@article{ZuehlkeRiebeBeitzetal.2016, author = {Z{\"u}hlke, Martin and Riebe, Daniel and Beitz, Toralf and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Andreotti, Sandro and Reinert, Knut and Zenichowski, Karl and Diener, Marc}, title = {High-performance liquid chromatography with electrospray ionization ion mobility spectrometry: Characterization, data management, and applications}, series = {Journal of separation science}, volume = {39}, journal = {Journal of separation science}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1615-9306}, doi = {10.1002/jssc.201600749}, pages = {4756 -- 4764}, year = {2016}, abstract = {The combination of high-performance liquid chromatography and electrospray ionization ion mobility spectrometry facilitates the two-dimensional separation of complex mixtures in the retention and drift time plane. The ion mobility spectrometer presented here was optimized for flow rates customarily used in high-performance liquid chromatography between 100 and 1500 mu L/min. The characterization of the system with respect to such parameters as the peak capacity of each time dimension and of the 2D spectrum was carried out based on a separation of a pesticide mixture containing 24 substances. While the total ion current chromatogram is coarsely resolved, exhibiting coelutions for a number of compounds, all substances can be separately detected in the 2D plane due to the orthogonality of the separations in retention and drift dimensions. Another major advantage of the ion mobility detector is the identification of substances based on their characteristic mobilities. Electrospray ionization allows the detection of substances lacking a chromophore. As an example, the separation of a mixture of 18 amino acids is presented. A software built upon the free mass spectrometry package OpenMS was developed for processing the extensive 2D data. The different processing steps are implemented as separate modules which can be arranged in a graphic workflow facilitating automated processing of data.}, language = {en} } @article{ZhouWuennemannKuhnetal.2016, author = {Zhou, Qihui and Wuennemann, Patrick and Kuhn, Philipp Till and de Vries, Joop and Helmin, Marta and B{\"o}ker, Alexander and van Kooten, Theo G. and van Rijn, Patrick}, title = {Mechanical Properties of Aligned Nanotopologies for Directing Cellular Behavior}, series = {Advanced materials interfaces}, volume = {3}, journal = {Advanced materials interfaces}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.201600275}, pages = {10}, year = {2016}, abstract = {Tailoring cell-surface interactions is important for the of design medical implants as well as regenerative medicine and tissue engineering materials. Here the single parameter system is transcended via translating hard nanotopology into soft polymeric hydrogel structures via hydrogel imprinting lithography. The response of these cells to the nanotopology of the same dimensions but with different mechanical properties displays unexpected behavior between "hard" tissue cells and "soft" tissue cells.}, language = {en} } @article{ZhongMetwalliRawolleetal.2016, author = {Zhong, Qi and Metwalli, Ezzeldin and Rawolle, Monika and Kaune, Gunar and Bivigou Koumba, Achille Mayelle and Laschewsky, Andre and Papadakis, Christine M. and Cubitt, Robert and Wang, Jiping and M{\"u}ller-Buschbaum, Peter}, title = {Influence of Hydrophobic Polystyrene Blocks on the Rehydration of Polystyrene-block-poly(methoxy diethylene glycol acrylate)-block-polystyrene Films Investigated by in Situ Neutron Reflectivity}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {49}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.5b02279}, pages = {317 -- 326}, year = {2016}, abstract = {The rehydration of thermoresponsive polystyrene-block-poly(methoxy diethylene glycol acrylate)-block-polystyrene (PS-b-PMDEGA-b-PS) films forming a lamellar microphase-separated structure is investigated by in situ neutron reflectivity in a D2O vapor atmosphere. The rehydration of collapsed PS-b-PMDEGA-b-PS films is realized by a temperature change from 45 to 23 degrees C and comprises (1) condensation and absorption of D2O, (2) evaporation of D2O, and (3) reswelling of the film due to internal rearrangement. The hydrophobic PS layers hinder the absorption of condensed D2O, and a redistribution of embedded D2O between the hydrophobic PS layers and the hydrophilic PMDEGA layers is observed. In contrast, the rehydration of semiswollen PS-b-PMDEGA-b-PS films (temperature change from 35 to 23 degrees C) shows two prominent differences: A thicker D2O layer condenses on the surface, causing a more enhanced evaporation of D2O. The rehydrated films differ in film thickness and volume fraction of D2O, which is due to the different thermal protocols, although the final temperature is identical.}, language = {en} } @article{ZhangBehlPengetal.2016, author = {Zhang, Pengfei and Behl, Marc and Peng, Xingzhou and Razzaq, Muhammad Yasar and Lendlein, Andreas}, title = {Ultrasonic Cavitation Induced Shape-Memory Effect in Porous Polymer Networks}, series = {Macromolecular rapid communications}, volume = {37}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201600439}, pages = {1897 -- 1903}, year = {2016}, abstract = {Inspired by the application of ultrasonic cavitation based mechanical force (CMF) to open small channels in natural soft materials (skin or tissue), it is explored whether an artificial polymer network can be created, in which shape-changes can be induced by CMF. This concept comprises an interconnected macroporous rhodium-phosphine (Rh-P) coordination polymer network, in which a CMF can reversibly dissociate the Rh-P microphases. In this way, the ligand exchange of Rh-P coordination bonds in the polymer network is accelerated, resulting in a topological rearrangement of molecular switches. This rearrangement of molecular switches enables the polymer network to release internal tension under ultrasound exposure, resulting in a CMF-induced shape-memory capability. The interconnected macroporous structure with thin pore walls is essential for allowing the CMF to effectively permeate throughout the polymer network. Potential applications of this CMF-induced shape-memory polymer can be mechanosensors or ultrasound controlled switches.}, language = {en} } @article{ZengFrascaRumschoetteletal.2016, author = {Zeng, Ting and Frasca, Stefano and Rumsch{\"o}ttel, Jens and Koetz, Joachim and Leimk{\"u}hler, Silke and Wollenberger, Ursula}, title = {Role of Conductive Nanoparticles in the Direct Unmediated Bioelectrocatalysis of Immobilized Sulfite Oxidase}, series = {Electroanalysis : an international journal devoted to fundamental and practical aspects of electroanalysis}, volume = {28}, journal = {Electroanalysis : an international journal devoted to fundamental and practical aspects of electroanalysis}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1040-0397}, doi = {10.1002/elan.201600246}, pages = {2303 -- 2310}, year = {2016}, language = {en} } @article{ZehbeZehbe2016, author = {Zehbe, Rolf and Zehbe, Kerstin}, title = {Strontium doped poly-epsilon-caprolactone composite scaffolds made by reactive foaming}, series = {The European journal of the history of economic thought}, volume = {67}, journal = {The European journal of the history of economic thought}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0928-4931}, doi = {10.1016/j.msec.2016.05.045}, pages = {259 -- 266}, year = {2016}, abstract = {In the reconstruction and regeneration of bone tissue, a primary goal is to initiate bone growth and to stabilize the surrounding bone. In this regard, a potentially useful component in biomaterials for bone tissue engineering is strontium, which acts as cationic active agent, triggering certain intracellular pathways and acting as so called dual action bone agent which inhibits bone resorption while stimulating bone regeneration. In this study we established a novel processing for the foaming of a polymer (poly-epsilon-caprolactone) and simultaneous chemical reaction of a mixture of calcium and strontium hydroxides to the respective carbonates using supercritical carbon dioxide. The resultant porous composite scaffold was optimized in composition and strontium content and was characterized via different spectroscopic (infrared and Raman spectroscopy, energy dispersive X-ray spectroscopy), imaging (SEM, mu CT), mechanical testing and in vitro methods (fluorescence vital staining, MTT-assay). As a result, the composite scaffold showed good in vitro biocompatibility with partly open pore structure and the expected chemistry. First mechanical testing results indicate sufficient mechanical stability to support future in vivo applications. (C) 2016 Elsevier B.V. All rights reserved.}, language = {en} } @article{ZabelWinterKellingetal.2016, author = {Zabel, Andr{\´e} and Winter, Alette and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {Tetrabromidocuprates(II)-Synthesis, Structure and EPR}, series = {International journal of molecular sciences}, volume = {17}, journal = {International journal of molecular sciences}, number = {4}, publisher = {MDPI}, address = {Basel}, doi = {10.3390/ijms17040596}, pages = {14}, year = {2016}, abstract = {Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several "onium" cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and gK) of the tensors could be determined and information on the structural changes in the [CuBr4]2- anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.}, language = {en} } @article{ZabelWinterKellingetal.2016, author = {Zabel, Andre and Winter, Alette and Kelling, Alexandra and Schilde, Uwe and Strauch, Peter}, title = {Tetrabromidocuprates(II)-Synthesis, Structure and EPR}, series = {International journal of molecular sciences}, volume = {17}, journal = {International journal of molecular sciences}, publisher = {MDPI}, address = {Basel}, issn = {1422-0067}, doi = {10.3390/ijms17040596}, pages = {14}, year = {2016}, abstract = {Metal-containing ionic liquids (ILs) are of interest for a variety of technical applications, e.g., particle synthesis and materials with magnetic or thermochromic properties. In this paper we report the synthesis of, and two structures for, some new tetrabromidocuprates(II) with several "onium" cations in comparison to the results of electron paramagnetic resonance (EPR) spectroscopic analyses. The sterically demanding cations were used to separate the paramagnetic Cu(II) ions for EPR measurements. The EPR hyperfine structure in the spectra of these new compounds is not resolved, due to the line broadening resulting from magnetic exchange between the still-incomplete separated paramagnetic Cu(II) centres. For the majority of compounds, the principal g values (g|| and g(perpendicular to)) of the tensors could be determined and information on the structural changes in the [CuBr4](2-) anions can be obtained. The complexes have high potential, e.g., as ionic liquids, as precursors for the synthesis of copper bromide particles, as catalytically active or paramagnetic ionic liquids.