@article{GuelzowHoernerStrauchetal.2017, author = {Guelzow, Jana and Hoerner, Gerald and Strauch, Peter and Stritt, Anika and Irran, Elisabeth and Grohmann, Andreas}, title = {Oxygen Delivery as a Limiting Factor in Modelling Dicopper(II) Oxidase Reactivity}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201605868}, pages = {7009 -- 7023}, year = {2017}, abstract = {Deprotonation of ligand-appended alkoxyl groups in mononuclear copper(II) complexes of N,O ligands L-1 and L-2, gave dinuclear complexes sharing symmetrical Cu2O2 cores. Molecular structures of these mono-and binuclear complexes have been characterized by XRD, and their electronic structures by UV/Vis, H-1 NMR, EPR and DFT; moreover, catalytic performance as models of catechol oxidase was studied. The binuclear complexes with anti-ferromagnetically coupled copper(II) centers are moderately active in quinone formation from 3,5-di-tert-butyl-catechol under the estab-lished conditions of oxygen saturation, but are strongly activated when additional dioxygen is administered during catalytic turnover. This unforeseen and unprecedented effect is attributed to increased maximum reaction rates v(max), whereas the substrate affinity KM remains unaffected. Oxygen administration is capable of (partially) removing limitations to turnover caused by product inhibition. Because product inhibition is generally accepted to be a major limitation of catechol oxidase models, we think that our observations will be applicable more widely.}, language = {en} } @article{VishnevetskayaHildebrandNiebuuretal.2017, author = {Vishnevetskaya, Natalya S. and Hildebrand, Viet and Niebuur, Bart-Jan and Grillo, Isabelle and Filippov, Sergey K. and Laschewsky, Andre and M{\"u}ller-Buschbaum, Peter and Papadakis, Christine M.}, title = {"Schizophrenic" Micelles from Doubly Thermoresponsive Polysulfobetaine-b-poly(N-isopropylmethacrylamide) Diblock Copolymers}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {50}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.7b00356}, pages = {3985 -- 3999}, year = {2017}, language = {en} } @article{SchwarzeMuellerSchmidtetal.2017, author = {Schwarze, Thomas and Mueller, Holger and Schmidt, Darya and Riemer, Janine and Holdt, Hans-J{\"u}rgen}, title = {Design of Na+-Selective Fluorescent Probes: A Systematic Study of the Na+-Complex Stability and the Na+/K+ Selectivity in Acetonitrile and Water}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201605986}, pages = {7255 -- 7263}, year = {2017}, abstract = {There is a tremendous demand for highly Na+-selective fluoroionophores to monitor the top analyte Na+ in life science. Here, we report a systematic route to develop highly Na+/K+ selective fluorescent probes. Thus, we synthesized a set of fluoroionophores 1, 3, 4, 5, 8 and 9 (see Scheme 1) to investigate the Na+/K+ selectivity and Na(+-)complex stability in CH3CN and H2O. These Na+-probes bear different 15-crown-5 moieties to bind Na+ stronger than K+. In the set of the diethylaminocoumarin-substituted fluoroionophores 1-5, the following trend of fluorescence quenching 1 > 3 > 2 > 4 > 5 in CH3CN was observed. Therefore, the flexibility of the aza-15-crown-5 moieties in 1-4 determines the conjugation of the nitrogen lone pair with the aromatic ring. As a consequence, 1 showed in CH3CN the highest Na+-induced fluorescence enhancement (FE) by a factor of 46.5 and a weaker K+ induced FE of 3.7. The Na+-complex stability of 1-4 in CH3CN is enhanced in the following order of 2 > 4 > 3 > 1, assuming that the O-atom of the methoxy group in the ortho-position, as shown in 2, strengthened the Na+-complex formation. Furthermore, we found for the N( o-methoxyphenyl) aza-15-crown-5 substituted fluoroionophores 2, 8 and 9 in H2O, an enhanced Na+-complex stability in the following order 8 > 2 > 9 and an increased Na+/K+ selectivity in the reverse order 9 > 2 > 8. Notably, the Na+-induced FE of 8 (FEF = 10.9), 2 (FEF = 5.0) and 9 (FEF = 2.0) showed a similar trend associated with a decreased K+-induced FE [8 (FEF = 2.7) > 2 (FEF = 1.5) > 9 (FEF = 1.1)]. Here, the Na+-complex stability and Na+/K+ selectivity is also influenced by the fluorophore moiety. Thus, fluorescent probe 8 (K-d = 48 mm) allows high-contrast, sensitive, and selective Na+ measurements over extracellular K+ levels. A higher Na+/K+ selectivity showed fluorescent probe 9, but also a higher Kd value of 223 mm. Therefore, 9 is a suitable tool to measure Na+ concentrations up to 300 mm at a fluorescence emission of 614 nm.