and electronic devices N2 - NaYF4:Yb:Er nanoparticles (UCNP) were synthesized under mild experimental conditions to obtain a pure cubic lattice. Upon annealing at different temperatures up to T-an = 700 degrees C phase transitions to the hexagonal phase and back to the cubic phase were induced. The UCNP materials obtained for different T-an were characterized with respect to the lattice phase using standard XRD and Raman spectroscopy as well as steady state and time resolved upconversion luminescence. The standard techniques showed that for the annealing temperature range 300 degrees C < T-an < 600 degrees C the hexagonal lattice phase was dominant. For T-an < 300 degrees C hardly any change in the lattice phase could be deduced, whereas for T-an > 600 degrees C a back transfer to the alpha-phase was observed. Complementarily, the luminescence upconversion properties of the annealed UCNP materials were characterized in steady state and time resolved luminescence measurements. Distinct differences in the upconversion luminescence intensity, the spectral intensity distribution and the luminescence decay kinetics were found for the cubic and hexagonal lattice phases, respectively, corroborating the results of the standard analytical techniques used. In laser power dependent measurements of the upconversion luminescence intensity it was found that the green (G1, G2) and red (R) emission of Er3+ showed different effects of T-an on the number of required photons reflecting the differences in the population routes of different energy levels involved. Furthermore, the intensity ratio of G(full)/R is highly effected by the laser power only when the beta-phase is present, whereas the G1/G2 intensity ratio is only slightly effected regardless of the crystal phase. Moreover, based on different upconversion luminescence kinetics characteristics of the cubic and hexagonal phase time-resolved area normalized emission spectra (TRANES) proved to be a very sensitive tool to monitor the phase transition between cubic and hexagonal phases. Based on the TRANES analysis it was possible to resolve the lattice phase transition in more detail for 200 degrees C < T-an < 300 degrees C, which was not possible with the standard techniques. Y1 - 2015 U6 - https://doi.org/10.1039/c5tc02218e SN - 2050-7526 SN - 2050-7534 VL - 3 IS - 42 SP - 11228 EP - 11238 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Klier, Dennis Tobias A1 - Kumke, Michael Uwe T1 - Upconversion Luminescence Properties of NaYF4:Yb:Er Nanoparticles Codoped with Gd3+ JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - The temperature-dependent upconversion luminescence of NaYF4:Yb:Er nanoparticles (UCNP) containing different contents of Gd3+ as additional dopant was characterized. The UCNP were synthesized in a hydrothermal synthesis and stabilized with citrate in order to transfer them to the water phase. Basic characterization was carried out using TEM and DLS to determine the average size of the UCNP. The XRD technique was used to investigate the crystal lattice of the UCNP. It was found that due to the presence of Gd3+, an alteration of the lattice phase from a to beta was induced which was also reflected in the observed upconversion luminescence properties of the UCNP. A detailed analysis of the upconversion luminescence spectraespecially at ultralow temperaturesrevealed the different effects of phonon coupling between the host lattice and the sensitizer (Yb3+) as well as the activator (Er3+). Furthermore, the upconversion luminescence intensity reached a maximum between 15 and 250 K depending on Gd3+ content. In comparison to the very complex temperature behavior of the upconversion luminescence in the temperature range <273 K, the luminescence intensity ratio of H-2(11/2)-> I-4(15/2) to S-4(3/2)-> I-4(15/2) (R = G1/G2) in a higher temperature range can be described by an Arrhenius-type equation. Y1 - 2015 U6 - https://doi.org/10.1021/jp5103548 SN - 1932-7447 VL - 119 IS - 6 SP - 3363 EP - 3373 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Klier, Dennis Tobias A1 - Kumke, Michael Uwe T1 - Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale JF - RSC Advances N2 - In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure beta crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP. Y1 - 2015 U6 - https://doi.org/10.1039/c5ra11502g SN - 2046-2069 VL - 5 IS - 82 SP - 67149 EP - 67156 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kolocouris, Antonios A1 - Koch, Andreas A1 - Kleinpeter, Erich A1 - Stylianakis, Ioannis T1 - 2-Substituted and 2,2-disubstituted adamantane derivatives as models for studying substituent chemical shifts and C-H-ax center dot center dot center dot Y-ax