}, language = {en} } @article{YanFangNoecheletal.2016, author = {Yan, Wan and Fang, Liang and N{\"o}chel, Ulrich and Kratz, Karl and Lendlein, Andreas}, title = {Influence of programming strain rates on the shape-memory performance of semicrystalline multiblock copolymers}, series = {Journal of polymer science : B, Polymer physics}, volume = {54}, journal = {Journal of polymer science : B, Polymer physics}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0887-6266}, doi = {10.1002/polb.24097}, pages = {1935 -- 1943}, year = {2016}, abstract = {Multiblock copolymers named PCL-PIBMD consisting of crystallizable poly(epsilon-caprolactone) segments and crystallizable poly[oligo(3S-iso-butylmorpholine-2,5-dione)] segments coupled by trimethyl hexamethylene diisocyanate provide a versatile molecular architecture for achieving shape-memory effects (SMEs) in polymers. The mechanical properties as well as the SME performance of PCL-PIBMD can be tailored by the variation of physical parameters during programming such as deformation strain or applied temperature protocols. In this study, we explored the influence of applying different strain rates during programming on the resulting nanostructure of PCL-PIBMD. Programming was conducted at 50 degrees C by elongation to epsilon(m)=50\% with strain rates of 1 or 10 or 50 mmmin(-1). The nanostructural changes were visualized by atomic force microscopy (AFM) measurements and investigated by in situ wide and small angle X-ray scattering experiments. With increasing the strain rate, a higher degree of orientation was observed in the amorphous domains. Simultaneously the strain-induced formation of new PIBMD crystals as well as the fragmentation of existing large PIBMD crystals occurred. The observed differences in shape fixity ratio and recovery stress of samples deformed with various strain rates can be attributed to their different nanostructures. The achieved findings can be relevant parameters for programming the shape-memory polymers with designed recovery forces. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 1935-1943}, language = {en} } @article{WuennemannNoyongKreuelsetal.2016, author = {Wuennemann, Patrick and Noyong, Michael and Kreuels, Klaus and Bruex, Roland and Gordiichuk, Pavlo and van Rijn, Patrick and Plamper, Felix A. and Simon, Ulrich and B{\"o}ker, Alexander}, title = {Microstructured Hydrogel Templates for the Formation of Conductive Gold Nanowire Arrays}, series = {Macromolecular rapid communications}, volume = {37}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201600287}, pages = {1446 -- 1452}, year = {2016}, abstract = {Microstructured hydrogel allows for a new template-guided method to obtain conductive nanowire arrays on a large scale. To generate the template, an imprinting process is used in order to synthesize the hydrogel directly into the grooves of wrinkled polydimethylsiloxane (PDMS). The resulting poly(N-vinylimidazole)-based hydrogel is defined by the PDMS stamp in pattern and size. Subsequently, tetrachloroaurate(III) ions from aqueous solution are coordinated within the humps of the N-vinylimidazole-containing polymer template and reduced by air plasma. After reduction and development of the gold, to achieve conductive wires, the extension perpendicular to the long axis (width) of the gold strings is considerably reduced compared to the dimension of the parental hydrogel wrinkles (from approximate to 1 mu m down to 200-300 nm). At the same time, the wire-to-wire distance and the overall length of the wires is preserved. The PDMS templates and hydrogel structures are analyzed with scanning force microscopy (SFM) and the gold structures via scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy. The conductivity measurements of the gold nanowires are performed in situ in the SEM, showing highly conductive gold leads. Hence, this method can be regarded as a facile nonlithographic top-down approach from micrometer-sized structures to nanometer-sized features.}, language = {en} } @article{WuGlebeBoeker2016, author = {Wu, Lei and Glebe, Ulrich and B{\"o}ker, Alexander}, title = {Synthesis of Hybrid Silica Nanoparticles Densely Grafted with Thermo and pH Dual-Responsive Brushes via Surface-Initiated ATRP}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {49}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.6b01792}, pages = {9586 -- 9596}, year = {2016}, language = {en} } @article{WongAstYuetal.2016, author = {Wong, Joseph K. -H. and Ast, Sandra and Yu, Mingfeng and Flehr, Roman and Counsell, Andrew J. and Turner, Peter and Crisologo, Patrick and Todd, Matthew H. and Rutledge, Peter J.}, title = {Synthesis and Evaluation of 1,8-Disubstituted-Cyclam/Naphthalimide Conjugates as Probes for Metal Ions}, series = {ChemistryOpen : including thesis treasury}, volume = {5}, journal = {ChemistryOpen : including thesis treasury}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2191-1363}, doi = {10.1002/open.201600010}, pages = {375 -- 385}, year = {2016}, abstract = {Fluorescent molecular probes for metal ions have a raft of potential applications in chemistry and biomedicine. We report the synthesis and photophysical characterisation of 1,8-disubstituted-cyclam/naphthalimide conjugates and their zinc complexes. An efficient synthesis of 1,8-bis-(2-azidoethyl)cyclam has been developed and used to prepare 1,8-disubstituted triazolyl-cyclam systems, in which the pendant group is connected to triazole C4. UV/Vis and fluorescence emission spectra, zinc binding experiments, fluorescence quantum yield and lifetime measurements and pH titrations of the resultant bis-naphthalimide ligand elucidate a complex pattern of photophysical behaviour. Important differences arise from the inclusion of two fluorophores in the one probe and from the variation of triazole substitution pattern (dye at C4 vs. N1). Introducing a second fluorophore greatly extends fluorescence lifetimes, whereas the altered substitution pattern at the cyclam amines exerts a major influence on fluorescence output and metal binding. Crystal structures of two key zinc complexes evidence variations in triazole coordination that mirror the solution-phase behaviour of these systems.}, language = {en} } @misc{WischkeLendlein2016, author = {Wischke, Christian and Lendlein, Andreas}, title = {Functional nanocarriers by miniaturization of polymeric materials}, series = {Nanomedicine}, volume = {11}, journal = {Nanomedicine}, publisher = {Future Medicine}, address = {London}, issn = {1743-5889}, doi = {10.2217/nnm.16.45}, pages = {1507 -- 1509}, year = {2016}, language = {en} } @article{WirthSchachtSaalfranketal.2016, author = {Wirth, Jonas and Schacht, Julia and Saalfrank, Peter and Paulus, Beate}, title = {Fluorination of the Hydroxylated alpha-Al2O3 (0001) and Its Implications for Water Adsorption: A Theoretical Study}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {120}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b10975}, pages = {9713 -- 9718}, year = {2016}, abstract = {Fluorination of the hydroxylated alpha-Al2O3 (0001) surface is studied using periodic density functional theory calculations. On the basis of a hypothetical reaction substituting surface hydroxyl groups with fluorine atoms, we find surface fluorination to be strongly exergonic but kinetically hindered. Fluorinated surface areas turn out to be rather hydrophobic as compared to hydroxylated areas, suggesting fluorination as a potential route for tuning oxide surface properties such as hydrophilicity.}, language = {en} } @article{WirthKirschWlosczyketal.2016, author = {Wirth, Jonas and Kirsch, Harald and Wlosczyk, Sebastian and Tong, Yujin and Saalfrank, Peter and Campen, Richard Kramer}, title = {Characterization of water dissociation on alpha-Al2O3(1(1)over-bar02): theory and experiment}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {18}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c6cp01397j}, pages = {14822 -- 14832}, year = {2016}, abstract = {The interaction of water with a-alumina (i.e. alpha-Al2O3) surfaces is important in a variety of applications and a useful model for the interaction of water with environmentally abundant aluminosilicate phases. Despite its significance, studies of water interaction with alpha-Al2O3 surfaces other than the (0001) are extremely limited. Here we characterize the interaction of water (D2O) with a well defined alpha-Al2O3(1 (1) over bar 02) surface in UHV both experimentally, using temperature programmed desorption and surface-specific vibrational spectroscopy, and theoretically, using periodic-slab density functional theory calculations. This combined approach makes it possible to demonstrate that water adsorption occurs only at a single well defined surface site (the so-called 1-4 configuration) and that at this site the barrier between the molecularly and dissociatively adsorbed forms is very low: 0.06 eV. A subset of OD stretch vibrations are parallel to this dissociation coordinate, and thus would be expected to be shifted to low frequencies relative to an uncoupled harmonic oscillator. To quantify this effect we solve the vibrational Schrodinger equation along the dissociation coordinate and find fundamental frequencies red-shifted by more than 1500 cm(-1). Within the context of this model, at moderate temperatures, we further find that some fraction of surface deuterons are likely delocalized: dissociatively and molecularly absorbed states are no longer distinguishable.