}, language = {en} } @article{RoggenbuckGoihlHanacketal.2017, author = {Roggenbuck, Dirk and Goihl, Alexander and Hanack, Katja and Holzloehner, Pamela and Hentschel, Christian and Veiczi, Miklos and Schierack, Peter and Reinhold, Dirk and Schulz, Hans-Ulrich}, title = {Serological diagnosis and prognosis of severe acute pancreatitis by analysis of serum glycoprotein 2}, series = {Clinical chemistry and laboratory medicine : journal of the Forum of the European Societies of Clinical Chemistry - the European Branch of the International Federation of Clinical Chemistry and Laboratory Medicine}, volume = {55}, journal = {Clinical chemistry and laboratory medicine : journal of the Forum of the European Societies of Clinical Chemistry - the European Branch of the International Federation of Clinical Chemistry and Laboratory Medicine}, publisher = {De Gruyter}, address = {Berlin}, issn = {1434-6621}, doi = {10.1515/cclm-2016-0797}, pages = {854 -- 864}, year = {2017}, abstract = {To better understand emerging adults' perceptions of family interactions and value transmission to the next generation, we examined Hmong American emerging adults' reflections on their parents' parenting. Participants discussed what parenting practices they would do differently and others they hoped to emulate with their future adolescent children. Thirty Hmong American emerging adults (18-25 years; M = 21.2 years; 50\% female) participated in interviews that focused retrospectively on the parent-adolescent relationship. Results revealed that emerging adults wanted to parent differently in three ways: less pressure about education, fewer restrictions, and more open communication. Emerging adults imagined being a similar parent in four ways: promoting education, promoting life values, giving guidance, and offering love and support. The findings highlight parenting practices that Hmong American emerging adults plan on transmitting (and not transmitting) to their own children, offering a glimpse into the type of parents the emerging adults may become.}, language = {en} } @article{RumschoettelKosmellaPrietzeletal.2017, author = {Rumschoettel, Jens and Kosmella, Sabine and Prietzel, Claudia Christina and Appelhans, Dietmar and Koetz, Joachim}, title = {DNA polyplexes with dendritic glycopolymer-entrapped gold nanoparticles}, series = {Colloids and surfaces : an international journal devoted to fundamental and applied research on colloid and interfacial phenomena in relation to systems of biological origin ; B, Biointerfaces}, volume = {154}, journal = {Colloids and surfaces : an international journal devoted to fundamental and applied research on colloid and interfacial phenomena in relation to systems of biological origin ; B, Biointerfaces}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0927-7765}, doi = {10.1016/j.colsurfb.2017.03.001}, pages = {74 -- 81}, year = {2017}, abstract = {Polyplexes, composed of Salmon DNA and very small gold nanoparticles embedded into a dendritic glycopolymer architecture of sugar-modified poly(ethyleneimine) (PEI-Mal) with a molar mass of about 25,000 g/mol, were characterized by dynamic light scattering (DLS), zeta potential measurements, micro differential scanning calorimetry (mu-DSC) and transmission electron microscopy (TEM). The PEI-Mal-entrapped gold nanoparticles of about 2 nm in diameter influence the polyplex formation of the hyperbranched PEI containing bulky maltose, and in consequence the DNA is more compactized in the inner part of spherical polyplex particles of about 150 nm in diameter. The resulting more compact core shell polyplex particles with embedded gold nanoparticles in the outer polymer shell will be used as components in forthcoming gene delivery experiments. (C) 2017 Elsevier B.V. All rights reserved.