cyclohexane contacts-results from experimental and theoretical NMR spectroscopic chemical shifts and DFT structures JF - Tetrahedron N2 - The complete H-1 and C-13 NMR chemical shifts assignment for various 2-substituted and 2,2-disubstituted adamantane derivatives 1-38 in CDCl3 solution was realized on the basis of NMR experiments combined with chemical structure information and DFT-GIAO (B3LYP/6-31+G(d,p)-GIAO) calculations of chemical shifts in solution. Substituent-induced C-13 NMR chemical shifts (SCS) are discussed. C-H-ax center dot center dot center dot Y-ax contacts are a textbook prototype of steric hindrance in organic chemistry. The nature of these contacts will be further investigated in this work on basis of new adamantane derivatives, which are substituted at C-2 to provide models for 1,4-C-H-ax center dot center dot center dot Y-ax and 1,5-C-H-ax center dot center dot center dot Y-ax contacts. The B3LYP/6-31+G(d,p) calculations predicted the presence of NBO hyperconjugative attractive interactions between C-H-ax and Y-ax groups along C-H-ax center dot center dot center dot Y-ax contacts. The H-1 NMR signal separation, Delta delta(gamma-CH2), reflects the strength of the H-bonded C-H-ax center dot center dot center dot Y-ax contact. (C) 2015 Elsevier Ltd. All rights reserved. KW - 2-Substituted adamantane derivatives KW - 2,2-Disubstituted adamantane derivatives KW - H-1 NMR KW - C-13 NMR KW - B3LYP/6-31+G(d,p) calculations KW - GIAO calculations KW - Substituent chemical shifts Y1 - 2015 U6 - https://doi.org/10.1016/j.tet.2015.01.044 SN - 0040-4020 VL - 71 IS - 16 SP - 2463 EP - 2481 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Koshkina, Olga A1 - Lang, Thomas A1 - Thiermann, Raphael A1 - Docter, Dominic A1 - Stauber, Roland H. A1 - Secker, Christian A1 - Schlaad, Helmut A1 - Weidner, Steffen A1 - Mohr, Benjamin A1 - Maskos, Michael A1 - Bertin, Annabelle T1 - Temperature-Triggered Protein Adsorption on Polymer-Coated Nanoparticles in Serum JF - Langmuir N2 - The protein corona, which forms on the nanoparticle's surface in most biological media, determines the nanoparticle's physicochemical characteristics. The formation of the protein corona has a significant impact on the biodistribution and clearance of nanoparticles in vivo. Therefore, the ability to influence the formation of the protein corona is essential to most biomedical applications, including drug delivery and imaging. In this study, we investigate the protein adsorption on nanoparticles with a hydrodynamic radius of 30 nm and a coating of thermoresponsive poly(2-isopropyl-2-oxazoline) in serum. Using multiangle dynamic light scattering (DLS) we demonstrate that heating of the nanoparticles above their phase separation temperature induces the formation of agglomerates, with a hydrodynamic radius of 1 mu m. In serum, noticeably stronger agglomeration occurs at lower temperatures compared to serum-free conditions. Cryogenic transmission electron microscopy (cryo-TEM) revealed a high packing density of agglomerates when serum was not present. In contrast, in the presence of serum, agglomerated nanoparticles were loosely packed, indicating that proteins are intercalated between them. Moreover, an increase in protein content is observed upon heating, confirming that protein adsorption is induced by the alteration of the surface during phase separation. After cooling and switching the surface back, most of the agglomerates were dissolved and the main fraction returned to the original size of approximately 30 nm as shown by asymmetrical flow-field flow fractionation (AF-FFF) and DLS. Furthermore, the amounts of adsorbed proteins are similar before and after heating the nanoparticles to above their phase-separation temperature. Overall, our results demonstrate that the thermoresponsivity of the polymer coating enables turning the corona formation on nanoparticles on and off in situ. As the local heating of body areas can be easily done in vivo, the thermoresponsive coating could potentially be used to induce the agglomeration of nanopartides and proteins and the accumulation of nanoparticles in a targeted body region. Y1 - 2015 U6 - https://doi.org/10.1021/acs.langmuir.5b00537 SN - 0743-7463 VL - 31 IS - 32 SP - 8873 EP - 8881 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kovach, Ildyko A1 - Kosmella, Sabine A1 - Prietzel, Claudia Christina A1 - Bagdahn, Christian A1 - Koetz, Joachim T1 - Nano-porous calcium phosphate balls JF - Colloids and surfaces : an international journal devoted to fundamental and applied research on colloid and interfacial phenomena in relation to systems of biological origin ; B, Biointerfaces N2 - By dropping a NaH2PO4 center dot H2O