}, language = {en} } @article{WhiteHeideSaalfranketal.2016, author = {White, Alec F. and Heide, Chiara Josephine and Saalfrank, Peter and Head-Gordon, Martin and Luppi, Eleonora}, title = {Computation of high-harmonic generation spectra of the hydrogen molecule using time-dependent configuration-interaction}, series = {Molecular physics}, volume = {114}, journal = {Molecular physics}, publisher = {Springer}, address = {Abingdon}, issn = {0026-8976}, doi = {10.1080/00268976.2015.1119900}, pages = {947 -- 956}, year = {2016}, abstract = {Here we apply and expand the knowledge developed in the case of the H atom to describe high-harmonic generation (HHG) for the H-2 molecule by using time-dependent configuration interaction with single excitations. The implications of using a finite atomic orbital basis set and the impact of a heuristic lifetime model which addresses ionisation losses are discussed. We also examine the influence of the angular momentum of the basis on the computed HHG spectra. Moreover, we discuss the impact of adding diffuse functions and ghost atoms in different geometrical configurations around the molecule. The effects of these additional centres on the HHG spectra are correlated with the physical interpretation of this nonlinear optical phenomenon as given by the three-step model, relating the maximal radial extent of the electron as predicted by the model to the radial extent of the Gaussian basis sets. [GRAPHICS] .}, language = {en} } @article{WessigGerngrossFreyseetal.2016, author = {Wessig, Pablo and Gerngross, Maik and Freyse, Daniel and Bruhn, P. and Przezdziak, Marc and Schilde, Uwe and Kelling, Alexandra}, title = {Molecular Rods Based on Oligo-spiro-thioketals}, series = {The journal of organic chemistry}, volume = {81}, journal = {The journal of organic chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {0022-3263}, doi = {10.1021/acs.joc.5b02670}, pages = {1125 -- 1136}, year = {2016}, abstract = {We report on an extension of the previously established concept of oligospiroketal (OSK) rods by replacing a part or all ketal moieties by thioketals leading to oligospirothioketal (OSTK) rods. In this way, some crucial problems arising from the reversible formation of ketals are circumvented. Furthermore, the stability of the rods toward hydrolysis is considerably improved. To successfully implement this concept, we first developed a number of new oligothiol building blocks and improved the synthetic accessibility of known oligothiols, respectively. Another advantage of thioacetals is that terephthalaldehyde (TAA) sleeves, which are too flexible in the case of acetals can be used in OSTK rods. The viability of the OSTK approach was demonstrated by the successful preparation of some OSTK rods with a length of some nanometers.}, language = {en} } @article{WessigBehrendsKumkeetal.2016, author = {Wessig, Pablo and Behrends, Nicole and Kumke, Michael Uwe and Eisold, Ursula and Meiling, Til and Hille, Carsten}, title = {Two-photon FRET pairs based on coumarin and DBD dyes}, series = {RSC Advances}, volume = {6}, journal = {RSC Advances}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2046-2069}, doi = {10.1039/c6ra03983a}, pages = {33510 -- 33513}, year = {2016}, abstract = {The synthesis and photophysical properties of two new FRET pairs based on coumarin as a donor and DBD dye as an acceptor are described. The introduction of a bromo atom dramatically increases the two-photon excitation (2PE) cross section providing a 2PE-FRET system, which is also suitable for 2PE-FLIM.}, language = {en} } @article{WessigBehrendsKumkeetal.2016, author = {Wessig, Pablo and Behrends, Nicole and Kumke, Michael Uwe and Eisold, Ursula}, title = {FRET Pairs with Fixed Relative Orientation of Chromophores}, series = {European journal of organic chemistry}, volume = {145}, journal = {European journal of organic chemistry}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.201600489}, pages = {4476 -- 4486}, year = {2016}, abstract = {Synthetic routes to different oligospirothioketal (OSTK) Forster resonance energy transfer (FRET) constructs are described and the photophysics of these constructs were explored in different solvents. The FRET efficiencies were determined from the experimental data and compared with theoretical values. The influence of the outstanding rigidity of the novel OSTK compounds on the FRET is discussed.}, language = {en} } @article{WentrupKochKleinpeter2016, author = {Wentrup, Curt and Koch, Rainer and Kleinpeter, Erich}, title = {Twisted C=C Double Bonds with Very Low Rotational Barriers in Dioxanediones and Isoxazolones Determined by Low-Temperature Dynamic NMR Spectroscopy and Computational Chemistry}, series = {European journal of organic chemistry}, journal = {European journal of organic chemistry}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.201600931}, pages = {4985 -- 4990}, year = {2016}, language = {en} } @article{WeilerMenzelPertschetal.2016, author = {Weiler, Markus and Menzel, Christoph and Pertsch, Thomas and Alaee, Rasoul and Rockstuhl, Carsten and Pacholski, Claudia}, title = {Bottom-Up Fabrication of Hybrid Plasmonic Sensors: Gold-Capped Hydrogel Microspheres Embedded in Periodic Metal Hole Arrays}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {8}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.6b08636}, pages = {26392 -- 26399}, year = {2016}, abstract = {The high potential of bottom-up fabrication strategies for realizing sophisticated optical sensors combining the high sensitivity of a surface plasmon resonance with the exceptional properties of stimuli-responsive hydrogel is demonstrated. The sensor is composed of a periodic hole array in a gold film whose holes are filled with gold-capped poly(N-isoproyl-acrylamide) (polyNIPAM) microspheres. The production of this sensor relies on a pure chemical approach enabling simple, time-efficient, and cost-efficient preparation of sensor platforms covering areas of cm(2). The transmission spectrum of this plasmonic sensor shows a strong interaction between propagating surface plasmon polaritons at the metal film surface and localized surface plasmon resonance of the gold cap on top of the polyNIPAM microspheres. Computer simulations support this experimental observation. These interactions lead to distinct changes in the transmission spectrum, which allow for the simultaneous, sensitive optical detection of refractive index changes in the surrounding medium and the swelling state of the embedded polyNIPAM microsphere under the gold cap. The volume of the polyNIPAM microsphere located underneath the gold cap can be changed by certain stimuli such as temperature, pH, ionic strength, and distinct molecules bound to the hydrogel matrix facilitating the detection of analytes which do not change the refractive index of the surrounding medium significantly.}, language = {en} } @phdthesis{Wei2016, author = {Wei, Chunxiang}, title = {On the role of monomer drops and swelling in aqueous heterophase polymerization}, school = {Universit{\"a}t Potsdam}, pages = {122}, year = {2016}, language = {en} } @article{WagnerLazarSchnakenbergetal.2016, author = {Wagner, Tom and Lazar, Jaroslav and Schnakenberg, Uwe and B{\"o}ker, Alexander}, title = {In situ Electrothemical Impedance Spectroscopy of Electrostatically Driven Selective Gold Nanoparticle Adsorption on Block Copolymer Lamellae}, series = {Trials}, volume = {8}, journal = {Trials}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.6b07708}, pages = {27282 -- 27290}, year = {2016}, abstract = {Electrostatic attraction between charged nano particles and oppositely charged nanopatterned polymeric films enables tailored structuring of functional nanoscopic surfaces. The bottom-up fabrication of organic/inorganic composites for example bears promising potential toward cheap fabrication of catalysts, optical sensors, and the manufacture of miniaturized electric circuitry. However, only little is known about the time-dependent adsorption behavior and the electronic or ionic charge transfer in the film bulk and at interfaces during nanoparticle assembly via electrostatic interactions. In situ electrochemical impedance spectroscopy (EIS) in combination with a microfluidic system for fast and reproducible liquid delivery was thus applied to monitor the selective deposition of negatively charged gold nanoparticles on top of positively charged poly(2-vinylpyridinium) (qP2VP) domains of phase separated lamellar poly(styrene)-block-poly(2-vinylpyridinium) (PS-b-qP2VP) diblock copolymer thin films. The acquired impedance data delivered information with respect to interfacial charge alteration, ionic diffusion, and the charge dependent nanoparticle adsorption kinetics, considering this yet unexplored system. We demonstrate that the selective adsorption of negatively charged gold nanoparticles (AuNPs) on positively charged qP2VP domains of lamellar PS-b-qP2VP thin films can indeed be tracked by EIS. Moreover, we show that the nanoparticle adsorption kinetics and the nanoparticle packing density are functions of the charge density in the qP2VP domains.}, language = {en} } @article{VorburgerNedielkovBrosigetal.2016, author = {Vorburger, Thomas and Nedielkov, Ruslan and Brosig, Alexander and Bok, Eva and Schunke, Emina and Steffen, Wojtek and Mayer, Sonja and Goetz, Friedrich and M{\"o}ller, Heiko Michael and Steuber, Julia}, title = {Role of the Na+-translocating NADH:quinone oxidoreductase in voltage generation and Na+ extrusion in Vibrio cholerae}, series = {Biochimica et biophysica acta : Bioenergetics}, volume = {1857}, journal = {Biochimica et biophysica acta : Bioenergetics}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0005-2728}, doi = {10.1016/j.bbabio.2015.12.010}, pages = {473 -- 482}, year = {2016}, abstract = {For Vibrio cholerae, the coordinated import and export of Na+ is crucial for adaptation to habitats with different osmolarities. We investigated the Na+-extruding branch of the sodium cycle in this human pathogen by in vivo Na-23-NMR spectroscopy. The Na+ extrusion activity of cells was monitored after adding glucose which stimulated respiration via the Na+-translocating NADH:quinone oxidoreductase (Na+-NQR). In a V. cholerae deletion mutant devoid of the Na+-NQR encoding genes (nqrA-F), rates of respiratory Na+ extrusion were decreased by a factor of four, but the cytoplasmic Na+ concentration was essentially unchanged. Furthermore, the mutant was impaired in formation of transmembrane voltage (Delta psi, inside negative) and did not grow under hypoosmotic conditions at pH 8.2 or above. This growth defect could be complemented by transformation with the plasmid encoded nqr operon. In an alkaline environment, Na+/H+ antiporters acidify the cytoplasm at the expense of the transmembrane voltage. It is proposed that, at alkaline pH and limiting Na+ concentrations, the Na+-NQR is crucial for generation of a transmembrane voltage to drive the import of H+ by electrogenic Na+/H+ antiporters. Our study provides the basis to understand the role of the Na+-NQR in pathogenicity of V. cholerae and other pathogens relying on this primary Na+ pump for respiration. (C) 2015 Elsevier B.V. All rights reserved.