}, language = {en} } @article{TebaldiCharanMavliutovaetal.2017, author = {Tebaldi, Marli Luiza and Charan, Himanshu and Mavliutova, Liliia and B{\"o}ker, Alexander and Glebe, Ulrich}, title = {Dual-Stimuli Sensitive Hybrid Materials: Ferritin-PDMAEMA by Grafting-From Polymerization}, series = {Macromolecular chemistry and physics}, volume = {218}, journal = {Macromolecular chemistry and physics}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1352}, doi = {10.1002/macp.201600529}, pages = {6}, year = {2017}, abstract = {The combination of stimuli-responsive polymers and proteins that can transport drugs is a promising approach for drug delivery. The formation of ferritin-poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) conjugates by atom-transfer radical polymerization from the protein macroinitiator is described. PDMAEMA is a dual-stimuli-responsive polymer and the thermo- and pH-responsive properties of the resulting conjugates are studied in detail with dynamic light scattering (DLS). Additionally, it is demonstrated that the lower critical solution temperature (LCST) of the protein-polymer conjugates can be further adjusted by the ionic strength of the solution. The conjugates are also characterized by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), matrix-assisted laser desorption ionization-time of flight (MALDI-ToF) mass spectrometry, and NMR spectroscopy. The obtained MALDI-ToF mass spectra are exceptional for protein-polymer conjugates and have not been so often reported.}, language = {en} } @article{ZuehlkeZenichowskiRiebeetal.2017, author = {Z{\"u}hlke, Martin and Zenichowski, Karl and Riebe, Daniel and Beitz, Toralf and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Subambient pressure electrospray ionization ion mobility spectrometry}, series = {International journal for ion mobility spectrometry : official publication of the International Society for Ion Mobility Spectrometry}, volume = {20}, journal = {International journal for ion mobility spectrometry : official publication of the International Society for Ion Mobility Spectrometry}, publisher = {Springer}, address = {Heidelberg}, issn = {1435-6163}, doi = {10.1007/s12127-017-0215-x}, pages = {47 -- 56}, year = {2017}, abstract = {The pressure dependence of sheath gas assisted electrospray ionization (ESI) was investigated based on two complementary experimental setups, namely an ESI-ion mobility (IM) spectrometer and an ESI capillary - Faraday plate setup housed in an optically accessible vacuum chamber. The ESI-IM spectrometer is capable of working in the pressure range between 300 and 1000 mbar. Another aim was the assessment of the analytical capabilities of a subambient pressure ESI-IM spectrometer. The pressure dependence of ESI was characterized by imaging the electrospray and recording current-voltage (I-U) curves. Qualitatively different behavior was observed in both setups. While the current rises continuously with the voltage in the capillary-plate setup, a sharp increase of the current was measured in the IM spectrometer above a pressure-dependent threshold voltage. The different character can be attributed to the detection of different species in both experiments. In the capillary-plate experiment, a multitude of charged species are detected while only desolvated ions attribute to the IM spectrometer signal. This finding demonstrates the utility of IM spectrometry for the characterization of ESI, since in contrast to the capillary-plate setup, the release of ions from the electrospray droplets can be observed. The I-U curves change significantly with pressure. An important result is the reduction of the maximum current with decreasing pressure. The connected loss of ionization efficiency can be compensated by a more efficient transfer of ions in the IM spectrometer at increased E/N. Thus, similar limits of detection could be obtained at 500 mbar and 1 bar.}, language = {en} } @article{LiebigSarhanSanderetal.2017, author = {Liebig, Ferenc and Sarhan, Radwan Mohamed and Sander, Mathias and Koopman, Wouter-Willem Adriaan and Schuetz, Roman and Bargheer, Matias and Koetz, Joachim}, title = {Deposition of Gold Nanotriangles in Large Scale Close-Packed Monolayers for X-ray-Based Temperature Calibration and SERS Monitoring of Plasmon-Driven Catalytic Reactions}, series = {ACS applied materials \& interfaces}, volume = {9}, journal = {ACS applied materials \& interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.7b07231}, pages = {20247 -- 20253}, year = {2017}, language = {en} } @article{SchuermannTanzerDabkowskaetal.2017, author = {Schuermann, Robin and Tanzer, Katrin and Dabkowska, Iwona and Denifl, Stephan and Bald, Ilko}, title = {Stability of the Parent Anion of the Potential Radiosensitizer 8-Bromoadenine Formed by Low-Energy (< 3 eV) Electron Attachment}, series = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, volume = {121}, journal = {The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces \& biophysical chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {1520-6106}, doi = {10.1021/acs.jpcb.7b02130}, pages = {5730 -- 5734}, year = {2017}, abstract = {8-Bromoadenine ((8Br)A) is a potential DNA radiosensitizer for cancer radiation therapy due to its efficient interaction with low-energy electrons (LEEs). LEEs are a short-living species generated during the radiation damage of DNA by high-energy radiation as it is applied in cancer radiation therapy. Electron attachment to (8Br)A in the gas phase results in a stable parent anion below 3 eV electron energy in addition to fragmentation products formed by resonant exocyclic bond cleavages. Density functional theory (DFT) calculations of the (8Br)A(-) anion reveal an exotic bond between the bromine and the C8 atom with a bond length of 2.6 angstrom, where the majority of the charge is located on bromine and the spin is mainly located on the C8 atom. The detailed understanding of such long-lived anionic states of nucleobase analogues supports the rational development of new therapeutic agents, in which the enhancement of dissociative electron transfer to the DNA backbone is critical to induce DNA strand breaks in cancerous tissue.}, language = {en} } @article{FudickarPavasheLinker2017, author = {Fudickar, Werner and Pavashe, Prashant and Linker, Torsten}, title = {Thiocarbohydrates on Gold Nanoparticles: Strong Influence of Stereocenters on Binding Affinity and Interparticle Forces}, series = {Chemistry - a European journal}, volume = {23}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201700846}, pages = {8685 -- 8693}, year = {2017}, abstract = {Carbohydrates carrying thiol groups at the C-2 position have been attached to gold nanoparticles (AuNPs) with stereocenters in close proximity to the surface for the first time. Their configurations can be clearly distinguished by the tendency of particle aggregation. AuNP surface plasmon resonance (SPR), X-ray photoelectron spectroscopy (XPS), and IR spectroscopy indicate that the thiocarbohydrates replace citrate molecules at different rates, causing aggregation and eventually precipitation. A quantitative formulation of this aggregation process shows that reactivities can vary by several magnitudes. Adsorption isotherms and kinetics also demonstrate that the number of thiocarbohydrates varies by a factor of two. Molecular mechanics force field (MMFF) calculations reveal their relative orientations. Based on these models, the different binding behavior can be ascribed to attractive van der Waals forces and hydrogen bonds. Such interactions occur either between the carbohydrate and AuNPs, by lateral intermolecular forces at the surface, or by interparticle attraction, in analogy to cell-surface carbohydrates of biological recognition systems. Aggregation of NPs therefore act as an indicator to differentiate between various carbohydrates with defined configurations.}, language = {en} } @article{ArminDurrantShoaee2017, author = {Armin, Ardalan and Durrant, James R. and Shoaee, Safa}, title = {Interplay Between Triplet-, Singlet-Charge Transfer States and Free Charge Carriers Defining Bimolecular Recombination Rate Constant of Organic Solar Cells}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {121}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.7b04825}, pages = {13969 -- 13976}, year = {2017}, abstract = {Despite the myriad of organic donor:acceptor materials, only few systems have emerged in the life of organic solar cells to, exhibit considerable reduced bimolecular recombination, with respect to the random encounter rate given by the Langevin equation. Monte Carlo simulations have revealed that the rate constant of the formation of electron-hole bound states depends on the random encounter of opposite charges and is nearly given by the Langevin equation for the domain sizes relevant to efficient bulk heterojunction systems. Recently, three studies :suggested that charge transfer states dissociating much faster than their decay rate to the ground state, can result in reduced bimolecular recombination by lowering the recombination rate to the ground state as a loss pathway. A separate study identified another loss pathway and suggested that forbidden back