precursor solution to a CaCl2 solution at 90 degrees C under continuous stirring in presence of two biopolymers, i.e. gelatin (G) and chitosan (C), supramolecular calcium phosphate (CP) card house structures are formed. Light microscopic investigations in combination with scanning electron microscopy show that the GC-based flower-like structure is constructed from very thin CP platelets. Titration experiments indicate that H-bonding between both biopolymers is responsible for the synergistic effect in presence of both polymers. Gelatin chitosan water complexes play an important role with regard to supramolecular ordering. FTIR spectra in combination with powder X-ray diffraction show that after burning off all organic components (heating up >600 degrees C) dicalcium and tricalcium phosphate crystallites are formed. From high resolution transmission electron microscopy (HR-TEM) it is obvious to conclude, that individual crystal platelets are dicalcium phosphates, which build up ball-like supramolecular structures. The results reveal that the GC guided crystal growth leads to nano-porous supramolecular structures, potentially attractive candidates for bone repair. (c) 2015 Elsevier B.V. All rights reserved. KW - Calcium phosphates KW - Bone repair material KW - Biomineralization KW - Supramolecular ball structure Y1 - 2015 U6 - https://doi.org/10.1016/j.colsurfb.2015.05.021 SN - 0927-7765 SN - 1873-4367 VL - 132 SP - 246 EP - 252 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Kroener, Dominik T1 - Laser-driven electron dynamics for circular dichroism in mass spectrometry: from onephoton excitations to multiphoton ionization JF - Physical chemistry, chemical physics : a journal of European Chemical Societies N2 - The distinction of enantiomers is a key aspect of chemical analysis. In mass spectrometry the distinction of enantiomers has been achieved by ionizing the sample with circularly polarized laser pulses and comparing the ion yields for light of opposite handedness. While resonant excitation conditions are expected to be most efficient, they are not required for the detection of a circular dichroism (CD) in the ion yield. However, the prediction of the size and sign of the circular dichroism becomes challenging if non-resonant multiphoton excitations are used to ionize the sample. Employing femtosecond laser pulses to drive electron wavepacket dynamics based on ab initio calculations, we attempt to reveal underlying mechanisms that determine the CD under non-resonant excitation conditions. Simulations were done for (R)-1,2-propylene oxide, using time-dependent configuration interaction singles with perturbative doubles (TD-CIS(D)) and the aug-cc-pVTZ basis set. Interactions between the electric field and the electric dipole and quadrupole as well as between the magnetic field and the magnetic dipole were explicitly accounted for. The ion yield was determined by treating states above the ionization potential as either stationary or non-stationary with energy-dependent lifetimes based on an approved heuristic approach. The observed population dynamics do not allow for a simple interpretation, because of highly non-linear interactions. Still, the various transition pathways are governed by resonant enantiospecific n-photon excitation, with preferably high transition dipole moments, which eventually dominate the CD in the ionized population. Y1 - 2015 U6 - https://doi.org/10.1039/c5cp02193f SN - 1463-9076 SN - 1463-9084 VL - 17 IS - 29 SP - 19643 EP - 19655 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Kröner, Dominik T1 - Laser-driven electron dynamics for circular dichroism in mass spectrometry BT - from one-photon excitations to multiphoton ionization JF - Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies N2 - The distinction of enantiomers is a key aspect of chemical analysis. In mass spectrometry the distinction of enantiomers has been achieved by ionizing the sample with circularly polarized laser pulses and comparing the ion yields for light of opposite handedness. While resonant excitation conditions are expected to be most efficient, they are not required for the detection of a circular dichroism (CD) in the ion yield. However, the prediction of the size and sign of the circular dichroism becomes challenging if non-resonant multiphoton excitations are used to ionize the sample. Employing femtosecond laser pulses to drive electron wavepacket dynamics based on ab initio calculations, we attempt to reveal underlying mechanisms that determine the CD under non-resonant excitation conditions. Simulations were done for (R)-1,2-propylene oxide, using time-dependent configuration interaction singles with perturbative doubles (TD-CIS(D)) and the aug-cc-pVTZ basis set. Interactions between the electric field and the electric dipole and quadrupole as well as between the magnetic field and the magnetic dipole were explicitly accounted for. The ion yield was determined by treating states above the ionization potential as either stationary or non-stationary with energy-dependent lifetimes based on an approved heuristic approach. The observed population dynamics do not allow for a simple interpretation, because of highly non-linear interactions. Still, the various transition pathways are governed by resonant enantiospecific n-photon excitation, with preferably high transition dipole moments, which eventually dominate the CD in the ionized population. Y1 - 2015 U6 - https://doi.org/10.1039/C5CP02193F SN - 1463-9076 SN - 1463-9084 VL - 29 IS - 17 SP - 19643 EP - 19655 PB - The Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Kröner, Dominik T1 - Laser-driven electron dynamics for circular dichroism in mass spectrometry BT - from one-photon excitations to multiphoton ionization N2 - The distinction of enantiomers is a key aspect of chemical analysis. In mass spectrometry the distinction of enantiomers has been achieved by ionizing the sample with circularly polarized laser pulses and comparing the ion yields for light of opposite handedness. While resonant excitation conditions are expected to be most efficient, they are not required for the detection of a circular dichroism (CD) in the ion yield. However, the prediction of the size and sign of the circular dichroism becomes challenging if non-resonant multiphoton excitations are used to ionize the sample. Employing femtosecond laser pulses to drive electron wavepacket dynamics based on ab initio calculations, we attempt to reveal underlying mechanisms that determine the CD under non-resonant excitation conditions. Simulations were done for (R)-1,2-propylene oxide, using time-dependent configuration interaction singles with perturbative doubles (TD-CIS(D)) and the aug-cc-pVTZ basis set. Interactions between the electric field and the electric dipole and quadrupole as well as between the magnetic field and the magnetic dipole were explicitly accounted for. The ion yield was determined by treating states above the ionization potential as either stationary or non-stationary with energy-dependent lifetimes based on an approved heuristic approach. The observed population dynamics do not allow for a simple interpretation, because of highly non-linear interactions. Still, the various transition pathways are governed by resonant enantiospecific n-photon excitation, with preferably high transition dipole moments, which eventually dominate the CD in the ionized population. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 201 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-82109 ER - TY - JOUR A1 - Kröner, Dominik A1 - Gaebel, Tina T1 - Circular Dichroism in Mass Spectrometry: Quantum Chemical Investigations for the Differences between (R)-3-Methylcyclopentanone and Its Cation JF - The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment & general theory N2 - In mass spectrometry enantiomers can be distinguished by multiphoton ionization employing circular polarized laser pulses. The circular dichroism (CD) is detected from the normalized difference in the ion yield after excitation with light of opposite handedness. While there are cases in which fragment and parent ions exhibit the same sign of the CD in the ion yield, several experiments show that they might also differ in sign and magnitude. Supported by experimental observations it has been proposed that the parent ion, once it has been formed, is further excited by the laser, which may result in a change of the CD in the ion yield of the formed fragments compared to the parent ion. To gain a deeper insight in possible excitation pathways we calculated and compared the electronic CD absorption spectra of neutral and cationic (R)-3-methylcyclopentanone, applying density functional theory. In addition, electron wavepacket dynamics were used to compare the CD of one- and two-photon transitions. Our results support the proposed subsequent excitation of the parent ion as a possible origin of the difference of the CD in the ion yield between parent ion and fragments. Y1 - 2015 U6 - https://doi.org/10.1021/acs.jpca.5b05247 SN - 1089-5639 VL - 119 IS - 34 SP - 9167 EP - 9177 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Kumke, Michael Uwe A1 - Klier, Dennis Tobias T1 - Upconversion NaYF4:Yb:Er nanoparticles co-doped with Gd3+ and Nd3+ for thermometry on the nanoscale N2 - In the present work, the upconversion luminescence properties of oleic acid capped NaYF4:Gd3+:Yb3+:Er3+ upconversion nanoparticles (UCNP) with pure β crystal phase and Nd3+ ions as an additional sensitizer were studied in the temperature range of 288 K < T < 328 K. The results of this study showed that the complex interplay of different mechanisms and effects, causing the special temperature behavior of the UCNP can be developed into thermometry on the nanoscale, e.g. to be applied in biological systems on a cellular level. The performance was improved by the use of Nd3+ as an additional dopant utilizing the cascade sensitization mechanism in tri-doped UCNP. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 304 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-102677 SP - 67149 EP - 67156 ER - TY - JOUR A1 - Leroux, Fabrice A1 - Rabu, Pierre A1 - Sommerdijk, Nico A. J. M. A1 - Taubert, Andreas T1 - Two-Dimensional Hybrid Materials: Transferring Technology from Biology to Society JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - Hybrid materials are at the forefront of modern research and technology; hence a large number of publications on hybrid materials has already appeared in the scientific literature. This essay focuses on the specifics and peculiarities of hybrid materials based on two-dimensional (2D) building blocks and confinements, for two reasons: (1) 2D materials have a very broad field of application, but they also illustrate many of the scientific challenges the community faces, both on a fundamental and an application level; (2) all authors of this essay are involved in research on 2D materials, but their perspective and vision of how the field will develop in the future and how it is possible to benefit from these new developments are rooted in very different scientific subfields. The current article will thus present a personal, yet quite broad, account of how hybrid materials, specifically 2D hybrid materials, will provide means to aid modern societies in fields as different as healthcare and energy. Y1 - 2015 U6 - https://doi.org/10.1002/ejic.201500153 SN - 1434-1948 SN - 1099-0682 IS - 7 SP - 1089 EP - 1095 PB - Wiley-VCH CY - Weinheim ER - TY - INPR A1 - Leroux, Fabrice A1 - Rabu, Pierre A1 - Sommerdijk, Nico A. J. M. A1 - Taubert, Andreas T1 - Hybrid Materials Engineering in Biology, Chemistry, and Physics T2 - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - The Guest Editors emphasize the rapidly growing research in advanced materials.Telecommunication, health and environment, energy and transportation, and sustainability are just a few examples where new materials have been key for technological advancement. Y1 - 2015 U6 - https://doi.org/10.1002/ejic.201500098 SN - 1434-1948 SN - 1099-0682 IS - 7 SP - 1086 EP - 1088 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Liedel, Clemens A1 - Lewin, Christian A1 - Tsarkova, Larisa A1 - Böker, Alexander T1 - Reversible Switching of Block Copolymer Nanopatterns by Orthogonal Electric Fields JF - Small N2 - It is demonstrated that the orientation of striped patterns can be reversibly switched between two perpendicular in-plane orientations upon exposure to electric fields. The results on thin films of symmetric polystyrene-block-poly(2-vinyl pyridine) polymer in the intermediate segregation regime disclose two types of reorientation mechanisms from perpendicular to parallel relative to the electric field orientation. Domains orient via grain rotation and via formation of defects such as stretched undulations and temporal phase transitions. The contribution of additional fields to the structural evolution is also addressed to elucidate the generality of the observed phenomena. In particular solvent effects are considered. This study reveals the stabilization of the meta-stable in-plane oriented lamella due to sequential swelling and quenching of the film. Further, the reorientation behavior of lamella domains blended with selective nanoparticles is addressed, which affect the interfacial tensions of the blocks and hence introduce another internal field to the studied system. Switching the orientation of aligned block copolymer patterns between two orthogonal directions may open new applications of nanomaterials as switchable electric nanowires or optical gratings. KW - alignments KW - block copolymers KW - electric fields KW - reorientation KW - solvent vapor annealing KW - polymers Y1 - 2015 U6 - https://doi.org/10.1002/smll.201502259 SN - 1613-6810 SN - 1613-6829 VL - 11 IS - 45 SP - 6058 EP - 6064 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Lohren, Hanna A1 - Bornhorst, Julia A1 - Galla, Hans-Joachim A1 - Schwerdtle, Tanja T1 - The blood–cerebrospinal fluid barrier BT - First evidence for an active transport of organic mercury compounds out of the brain