}, language = {en} } @article{VishnevetskayaHildebrandNiebuuretal.2016, 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 = {Aggregation Behavior of Doubly Thermoresponsive Polysulfobetaine-b-poly(N-isopropylacrylamide) Diblock Copolymers}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {49}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.6b01186}, pages = {6655 -- 6668}, year = {2016}, abstract = {A 2-fold thermoresponsive diblock copolymer PSPP430-b-PNIPAM(200) consisting of a zwitterionic polysulfobetaine (PSPP) block and a nonionic poly(N-isopropylacrylamide) (PNIPAM) block is prepared by successive RAFT polymerizations. In aqueous solution, the corresponding homopolymers PSPP and PNIPAM feature both upper and lower critical solution temperature (UCST and LCST) behavior, respectively. The diblock copolymer exhibits thermally induced "schizophrenic" aggregation behavior in aqueous solutions. Moreover, the ion sensitivity of the, cloud point of the zwitterionic PSPP block to both the ionic strength and the nature of the salt offers the possibility to create switchable systems which respond sensitively to changes of the temperature and of the electrolyte type and concentration. The diblock copolymer solutions in D2O are investigated by means of turbidimetry and small-angle neutron scattering (SANS) with respect to the phase behavior and the self-assembled structures in dependence on temperature and electrolyte content. Marked, differences of the aggregation below the UCST-type and above the LCST-type transition are observed. The addition of a small amount of NaBr (0.004 M) does not affect the overall behavior, and only the UCST-type transition and aggregate structures are slightly altered, reflecting the well-known ion sensitivity of the zwitterionic PSPP block.}, language = {en} } @article{VillatoroZuehlkeRiebeetal.2016, author = {Villatoro, Jos{\´e} Andr{\´e}s and Z{\"u}hlke, Martin and Riebe, Daniel and Riedel, Jens and Beitz, Toralf and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {IR-MALDI ion mobility spectrometry}, series = {Analytical and bioanalytical chemistry : a merger of Fresenius' journal of analytical chemistry and Analusis}, volume = {408}, journal = {Analytical and bioanalytical chemistry : a merger of Fresenius' journal of analytical chemistry and Analusis}, publisher = {Springer}, address = {Heidelberg}, issn = {1618-2642}, doi = {10.1007/s00216-016-9739-x}, pages = {6259 -- 6268}, year = {2016}, abstract = {The novel combination of infrared matrix-assisted laser dispersion and ionization (IR-MALDI) with ion mobility (IM) spectrometry makes it possible to investigate biomolecules in their natural environment, liquid water. As an alternative to an ESI source, the IR-MALDI source was implemented in an in-house-developed ion mobility (IM) spectrometer. The release of ions directly from an aqueous solution is based on a phase explosion, induced by the absorption of an IR laser pulse (lambda = 2.94 mu m, 6 ns pulse width), which disperses the liquid as nano- and micro-droplets. The prerequisites for the application of IR-MALDI-IM spectrometry as an analytical method are narrow analyte ion signal peaks for a high spectrometer resolution. This can only be achieved by improving the desolvation of ions. One way to full desolvation is to give the cluster ions sufficient time to desolvate. Two methods for achieving this are studied: the implementation of an additional drift tube, as in ESI-IM-spectrometry, and the delayed extraction of the ions. As a result of this optimization procedure, limits of detection between 5 nM and 2.5 mu M as well as linear dynamic ranges of 2-3 orders of magnitude were obtained for a number of substances. The ability of this method to analyze simple mixtures is illustrated by the separation of two different surfactant mixtures.}, language = {en} } @article{VillatoroZuehlkeRiebeetal.2016, author = {Villatoro, Jos{\´e} Andr{\´e}s and Z{\"u}hlke, Martin and Riebe, Daniel and Beitz, Toralf and Weber, Marcus and Riedel, Jens and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {IR-MALDI ion mobility spectrometry: physical source characterization and application as HPLC detector}, series = {International journal for ion mobility spectrometry : official publication of the International Society for Ion Mobility Spectrometry}, volume = {19}, 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/s12127-016-0208-1}, pages = {197 -- 207}, year = {2016}, abstract = {Infrared matrix-assisted laser dispersion and ionization (IR-MALDI) in combination with ion mobility (IM) spectrometry enables the direct analysis of biomolecules in aqueous solution. The release of ions directly from an aqueous solution is based on a phase explosion, induced by the absorption of an IR laser pulse, which disperses the liquid as vapor, nano-and micro-droplets. The ionization process is characterized initially by a broad spatial distribution of the ions, which is a result of complex fluid dynamics and desolvation kinetics. These processes have a profound effect on the shape and width of the peaks in the IM spectra. In this work, the transport of ions by the phase explosion-induced shockwave could be studied independently from the transport by the electric field. The shockwave-induced mean velocities of the ions at different time scales were determined through IM spectrometry and shadowgraphy. The results show a deceleration of the ions from 118 m.s(-1) at a distance of 400 mu m from the liquid surface to 7.1 m.s(-1) at a distance of 10 mm, which is caused by a pile-up effect. Furthermore, the desolvation kinetics were investigated and a first-order desolvation constant of 325 +/- 50 s(-1) was obtained. In the second part, the IR-MALDI-IM spectrometer is used as an HPLC detector for the two-dimensional separation of a pesticide mixture.}, language = {en} } @article{VargasRuizSchulreichKostevicetal.2016, author = {Vargas-Ruiz, Salome and Schulreich, Christoph and Kostevic, Angelika and Tiersch, Brigitte and Koetz, Joachim and Kakorin, Sergej and von Klitzing, Regine and Jung, Martin and Hellweg, Thomas and Wellert, Stefan}, title = {Extraction of model contaminants from solid surfaces by environmentally compatible microemulsions}, series = {Journal of colloid and interface science}, volume = {471}, journal = {Journal of colloid and interface science}, publisher = {Elsevier}, address = {San Diego}, issn = {0021-9797}, doi = {10.1016/j.jcis.2016.03.006}, pages = {118 -- 126}, year = {2016}, abstract = {In the present contribution, we evaluate the efficiency of eco-friendly microemulsions to decontaminate solid surfaces by monitoring the extraction of non-toxic simulants of sulfur mustard out of model surfaces. The extraction process of the non-toxic simulants has been monitored by means of spectroscopic and chromatographic techniques. The kinetics of the removal process was analyzed by different empirical models. Based on the analysis of the kinetics, we can assess the influence of the amounts of oil and water and the microemulsion structure on the extraction process. (C) 2016 Elsevier Inc. All rights reserved.}, language = {en} } @article{VacogneSchopfererSchlaad2016, author = {Vacogne, Charlotte D. and Schopferer, Michael and Schlaad, Helmut}, title = {Physical Gelation of alpha-Helical Copolypeptides}, series = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, volume = {17}, journal = {Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences}, publisher = {American Chemical Society}, address = {Washington}, issn = {1525-7797}, doi = {10.1021/acs.biomac.6b00427}, pages = {2384 -- 2391}, year = {2016}, abstract = {Owing to its rod-like alpha-helical secondary structure, the synthetic polypeptide poly(gamma-benzyl-L-glutamate) (PBLG) can form physical and thermoreversible gels in helicogenic solvents such as toluene. The versatility of PBLG can be increased by introducing functionalizable comonomers, such as allylglycine (AG). In this work we examined the secondary structure of PBLG and a series of statistical poly(gamma-benzyl-L-glutamate-co-allylglycine) copolypeptides, varying in composition and chain length, by circular dichroism (CD), Fourier-transform infrared (FTIR) and Raman spectroscopy, and wide-angle X-ray scattering (WAXS). The secondary structure of PBLG and the copolypeptides presented dissimilarities that increased with increasing AG molar fraction, especially when racemic AG units were incorporated. The physical gelation behavior of these copolypeptides was analyzed by temperature-sweep H-1 NMR and rheological measurements. The study revealed that both copolypeptide composition and chain length affected secondary structure, gelation temperature, and gel stiffness.}, language = {en} } @phdthesis{Taeuber2016, author = {T{\"a}uber, Karoline}, title = {Porous Membranes from Imidazolium- and Pyridinium-based Poly(ionic liquid)s with Targeted Properties}, school = {Universit{\"a}t Potsdam}, pages = {115}, year = {2016}, language = {en} } @article{TritschlerZlotnikovFratzletal.2016, author = {Tritschler, Ulrich and Zlotnikov, Igor and Fratzl, Peter and Schlaad, Helmut and Gruener, Simon and Coelfen, Helmut}, title = {Gas barrier properties of bio-inspired Laponite-LC polymer hybrid films}, series = {PLoS one}, volume = {11}, journal = {PLoS one}, publisher = {IOP Publ. Ltd.}, address = {Bristol}, issn = {1748-3182}, doi = {10.1088/1748-3190/11/3/035005}, pages = {12}, year = {2016}, abstract = {Bio-inspired Laponite (clay)-liquid crystal (LC) polymer composite materials with high clay fractions (>80\%) and a high level of orientation of the clay platelets, i.e. with structural features similar to the ones found in natural nacre, have been shown to exhibit a promising behavior in the context of reduced oxygen transmission. Key characteristics of these bio-inspired composite materials are their high inorganic content, high level of exfoliation and orientation of the clay platelets, and the use of a LC polymer forming the organic matrix in between the Laponite particles. Each single feature may be beneficial to increase the materials gas barrier property rendering this composite a promising system with advantageous barrier capacities. In this detailed study, Laponite/LC polymer composite coatings with different clay loadings were investigated regarding their oxygen transmission rate. The obtained gas barrier performance was linked to the quality, respective Laponite content and the underlying composite micro-and nanostructure of the coatings. Most efficient oxygen barrier properties were observed for composite coatings with 83\% Laponite loading that exhibit a structure similar to sheet-like nacre. Further on, advantageous mechanical properties of these Laponite/LC polymer composites reported previously give rise to a multifunctional composite system.