electron transfer from triplet charge transfer states to triplet excitons is a key to achieving reduced recombination. Herein we further explain the reduced bimolecular recombination by investigating the limitations of these two proposals. By solving kinetic rate equations for a BHJ system with realistic rates, we show that both of these previously presented conditions must only be held at the same time fora system to exhibit non-Langevin behavior. We demonstrate that suppression of both of the parallel loss channels of singlet and triplet states can be achieved through increasing the dissociation rate of the charge transfer states; a crucial requirement to achieve a high charge carrier extraction efficiency.}, language = {en} } @article{PehLiedelTaubertetal.2017, author = {Peh, Eddie and Liedel, Clemens and Taubert, Andreas and Tauer, Klaus}, title = {Composition inversion to form calcium carbonate mixtures}, series = {CrystEngComm}, volume = {19}, journal = {CrystEngComm}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1466-8033}, doi = {10.1039/c7ce00433h}, pages = {3573 -- 3583}, year = {2017}, abstract = {Composition inversion takes place in equimolar solid mixtures of sodium or ammonium carbonate and calcium chloride with respect to the combination of anions and cations leading to the corresponding chloride and calcite in complete conversion. The transformation takes place spontaneously under a variety of different situations, even in a powdery mixture resting under ambient conditions. Powder X-ray diffraction data and scanning electron microscopy micrographs are presented to describe the course of the reaction and to characterize the reaction products. The incomplete reaction in the interspace between two compressed tablets of pure starting materials leads to an electric potential due to the presence of uncompensated charges.}, language = {en} } @article{KnechtReiterSchlaadetal.2017, author = {Knecht, Volker and Reiter, Guenter and Schlaad, Helmut and Reiter, Renate}, title = {Structure Formation in Langmuir Peptide Films As Revealed from Coarse-Grained Molecular Dynamics Simulations}, series = {Langmuir}, volume = {33}, journal = {Langmuir}, publisher = {American Chemical Society}, address = {Washington}, issn = {0743-7463}, doi = {10.1021/acs.langmuir.7b01455}, pages = {6492 -- 6502}, year = {2017}, abstract = {Molecular dynamics simulations in conjunction with the Martini coarse-grained model have been used to investigate the (nonequilibrium) behavior of helical 22-residue poly(gamma-benzyl-L-glutamate) (PBLG) peptides at the water/vapor interface. Preformed PBLG mono- or bilayers homogeneously covering the water surface laterally collapse in tens of nanoseconds, exposing significant proportions of empty water surface. This behavior was also observed in recent AFM experiments at similar areas per monomer, where a complete coverage had been assumed in earlier work. In the simulations, depending on the area per monomer, either elongated clusters or fibrils form, whose heights (together with the portion of empty water surface) increase over time. Peptides tend to align with respect to the fiber axis or with the major principal axis of the cluster, respectively. The aspect ratio of the cluster observed is 1.7 and, hence, comparable to though somewhat smaller than the aspect ratio of the peptides in alpha-helical conformation, which is 2.2. The heights of the fibrils is 3 nm after 20 ns and increases to 4.5 nm if the relaxation time is increased by 2 orders of magnitude, in agreement with the experiment. Aggregates with heights of about 3 or 4.5 nm are found to correspond to local bi- or trilayer structures, respectively.}, language = {en} } @article{SungKochovskiZhangetal.2017, author = {Sung, Jian-Ke and Kochovski, Zdravko and Zhang, Wei-Yi and Kirmse, Holm and Lu, Yan and Antonietti, Markus and Yuan, Jiayin}, title = {General Synthetic Route toward Highly Dispersed Metal Clusters Enabled by Poly(ionic liquid)s}, series = {Journal of the American Chemical Society}, volume = {139}, journal = {Journal of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0002-7863}, doi = {10.1021/jacs.7b03357}, pages = {8971 -- 8976}, year = {2017}, abstract = {The ability to synthesize a broad spectrum of metal clusters (MCs) with their size controllable on a subnanometer scale presents an enticing prospect for exploring nanosize-dependent properties. Here we report an innovative design of a capping agent from a polytriazolium poly(ionic liquid) (PIL) in a vesicular form in solution that allows for crafting a variety of MCs including transition metals, noble metals, and their bimetallic alloy with precisely controlled sizes (similar to 1 nm) and record-high catalytic performance. The ultrastrong stabilization power is a result of an unusual synergy between the conventional binding sites in the heterocyclic cations in PIL and an in situ generated polycarbene structure induced simultaneously to the reduction reaction.