JF - Metallomics : integrated biometal science N2 - Exposure to organic mercury compounds promotes primarily neurological effects. Although methylmercury is recognized as a potent neurotoxicant, its transfer into the central nervous system (CNS) is not fully evaluated. While methylmercury and thiomersal pass the blood–brain barrier, limited data are available regarding the second brain regulating interface, the blood–cerebrospinal fluid (CSF) barrier. This novel study was designed to investigate the effects of organic as well as inorganic mercury compounds on, and their transfer across, a porcine in vitro model of the blood–CSF barrier for the first time. The barrier system is significantly more sensitive towards organic Hg compounds as compared to inorganic compounds regarding the endpoints cytotoxicity and barrier integrity. Whereas there are low transfer rates from the blood side to the CSF side, our results strongly indicate an active transfer of the organic mercury compounds out of the CSF. These results are the first to demonstrate an efflux of organic mercury compounds regarding the CNS and provide a completely new approach in the understanding of mercury compounds specific transport. Y1 - 2015 U6 - https://doi.org/10.1039/C5MT00171D SN - 1756-5901 SN - 1756-591X VL - 10 IS - 7 SP - 1420 EP - 1430 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Lohren, Hanna A1 - Bornhorst, Julia A1 - Galla, Hans-Joachim A1 - Schwerdtle, Tanja T1 - The blood–cerebrospinal fluid barrier BT - First evidence for an active transport of organic mercury compounds out of the brain N2 - Exposure to organic mercury compounds promotes primarily neurological effects. Although methylmercury is recognized as a potent neurotoxicant, its transfer into the central nervous system (CNS) is not fully evaluated. While methylmercury and thiomersal pass the blood–brain barrier, limited data are available regarding the second brain regulating interface, the blood–cerebrospinal fluid (CSF) barrier. This novel study was designed to investigate the effects of organic as well as inorganic mercury compounds on, and their transfer across, a porcine in vitro model of the blood–CSF barrier for the first time. The barrier system is significantly more sensitive towards organic Hg compounds as compared to inorganic compounds regarding the endpoints cytotoxicity and barrier integrity. Whereas there are low transfer rates from the blood side to the CSF side, our results strongly indicate an active transfer of the organic mercury compounds out of the CSF. These results are the first to demonstrate an efflux of organic mercury compounds regarding the CNS and provide a completely new approach in the understanding of mercury compounds specific transport. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 200 Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-82089 ER - TY - JOUR A1 - Lorenz, Ulf A1 - Saalfrank, Peter T1 - Measures for the non-Markovianity of a harmonic oscillator coupled to a discrete bath derived from numerically exact references JF - The European physical journal : D, Atomic, molecular, optical and plasma physics N2 - System-bath problems in physics and chemistry are often described by Markovian master equations. However, the Markov approximation, i.e., neglect of bath memory effects is not always justified, and different measures of non-Markovianity have been suggested in the literature to judge the validity of this approximation. Here we calculate several computable measures of non-Markovianity for the non-trivial problem of a harmonic oscillator coupled to a large number of bath oscillators. The Multi Configurational Time Dependent Hart ree nietliod is used to provide a numerically converged solution of the system-bath Schrodinger equation, from which the appropriate quantities can be calculated. In particular, we consider measures based on trace-distances and quantum discord for a variety of initial states. These quantities have proven useful in the case of two-level and other small model systems Tpically encountered in quantum optics; but are less straightforward to interpret for the more complex model systems that are relevant for chemical physics. Y1 - 2015 U6 - https://doi.org/10.1140/epjd/e2014-50727-8 SN - 1434-6060 SN - 1434-6079 VL - 69 IS - 2 PB - Springer CY - New York ER - TY - GEN A1 - Lorenz, Ulf A1 - Saalfrank, Peter T1 - Comparing thermal wave function methods for multi-configuration time-dependent Hartree simulations (vol 140, 044106, 2014) T2 - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr Y1 - 2015 U6 - https://doi.org/10.1063/1.4938051 SN - 0021-9606 SN - 1089-7690 VL - 143 IS - 22 PB - American Institute of Physics CY - Melville ER -