}, language = {en} } @article{TrautweinFredrikssonMoelleretal.2016, author = {Trautwein, Matthias and Fredriksson, Kai and M{\"o}ller, Heiko Michael and Exner, Thomas E.}, title = {Automated assignment of NMR chemical shifts based on a known structure and 4D spectra}, series = {Journal of biomolecular NMR}, volume = {65}, journal = {Journal of biomolecular NMR}, publisher = {Springer}, address = {Dordrecht}, issn = {0925-2738}, doi = {10.1007/s10858-016-0050-0}, pages = {217 -- 236}, year = {2016}, abstract = {Apart from their central role during 3D structure determination of proteins the backbone chemical shift assignment is the basis for a number of applications, like chemical shift perturbation mapping and studies on the dynamics of proteins. This assignment is not a trivial task even if a 3D protein structure is known and needs almost as much effort as the assignment for structure prediction if performed manually. We present here a new algorithm based solely on 4D [H-1, N-15]-HSQC-NOESY-[H-1, N-15]-HSQC spectra which is able to assign a large percentage of chemical shifts (73-82 \%) unambiguously, demonstrated with proteins up to a size of 250 residues. For the remaining residues, a small number of possible assignments is filtered out. This is done by comparing distances in the 3D structure to restraints obtained from the peak volumes in the 4D spectrum. Using dead-end elimination, assignments are removed in which at least one of the restraints is violated. Including additional information from chemical shift predictions, a complete unambiguous assignment was obtained for Ubiquitin and 95 \% of the residues were correctly assigned in the 251 residue-long N-terminal domain of enzyme I. The program including source code is available at https://github.com/thomasexner/4Dassign.}, language = {en} } @article{TitovSaalfrank2016, author = {Titov, Evgenii and Saalfrank, Peter}, title = {Exciton Splitting of Adsorbed and Free 4-Nitroazobenzene Dimers: A Quantum Chemical Study}, series = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, volume = {120}, journal = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, publisher = {American Chemical Society}, address = {Washington}, issn = {1089-5639}, doi = {10.1021/acs.jpca.5b10376}, pages = {3055 -- 3070}, year = {2016}, abstract = {Molecular photoswitches such as azobenzenes, which undergo photochemical trans <-> cis isomerizations, are often mounted for possible applications on a surface and/or surrounded by other switches, for example, in self-assembled monolayers. This may suppress the isomerization cross section due to possible steric reasons, or, as recently speculated, by exciton coupling to. neighboring switches, leading to ultrafast electronic quenching (Gahl et al., J. Am. Chem. Soc. 2010, 132, 1831). The presence of exciton coupling has been anticipated from a blue shift of the optical absorption band, compared to molecules in solution. From the theory side the need arises to properly analyze and quantify the change of absorption spectra of interacting and adsorbed switches. In particular, suitable methods should be identified, and effects of intermolecule and molecule surface interactions on spectra should be disentangled. In this paper by means of time-dependent Hartree-Fock. (TD-HF), various flavors of time-dependent density functional theory (TD-DFT), and the correlated wave function based, coupled cluster (CC2) method we investigated the 4-nitroazobenzene molecule as an:example: The low-lying singlet excited states in the isolated trans monomer and dieter as well as their composites with a silicon pentamantane nanocluster, which serves also as a crude model for a silicon surface, were determined. As most important results we found that (i) HF, CC2, range-separated density functionals, or global hybrids with large amount of exact exchange are able to describe exciton (Davydov) splitting properly, while hybrids with small amount of exact exchange fail producing spurious charge transfer. (ii) The exciton splitting in a free dimer would lead to a blue shift of the absorption signal; however, this effect is almost nullified or even overcompensated by the shift arising from van der Waals interactions between the two molecules. (iii) Adsorption on the Si "surface" leads to a further, strong red shift for the present system. (iv) At a next-nearest neighbor distance (of similar to 3.6 angstrom), the exciton splitting is similar to 0.3 eV, with or without "surface", suggesting a rapid quenching of the molecular pi ->pi* excitation. At larger distances, exciton splitting decreases rapidly.}, language = {en} } @article{TitovGranucciGoetzeetal.2016, author = {Titov, Evgenii and Granucci, Giovanni and Goetze, Jan Philipp and Persico, Maurizio and Saalfrank, Peter}, title = {Dynamics of Azobenzene Dimer Photoisomerization: Electronic and Steric Effects}, series = {The journal of physical chemistry letters}, volume = {7}, journal = {The journal of physical chemistry letters}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpciett.6b01401}, pages = {3591 -- 3596}, year = {2016}, abstract = {While azobenzenes readily photoswitch in solution, their photoisomerization in densely packed self-assembled monolayers (SAMs) can be suppressed. Reasons for this can be steric hindrance and/or electronic quenching, e.g., by exciton coupling. We address these possibilities by means of nonadiabatic molecular dynamics with trajectory surface hopping calculations, investigating the trans -> cis isomerization of azobenzene after excitation into the pi pi* absorption band. We consider a free monomer, an isolated dimer and a dimer embedded in a SAM-like environment of additional azobenzene molecules, imitating in this way the gradual transition from an unconstrained over an electronically coupled to an electronically coupled and sterically hindered, molecular switch. Our simulations reveal that in comparison to the single molecule the quantum yield of the trans -> cis photoisomerization is similar for the isolated dimer, but greatly reduced in the sterically constrained situation. Other implications of dimerization and steric constraints are also discussed.}, language = {en} } @article{ThielkeSeckerSchlaadetal.2016, author = {Thielke, Michael W. and Secker, Christian and Schlaad, Helmut and Theato, Patrick}, title = {Electrospinning of Crystallizable Polypeptoid Fibers}, series = {Macromolecular rapid communications}, volume = {37}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201500502}, pages = {100 -- 104}, year = {2016}, abstract = {A unique fabrication process of low molar mass, crystalline polypeptoid fibers is described. Thermoresponsive fiber mats are prepared by electrospinning a homogeneous blend of semicrystalline poly(N-(n-propyl) glycine) (PPGly; 4.1 kDa) with high molar mass poly(ethylene oxide) (PEO). Annealing of these fibers at approximate to 100 degrees C selectively removes the PEO and produces stable crystalline fiber mats of pure PPGly, which are insoluble in aqueous solution but can be redissolved in methanol or ethanol. The formation of water-stable polypeptoid fiber mats is an important step toward their utilization in biomedical applications such as tissue engineering or wound dressing.}, language = {en} } @article{TetaliJankowskiLuetzowetal.2016, author = {Tetali, Sarada D. and Jankowski, Vera and Luetzow, Karola and Kratz, Karl and Lendlein, Andreas and Jankowski, Joachim}, title = {Adsorption capacity of poly(ether imide) microparticles to uremic toxins}, series = {Clinical hemorheology and microcirculation : blood flow and vessels}, volume = {61}, journal = {Clinical hemorheology and microcirculation : blood flow and vessels}, publisher = {IOS Press}, address = {Amsterdam}, issn = {1386-0291}, doi = {10.3233/CH-152026}, pages = {657 -- 665}, year = {2016}, abstract = {Uremia is a phenomenon caused by retention of uremic toxins in the plasma due to functional impairment of kidneys in the elimination of urinary waste products. Uremia is presently treated by dialysis techniques like hemofiltration, dialysis or hemodiafiltration. However, these techniques in use are more favorable towards removing hydrophilic than hydrophobic uremic toxins. Hydrophobic uremic toxins, such as hydroxy hipuric acid (OH-HPA), phenylacetic acid (PAA), indoxyl sulfate (IDS) and p-cresylsulfate (pCRS), contribute substantially to the progression of chronic kidney disease (CKD) and cardiovascular disease. Therefore, objective of the present study is to test adsorption capacity of highly porous microparticles prepared from poly(ether imide) (PEI) as an alternative technique for the removal of uremic toxins. Two types of nanoporous, spherically shaped microparticles were prepared from PEI by a spraying/coagulation process. PEI particles were packed into a preparative HPLC column to which a mixture of the four types of uremic toxins was injected and eluted with ethanol. Eluted toxins were quantified by analytical HPLC. PEI particles were able to adsorb all four toxins, with the highest affinity for PAA and pCR. IDS and OH-HPA showed a partially non-reversible binding. In summary, PEI particles are interesting candidates to be explored for future application in CKD.}, language = {en} } @article{SunCernochVoelkeletal.2016, author = {Sun, Jing and Cernoch, Peter and V{\"o}lkel, Antje and Wei, Yuhan and Ruokolainen, Janne and Schlaad, Helmut}, title = {Aqueous Self-Assembly of a Protein-Mimetic Ampholytic Block Copolypeptide}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {49}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.6b00817}, pages = {5494 -- 5501}, year = {2016}, abstract = {This report describes the aggregation behavior of an ABC-type ampholytic block copolypeptide, poly(ethylene oxide)-block-poly(L-lysine)-block-poly(L-glutamate), in aqueous media in dependence of pH. Polypeptide secondary structures and self-assemblies are investigated by circular dichroism (CD), Fourier transform infrared (FT-IR) and NMR spectroscopy, zeta potential measurements, analytical ultracentrifugation (AUC), dynamic/static light scattering (DLS/SLS), and cryogenic transmission electron microscopy (cryoTEM). The polymer chains tend to form vesicles when the hydrophobic polypeptide helix is located at the chain end (acidic pH) and are existing as single chains when it is located in the center and flanked by the two hydrophilic segments (basic pH). Precipitation occurs in the intermediate pH range due to polyion complexation of the charged polypeptide segments.