}, language = {en} } @article{KleinpeterWernerLinker2017, author = {Kleinpeter, Erich and Werner, Peter and Linker, Torsten}, title = {Synthesis and NMR spectroscopic conformational analysis of benzoic acid esters of mono- and 1,4-dihydroxycyclohexane, 4-hydroxycyclohexanone and the -ene analogue - The more polar the molecule the more stable the axial conformer}, series = {Tetrahedron}, volume = {73}, journal = {Tetrahedron}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4020}, doi = {10.1016/j.tet.2017.04.029}, pages = {3801 -- 3809}, year = {2017}, abstract = {para-Substituted benzoic acid esters of cyclohexanol, 1,4-dihydroxycyclohexane, 4-hydroxy-cyclohexanone and of the corresponding exo-methylene derivative were synthesized and the conformational equilibria of the cyclohexane skeleton studied by low temperature H-1 and C-13 NMR spectroscopy. The geometry optimized structures of the axial/equatorial chair conformers were computed at the DFT level of theory. Only one preferred conformation of the ester group was obtained for both the axial and the equatorial conformer, respectively. The content of the axial conformer increases with growing polarity of the 6-membered ring moiety; hereby, in addition, the effect of sp(2) hybridization/polarity of C(4)= O/C(4)= CH2 on the present conformational equilibria is critically evaluated. Another dynamic process could be studied, for the first time in this kind of compounds. (C) 2017 Elsevier Ltd. All rights reserved.}, language = {en} } @article{MeiJaftaLauermannetal.2017, author = {Mei, Shilin and Jafta, Charl J. and Lauermann, Iver and Ran, Qidi and Kaergell, Martin and Ballauff, Matthias and Lu, Yan}, title = {Porous Ti4O7 Particles with Interconnected-Pore Structure as a High-Efficiency Polysulfide Mediator for Lithium-Sulfur Batteries}, series = {Advanced functional materials}, volume = {27}, journal = {Advanced functional materials}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.201701176}, pages = {10}, year = {2017}, abstract = {Multifunctional Ti4O7 particles with interconnected-pore structure are designed and synthesized using porous poly(styrene-b-2-vinylpyridine) particles as a template. The particles can work efficiently as a sulfur-host material for lithium-sulfur batteries. Specifically, the well-defined porous Ti4O7 particles exhibit interconnected pores in the interior and have a high-surface area of 592 m(2) g(-1); this shows the advantage of mesopores for encapsulating of sulfur and provides a polar surface for chemical binding with polysulfides to suppress their dissolution. Moreover, in order to improve the conductivity of the electrode, a thin layer of carbon is coated on the Ti4O7 surface without destroying its porous structure. The porous Ti4O7 and carbon-coated Ti4O7 particles show significantly improved electrochemical performances as cathode materials for Li-S batteries as compared with those of TiO2 particles.}, language = {en} } @article{KhademHilleLoehmannsroebenetal.2017, author = {Khadem, S. M. J. and Hille, Carsten and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Sokolov, Igor M.}, title = {Spot variation fluorescence correlation spectroscopy by data post-processing}, series = {Scientific reports}, volume = {7}, journal = {Scientific reports}, publisher = {Nature Publ. Group}, address = {London}, issn = {2045-2322}, doi = {10.1038/s41598-017-05672-8}, pages = {1 -- 9}, year = {2017}, abstract = {Spot variation fluorescence correlation spectroscopy (SV-FCS) is a variant of the FCS techniques which may give useful information about the structural organisation of the medium in which the diffusion takes place. We show that the same results can be obtained by post-processing the photon count data from ordinary FCS measurements. By using