}, language = {en} } @article{SunRynoZhongetal.2016, author = {Sun, Haitao and Ryno, Sean and Zhong, Cheng and Ravva, Mahesh Kumar and Sun, Zhenrong and K{\"o}rzd{\"o}rfer, Thomas and Bredas, Jean-Luc}, title = {Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)-Tuned Range-Separated Density Functional Approach}, series = {Journal of chemical theory and computation}, volume = {12}, journal = {Journal of chemical theory and computation}, publisher = {American Chemical Society}, address = {Washington}, issn = {1549-9618}, doi = {10.1021/acs.jctc.6b00225}, pages = {2906 -- 2916}, year = {2016}, abstract = {We propose a new methodology for the first principles description of the electronic properties relevant for charge transport in organic molecular crystals. This methodology, which is based on the combination of a nonempirical, optimally tuned range separated hybrid functional with the polarizable continuum model, is applied to a series of eight representative molecular semiconductor crystals. We show that it provides ionization energies, electron affinities, and transport gaps in very good agreement with experimental values, as well as with the results of many-body perturbation theory-within the GW approximation at a fraction of the computational cost. Hence, this approach represents an easily applicable and computationally efficient tool to estimate the gas-to crystal phase shifts of the frontier-orbital quasiparticle energies in organic electronic materials.}, language = {en} } @article{StrauchKossmannKellingetal.2016, author = {Strauch, Peter and Kossmann, Alexander and Kelling, Alexandra and Schilde, Uwe}, title = {EPR on bis(1,2-dithiosquarato)cuprate(II) in the bis(1,2-dithiosquarato)nickelate(II) host lattice - structure and spectroscopy}, series = {Chemical papers}, volume = {70}, journal = {Chemical papers}, publisher = {De Gruyter}, address = {Berlin}, issn = {0366-6352}, doi = {10.1515/chempap-2015-0154}, pages = {61 -- 68}, year = {2016}, abstract = {EPR spectroscopy is a well suited analytical tool to monitor the electronic situation around paramagnetic metal centres as copper(II) and therefore the structural influences on the paramagnetic ion. 1,2-Dithiosquaratometalates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. Synthesis and characterisation of bis(benzyltributylammonium)1,2-dithiosquaratonickelate(II), (BzlBu(3)N)(2)[Ni(dtsq)(2)], and bis(benzyltributylammonium)1,2-dithiosquaratocuprate(II), (BzlBu(3)N)(2)[Cu(dtsq)(2)], with benzyltributylammonium as the counter ion is reported and the X-ray structures of two complexes, (BzlBu(3)N)(2)[Ni(dtsq)(2)] and (BzlBu(3)N)(2)[Cu(dtsq)(2)], are presented. Both complexes, crystallising in the monoclinic space group P2(1)/c, are isostructural with only small differences in the coordination sphere due to the different metal ions. The diamagnetic nickel complex is therefore well suited as a host lattice for the paramagnetic Cu(II) complex to measure EPR for additional structural information. (c) 2015 Institute of Chemistry, Slovak Academy of Sciences}, language = {en} } @article{StorchMaierWessigetal.2016, author = {Storch, Golo and Maier, Frank and Wessig, Pablo and Trapp, Oliver}, title = {Rotational Barriers of Substituted BIPHEP Ligands: A Comparative Experimental and Theoretical Study}, series = {European journal of organic chemistry}, volume = {22}, journal = {European journal of organic chemistry}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.201600836}, pages = {5123 -- 5126}, year = {2016}, abstract = {The interconversion barriers of 14 different 3,3- and 5,5-disubstituted tropos BIPHEP [2,2-bis(diphenylphosphino)-1,1-biphenyl] and BIPHEP(O) [2,2-bis(diphenylphosphoryl)-1,1-biphenyl] ligands were investigated by enantioselective dynamic high performance liquid chromatography (DHPLC) and DFT calculations using the B3LYP/6-31G* and M06-2X/6-31G* levels of theory. The experimentally determined enantiomerization barriers varied from 86.8 to 101.4 kJmol(-1) and were found to be in excellent agreement with the calculated data. The root-mean-square deviations are 7.3 kJmol(-1) for the B3LYP functional and 11.3 kJmol(-1) for the M06-2X method.}, language = {en} } @article{SteeplesKellingSchildeetal.2016, author = {Steeples, Elliot and Kelling, Alexandra and Schilde, Uwe and Esposito, Davide}, title = {Amino acid-derived N-heterocyclic carbene palladium complexes for aqueous phase Suzuki-Miyaura couplings}, series = {New journal of chemistry}, volume = {40}, journal = {New journal of chemistry}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1144-0546}, doi = {10.1039/c5nj03337c}, pages = {4922 -- 4930}, year = {2016}, abstract = {In this work, three ligands produced from amino acids were synthesized and used to produce five bis- and PEPPSI-type palladium-NHC complexes using a novel synthesis route from sustainable starting materials. Three of these complexes were used as precatalysts in the aqueous-phase Suzuki-Miyaura coupling of various substrates displaying high activity. TEM and mercury poisoning experiments provide evidence for Pd-nanoparticle formation stabilized in water.}, language = {en} } @article{SoliveresManningPratietal.2016, author = {Soliveres, Santiago and Manning, Peter and Prati, Daniel and Gossner, Martin M. and Alt, Fabian and Arndt, Hartmut and Baumgartner, Vanessa and Binkenstein, Julia and Birkhofer, Klaus and Blaser, Stefan and Bluethgen, Nico and Boch, Steffen and Boehm, Stefan and Boerschig, Carmen and Buscot, Francois and Diekoetter, Tim and Heinze, Johannes and Hoelzel, Norbert and Jung, Kirsten and Klaus, Valentin H. and Klein, Alexandra-Maria and Kleinebecker, Till and Klemmer, Sandra and Krauss, Jochen and Lange, Markus and Morris, E. Kathryn and Mueller, Joerg and Oelmann, Yvonne and Overmann, J{\"o}rg and Pasalic, Esther and Renner, Swen C. and Rillig, Matthias C. and Schaefer, H. Martin and Schloter, Michael and Schmitt, Barbara and Schoening, Ingo and Schrumpf, Marion and Sikorski, Johannes and Socher, Stephanie A. and Solly, Emily F. and Sonnemann, Ilja and Sorkau, Elisabeth and Steckel, Juliane and Steffan-Dewenter, Ingolf and Stempfhuber, Barbara and Tschapka, Marco and Tuerke, Manfred and Venter, Paul and Weiner, Christiane N. and Weisser, Wolfgang W. and Werner, Michael and Westphal, Catrin and Wilcke, Wolfgang and Wolters, Volkmar and Wubet, Tesfaye and Wurst, Susanne and Fischer, Markus and Allan, Eric}, title = {Locally rare species influence grassland ecosystem multifunctionality}, series = {Philosophical transactions of the Royal Society of London : B, Biological sciences}, volume = {371}, journal = {Philosophical transactions of the Royal Society of London : B, Biological sciences}, publisher = {Royal Society}, address = {London}, issn = {0962-8436}, doi = {10.1098/rstb.2015.0269}, pages = {3175 -- 3185}, year = {2016}, abstract = {Species diversity promotes the delivery of multiple ecosystem functions (multifunctionality). However, the relative functional importance of rare and common species in driving the biodiversity multifunctionality relationship remains unknown. We studied the relationship between the diversity of rare and common species (according to their local abundances and across nine different trophic groups), and multifunctionality indices derived from 14 ecosystem functions on 150 grasslands across a land use intensity (LUI) gradient. The diversity of above- and below-ground rare species had opposite effects, with rare above-ground species being associated with high levels of multifunctionality, probably because their effects on different functions did not trade off against each other. Conversely, common species were only related to average, not high, levels of multifunctionality, and their functional effects declined with LUI. Apart from the community level effects of diversity, we found significant positive associations between the abundance of individual species and multifunctionality in 6\% of the species tested. Species specific functional effects were best predicted by their response to LUI: species that declined in abundance with land use intensification were those associated with higher levels of multifunctionality. Our results highlight the importance of rare species for ecosystem multifunctionality and help guiding future conservation priorities.}, language = {en} } @article{SengeFlanaganRyanetal.2016, author = {Senge, Mathias O. and Flanagan, Keith J. and Ryan, Aoife A. and Ryppa, Claudia and Donath, Mandy and Twamley, Brendan}, title = {Conformational and structural studies of meso monosubstituted metalloporphyrins-Edge-on molecular interactions of porphyrins in crystals}, series = {Tetrahedron}, volume = {72}, journal = {Tetrahedron}, publisher = {Elsevier}, address = {Oxford}, issn = {0040-4020}, doi = {10.1016/j.tet.2015.11.008}, pages = {105 -- 115}, year = {2016}, abstract = {A series of meso monosubstituted metalloporphyrins were synthesized to assess the structural chemistry of porphyrins with only one substituent. The structures of four nickel(II) and zinc(II) complexes with either alkyl or aryl residues indicate primarily planar macrocycles. This gives rise to a different type of pi-interactions in the crystal and the formation of dimeric, trimeric or tetrameric porphyrin units that function as building blocks for the overall crystal structure. Notably, some structures exhibit a unique edge-on packing of porphyrins, while the molecules of (5-n-butylporphyrinato)nickel(II) forms an unusual bilayer type structure where rows of two porphyrin macrocycles are separated by the alkyl residues arranged in a head-to-head fashion. This adds to the canon of intermolecular porphyrin packing arrangements and is of relevance for the preparation of ordered nanoscopic porphyrin devices. (C) 2015 Elsevier Ltd. All rights reserved.}, language = {en} } @article{SeckerVoelkelTierschetal.2016, author = {Secker, Christian and Voelkel, Antje and Tiersch, Brigitte and Koetz, Joachim and Schlaad, Helmut}, title = {Thermo-Induced Aggregation and Crystallization of Block Copolypeptoids in Water}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {49}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.5b02481}, pages = {979 -- 985}, year = {2016}, abstract = {Block copolypeptoids comprising a thermosensitive, crystallizable poly(N-(n-propyl)glycine) block and a watersoluble poly(N-methylglycine) block, P70My (y = 23, 42, 76, 153, and 290), were synthesized bY ring-opening polymerization of the corresponding N-alkylglycine N-carboxyanhydrides (NCAs) and examined according to their thermo-induced aggregation and crystallization in water by turbidimetty, micro-differential scanning calorimetry (micro-DSC); cryogenic scanning electron microscopy (cryo-SEM), analytical ultracentrifugation (AUC), and static light scattering (SLS). At a temperature above the cloud point temperature, the initially formed micellar aggregates started to crystallize and grow into larger complex assemblies of about 100-500 nm, exhibiting flower-like (P70M23), ellipsoidal (P70M42 and P70M72) or irregular shapes (P70M153 and.P70M290).}, language = {en} } @article{SechiFreitasWuennemannetal.2016, author = {Sechi, Antonio and Freitas, Joana M. G. and W{\"u}nnemann, Patrick and T{\"o}pel, Alexander and Paschoalin, Rafaella Takehara and Ullmann, Sabrina and Schr{\"o}der, Ricarda and Aydin, G{\"u}lcan and R{\"u}tten, Stephan and B{\"o}ker, Alexander and Zenke, Martin and Pich, Andrij}, title = {Surface-Grafted Nanogel Arrays Direct Cell Adhesion and Motility}, series = {Advanced materials interfaces}, volume = {3}, journal = {Advanced materials interfaces}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {2196-7350}, doi = {10.1002/admi.201600455}, pages = {13}, year = {2016}, abstract = {It has long been appreciated that material chemistry and topology profoundly affect cell adhesion and migration. Here, aqueous poly(N- isopropyl acrylamide) nanogels are designed, synthesized and printed in form of colloidal arrays on glass substrates using wrinkled polydimethylsiloxane templates. Using low-temperature plasma treatment, nanogels are chemically grafted onto glass supports thus leading to highly stable nanogel layers in cell culture media. Liquid cell atomic force microscopy investigations show that surface-grafted nanogels retain their swelling behavior in aqueous media and that extracellular matrix protein coating do not alter their stability and topography. It is demonstrated that surface-grafted nanogels could serve as novel substrates for the analysis of cell adhesion and migration. Nanogels influence size, speed, and dynamics of focal adhesions and cell motility forcing cells to move along highly directional trajectories. Moreover, modulation of nanogel state or spacing serves as an effective tool for regulation of cell motility. It is suggested that nanogel arrays deposited on solid surfaces could be used to provide a precise and tunable system to understand and control cell migration. Additionally, such nanogel arrays will contribute to the development of implantable systems aimed at supporting and enhancing cell migration during, for instance, wound healing and tissue regeneration.}, language = {en} } @article{SchuermannBald2016, author = {Sch{\"u}rmann, Robin Mathis and Bald, Ilko}, title = {Decomposition of DNA Nucleobases by Laser Irradiation of Gold Nanoparticles Monitored by Surface-Enhanced Raman Scattering}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {120}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.5b10564}, pages = {3001 -- 3009}, year = {2016}, abstract = {Different approaches have been proposed to treat cancer cells using gold nanoparticles (AuNPs) in combination with radiation ranging from infrared lasers to high-energy ion beams. Here we study the decomposition of the DNA/RNA nucleobases thymine (T) and uracil (U) and the well-known radiosensitizer 5-bromouracil (BrU) in close vicinity to AuNPs, which are irradiated with a nanosecond pulsed laser (532 nm) matching the surface plasmon resonance of the AuNPs. The induced damage of nucleobases is analyzed by UV-vis absorption spectroscopy and surface-enhanced Raman scattering (SERS). A clear DNA damage is observed upon laser irradiation. SERS spectra indicate the fragmentation of the aromatic ring system of T and U as the dominant form of damage, whereas with BrU mainly the cleavage of the Br-C bond and formation of Br- ions is observed. This is accompanied by a partial transformation of BrU into U. The observed damage is at least partly ascribed to the intermediate formation of low energy electrons from the laser-excited AuNPs and subsequent dissociative electron attachment to T, U, and BrU. These reactions represent basic DNA damage pathways occurring on the one hand in plasmon-assisted cancer therapy and on the other hand in conventional cancer radiation therapy using AuNPs as sensitizing agents.}, language = {en} } @article{SchueringsNevskyiEliaschetal.2016, author = {Sch{\"u}rings, Marco-Philipp and Nevskyi, Oleksii and Eliasch, Kamill and Michel, Ann-Katrin and Liu, Bing and Pich, Andrij and B{\"o}ker, Alexander and von Plessen, Gero and W{\"o}ll, Dominik}, title = {Diffusive Motion of Linear Microgel Assemblies in Solution}, series = {Polymers}, volume = {8}, journal = {Polymers}, publisher = {MDPI}, address = {Basel}, issn = {2073-4360}, doi = {10.3390/polym8120413}, pages = {14}, year = {2016}, abstract = {Due to the ability of microgels to rapidly contract and expand in response to external stimuli, assemblies of interconnected microgels are promising for actuation applications, e.g., as contracting fibers for artificial muscles. Among the properties determining the suitability of microgel assemblies for actuation are mechanical parameters such as bending stiffness and mobility. Here, we study the properties of linear, one-dimensional chains of poly(N-vinylcaprolactam) microgels dispersed in water. They were fabricated by utilizing wrinkled surfaces as templates and UV-cross-linking the microgels. We image the shapes of the chains on surfaces and in solution using atomic force microscopy (AFM) and fluorescence microscopy, respectively. In solution, the chains are observed to execute translational and rotational diffusive motions. Evaluation of the motions yields translational and rotational diffusion coefficients and, from the translational diffusion coefficient, the chain mobility. The microgel chains show no perceptible bending, which yields a lower limit on their bending stiffness.}, language = {en} } @article{SchoeneSchulzLendlein2016, author = {Sch{\"o}ne, Anne-Christin and Schulz, Burkhard and Lendlein, Andreas}, title = {Stimuli Responsive and Multifunctional Polymers: Progress in Materials and Applications}, series = {Macromolecular rapid communications}, volume = {37}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201600650}, pages = {1856 -- 1859}, year = {2016}, language = {en} } @article{SchoeneKratzSchulzetal.2016, author = {Sch{\"o}ne, Anne-Christin and Kratz, Karl and Schulz, Burkhard and Lendlein, Andreas}, title = {The relevance of hydrophobic segments in multiblock copolyesterurethanes for their enzymatic degradation at the air-water interface}, series = {Polymer : the international journal for the science and technology of polymers}, volume = {102}, journal = {Polymer : the international journal for the science and technology of polymers}, publisher = {Elsevier}, address = {Oxford}, issn = {0032-3861}, doi = {10.1016/j.polymer.2016.09.001}, pages = {92 -- 98}, year = {2016}, abstract = {The interplay of an enzyme with a multiblock copolymer PDLCL containing two segments of different hydrophilicity and degradability is explored in thin films at the air-water interface. The enzymatic degradation was studied in homogenous Langmuir monolayers, which are formed when containing more than 40 wt\% oligo(epsilon-caprolactone) (OCL). Enzymatic degradation rates were significantly reduced with increasing content of hydrophobic oligo(omega-pentadecalactone) (OPDL). The apparent deceleration of the enzymatic process is caused by smaller portion of water-soluble degradation fragments formed from degradable OCL fragments. Beside the film degradation, a second competing process occurs after adding lipase from Pseudomonas cepacia into the subphase, namely the enrichment of the lipase molecules in the polymeric monolayer. The incorporation of the lipase into the Langmuir film is experimentally revealed by concurrent surface area enlargement and by Brewster angle microscopy (BAM). Aside from the ability to provide information about the degradation behavior of polymers, the Langmuir monolayer degradation (LMD) approach enables to investigate polymer-enzyme interactions for non-degradable polymers. (C) 2016 Elsevier Ltd. All rights reserved.}, language = {en} } @article{SchoeneKratzSchulzetal.2016, author = {Sch{\"o}ne, Anne-Christin and Kratz, Karl and Schulz, Burkhard and Lendlein, Andreas}, title = {Polymer architecture versus chemical structure as adjusting tools for the enzymatic degradation of oligo(epsilon-caprolactone) based films at the air-water interface}, series = {Polymer Degradation and Stability}, volume = {131}, journal = {Polymer Degradation and Stability}, publisher = {Elsevier}, address = {Oxford}, issn = {0141-3910}, doi = {10.1016/j.polymdegradstab.2016.07.010}, pages = {114 -- 121}, year = {2016}, abstract = {The enzymatic degradation of oligo(epsilon-caprolactone) (OCL) based films at the air-water interface is investigated by Langmuir monolayer degradation (LMD) experiments to elucidate the influence of the molecular architecture and of the chemical structure on the chain scission process. For that purpose, the interactions of 2D monolayers of two star-shaped poly(epsilon-caprolactone)s (PCLs) and three linear OCL based copolyesterurethanes (P(OCL-U)) with the lipase from Pseudomonas cepacia are evaluated in comparison to linear OCL. While the architecture of star-shaped PCL Langmuir layers slightly influences their degradability compared to OCL films, significantly retarded degradations are observed for P(OCL-U) films containing urethane junction units derived from 2, 2 (4), 4-trimethyl hexamethylene diisocyanate (TMDI), hexamethylene diisocyanate (HDI) or lysine ethyl ester diisocyanate (LDI). The enzymatic degradation of the OCL based 2D structures is related to the presence of hydrophilic groups within the macromolecules rather than to the packing density of the film or to the molecular weight. The results reveal that the LMD technique allows the parallel analysis of both the film/enzyme interactions and the degradation process on the molecular level. (C) 2016 Elsevier Ltd. All rights reserved.