this method, one obtains the fluorescence autocorrelation functions for sizes of confocal volume, which are effectively smaller than that of the initial FCS measurement. The photon counts of the initial experiment are first transformed into smooth intensity trace using kernel smoothing method or to a piecewise-continuous intensity trace using binning and then a non-linear transformation is applied to this trace. The result of this transformation mimics the photon count rate in an experiment performed with a smaller confocal volume. The applicability of the method is established in extensive numerical simulations and directly supported in in-vitro experiments. The procedure is then applied to the diffusion of AlexaFluor647-labeled streptavidin in living cells.}, language = {en} } @article{KleinpeterKoch2017, author = {Kleinpeter, Erich and Koch, Andreas}, title = {Identification of mesomeric substructures by through-space NMR shieldings (TSNMRS). Trimethine cyanine/merocyanine-like or aromatic pi-electron delocalization?}, series = {Tetrahedron}, volume = {73}, journal = {Tetrahedron}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4020}, doi = {10.1016/j.tet.2017.05.062}, pages = {4265 -- 4274}, year = {2017}, abstract = {The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of amino-substituted heteraromatic six-membered ring systems such as pyrylium/thiopyrylium analogues have been calculated using the GIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to quantify and visualize the existing aromaticity of the studied compounds. Due to strong conjugation of six-membered ring pi-electrons and lone pairs of the exo-cyclic amino substituents (restricted rotation about partial C,N double bonds) the interplay of still aromatic and already dominating trimethine cyanine/merocyanine-like substructures can be estimated. (C) 2017 Elsevier Ltd. All rights reserved.}, language = {en} } @article{BogomolovaSeckerKoetzetal.2017, author = {Bogomolova, Anna and Secker, Christian and Koetz, Joachim and Schlaad, Helmut}, title = {Thermo-induced multistep assembly of double-hydrophilic block copolypeptoids in water}, series = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, volume = {295}, journal = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, publisher = {Springer}, address = {New York}, issn = {0303-402X}, doi = {10.1007/s00396-017-4044-6}, pages = {1305 -- 1312}, year = {2017}, abstract = {The aqueous solution behavior of thermoresponsive-hydrophilic block copolypeptoids, i.e., poly(N-(n-propyl)glycine) (x) -block-poly(N-methylglycine) (y) (x = 70; y = 23, 42, 76), in the temperature range of 20-45 A degrees C is studied. Turbidimetric analyses of the 0.1 wt\% aqueous solutions reveal two cloud points at T (cp)similar to 30 and 45 A degrees C and a clearing point in between at T (cl)similar to 42 A degrees C. Temperature-dependent dynamic light scattering (DLS) suggest that right above the first collapse temperature, single polymer molecules assemble into large structures which upon further heating, i.e., at the clearing point temperature, disassemble into micelle-like structures. Upon further heating, the aggregates start to grow again in size, as recognized by the second cloud point, through a crystallization process.}, language = {en} } @article{DaniTauberZhangetal.2017, author = {Dani, Alessandro and Tauber, Karoline and Zhang, Weiyi and Schlaad, Helmut and Yuan, Jiayin}, title = {Stable Covalently Photo-Crosslinked Poly(Ionic Liquid) Membrane with Gradient Pore Size}, series = {Macromolecular rapid communications}, volume = {38}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201700167}, pages = {4}, year = {2017}, abstract = {Porous polyelectrolyte membranes stable in a highly ionic environment are obtained by covalent crosslinking of an imidazolium-based poly(ionic liquid). The crosslinking reaction involves the UV light-induced thiol-ene (click) chemistry, and the phase separation, occurring during the crosslinking step, generates a fully interconnected porous structure in the membrane. The porosity is on the order of the micrometer scale and the membrane shows a gradient of pore size across the membrane cross-section. The membrane can separate polystyrene latex particles of different size and undergoes actuation in contact with acetone due to the asymmetric porous structure.}, language = {en} }