}, language = {en} } @article{SchoenbornSaalfrankKlamroth2016, author = {Sch{\"o}nborn, Jan Boyke and Saalfrank, Peter and Klamroth, Tillmann}, title = {Controlling the high frequency response of H-2 by ultra-short tailored laser pulses: A time-dependent configuration interaction study}, series = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, volume = {144}, journal = {The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-9606}, doi = {10.1063/1.4940316}, pages = {9}, year = {2016}, abstract = {We combine the stochastic pulse optimization (SPO) scheme with the time-dependent configuration interaction singles method in order to control the high frequency response of a simple molecular model system to a tailored femtosecond laser pulse. For this purpose, we use H-2 treated in the fixed nuclei approximation. The SPO scheme, as similar genetic algorithms, is especially suited to control highly non-linear processes, which we consider here in the context of high harmonic generation. Here, we will demonstrate that SPO can be used to realize a "non-harmonic" response of H2 to a laser pulse. Specifically, we will show how adding low intensity side frequencies to the dominant carrier frequency of the laser pulse and stochastically optimizing their contribution can create a high-frequency spectral signal of significant intensity, not harmonic to the carrier frequency. At the same time, it is possible to suppress the harmonic signals in the same spectral region, although the carrier frequency is kept dominant during the optimization. (C) 2016 AIP Publishing LLC.}, language = {en} } @article{SchwarzeSchneiderRiemeretal.2016, author = {Schwarze, Thomas and Schneider, Radu and Riemer, Janine and Holdt, Hans-J{\"u}rgen}, title = {A Highly K+-Selective Fluorescent Probe - Tuning the K+-Complex Stability and the K+/Na+ Selectivity by Varying the Lariat-Alkoxy Unit of a Phenylaza[18]crown-6 Ionophore}, series = {Chemistry : an Asian journal ; an ACES journal}, volume = {11}, journal = {Chemistry : an Asian journal ; an ACES journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1861-4728}, doi = {10.1002/asia.201500956}, pages = {241 -- 247}, year = {2016}, abstract = {A desirable goal is to synthesize easily accessible and highly K+/Na+-selective fluoroionophores to monitor physiological K+ levels in vitro and in vivo. Therefore, highly K+/Na+-selective ionophores have to be developed. Herein, we obtained in a sequence of only four synthetic steps a set of K+-responsive fluorescent probes 4, 5 and 6. In a systematic study, we investigated the influence of the alkoxy substitution in ortho position of the aniline moiety in -conjugated aniline-1,2,3-triazole-coumarin-fluoroionophores 4, 5 and 6 [R=MeO (4), EtO (5) and iPrO (6)] towards the K+-complex stability and K+/Na+ selectivity. The highest K+-complex stability showed fluoroionophore 4 with a dissociation constant K-d of 19mm, but the K-d value increases to 31mm in combined K+/Na+ solutions, indicating a poor K+/Na+ selectivity. By contrast, 6 showed even in the presence of competitive Na+ ions equal K-d values (K-d(K+)=45mm and K-d(K+/Na+)=45mm) and equal K+-induced fluorescence enhancement factors (FEFs=2.3). Thus, the fluorescent probe 6 showed an outstanding K+/Na+ selectivity and is a suitable fluorescent tool to measure physiological K+ levels in the range of 10-80mm in vitro. Further, the isopropoxy-substituted N-phenylaza[18]crown-6 ionophore in 6 is a highly K+-selective building block with a feasible synthetic route.}, language = {en} } @article{SchulzePrietzelKoetz2016, author = {Schulze, Nicole and Prietzel, Claudia Christina and Koetz, Joachim}, title = {Polyampholyte-mediated synthesis of anisotropic gold nanoplatelets}, series = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, volume = {294}, journal = {Colloid and polymer science : official journal of the Kolloid-Gesellschaft}, publisher = {Springer}, address = {New York}, issn = {0303-402X}, doi = {10.1007/s00396-016-3890-y}, pages = {1297 -- 1304}, year = {2016}, abstract = {This paper focused on the synthesis of triangular nanoplatelets in the presence of a tubular network structure. The tubular network structure is formed by adding a strongly alternating polyampholyte, i.e., PalPhBisCarb, to a mixed vesicle system with a negatively charged bilayer containing phosphatidylcholin and AOT. Using the tubular network as a reducing agent in a one-step procedure, triangular and hexagonal nanoplatelets are formed. One can show that the nanoplatelet yield is enhanced by increasing the temperature and decreasing the reaction time. The platelet edge length can be decreased by heating the system up to 100 A degrees C. Due to specific interactions between PalPhBisCarb and the AOT/phospholipid bilayer, stacking and welding effects lead to the formation of ordered platelet structures. The reaction pathway to flat gold nanotriangles is discussed with regard to the twin plane growth model of gold nanoplates.}, language = {en} } @article{ScholzFlossSaalfranketal.2016, author = {Scholz, Robert and Floss, Gereon and Saalfrank, Peter and F{\"u}chsel, Gernot and Loncaric, Ivor and Juaristi, J. I.}, title = {Femtosecond-laser induced dynamics of CO on Ru(0001): Deep insights from a hot-electron friction model including surface motion}, series = {Physical review : B, Condensed matter and materials physics}, volume = {94}, journal = {Physical review : B, Condensed matter and materials physics}, publisher = {American Physical Society}, address = {College Park}, issn = {2469-9950}, doi = {10.1103/PhysRevB.94.165447}, pages = {17}, year = {2016}, abstract = {A Langevin model accounting for all six molecular degrees of freedom is applied to femtosecond-laser induced, hot-electron driven dynamics of Ru(0001)(2 x 2): CO. In our molecular dynamics with electronic friction approach, a recently developed potential energy surface based on gradient-corrected density functional theory accounting for van der Waals interactions is adopted. Electronic friction due to the coupling of molecular degrees of freedom to electron-hole pairs in the metal are included via a local density friction approximation, and surface phonons by a generalized Langevin oscillator model. The action of ultrashort laser pulses enters through a substrate-mediated, hot-electron mechanism via a time-dependent electronic temperature (derived from a two-temperature model), causing random forces acting on the molecule. The model is applied to laser induced lateral diffusion of CO on the surface, "hot adsorbate" formation, and laser induced desorption. Reaction probabilities are strongly enhanced compared to purely thermal processes, both for diffusion and desorption. Reaction yields depend in a characteristic (nonlinear) fashion on the applied laser fluence, as well as branching ratios for various reaction channels. Computed two-pulse correlation traces for desorption and other indicators suggest that aside from electron-hole pairs, phonons play a non-negligible role for laser induced dynamics in this system, acting on a surprisingly short time scale. Our simulations on precomputed potentials allow for good statistics and the treatment of long-time dynamics (300 ps), giving insight into this system which hitherto has not been reached. We find generally good agreement with experimental data where available and make predictions in addition. A recently proposed laser induced population of physisorbed precursor states could not be observed with the present low-coverage model.}, language = {en} } @article{SchneiderWeigertLesnyaketal.2016, author = {Schneider, Rudolf and Weigert, F. and Lesnyak, V. and Leubner, S. and Lorenz, T. and Behnke, Thomas and Dubavik, A. and Joswig, J. -O. and Resch-Genger, U. and Gaponik, N. and Eychmueller, A.}, title = {pH and concentration dependence of the optical properties of thiol-capped CdTe nanocrystals in water and D2O}, series = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, volume = {18}, journal = {Physical chemistry, chemical physics : a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c6cp03123d}, pages = {19083 -- 19092}, year = {2016}, abstract = {The optical properties of semiconductor nanocrystals (SC NCs) are largely controlled by their size and surface chemistry, i.e., the chemical composition and thickness of inorganic passivation shells and the chemical nature and number of surface ligands as well as the strength of their bonds to surface atoms. The latter is particularly important for CdTe NCs, which - together with alloyed CdxHg1\&\#8722;xTe - are the only SC NCs that can be prepared in water in high quality without the need for an additional inorganic passivation shell. Aiming at a better understanding of the role of stabilizing ligands for the control of the application-relevant fluorescence features of SC NCs, we assessed the influence of two of the most commonly used monodentate thiol ligands, thioglycolic acid (TGA) and mercaptopropionic acid (MPA), on the colloidal stability, photoluminescence (PL) quantum yield (QY), and PL decay behavior of a set of CdTe NC colloids. As an indirect measure for the strength of the coordinative bond of the ligands to SC NC surface atoms, the influence of the pH (pD) and the concentration on the PL properties of these colloids was examined in water and D2O and compared to the results from previous dilution studies with a set of thiol-capped Cd1\&\#8722;xHgxTe SC NCs in D2O. As a prerequisite for these studies, the number of surface ligands was determined photometrically at different steps of purification after SC NC synthesis with Ellman's test. Our results demonstrate ligand control of the pH-dependent PL of these SC NCs, with MPA-stabilized CdTe NCs being less prone to luminescence quenching than TGA-capped ones. For both types of CdTe colloids, ligand desorption is more pronounced in H2O compared to D2O, underlining also the role of hydrogen bonding and solvent molecules.}, language = {en} } @article{SchmidtLorenz2016, author = {Schmidt, Burkhard and Lorenz, Ulf}, title = {WavePacket}, series = {Computer physics communications : an international journal devoted to computational physics and computer programs in physics}, volume = {213}, journal = {Computer physics communications : an international journal devoted to computational physics and computer programs in physics}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0010-4655}, doi = {10.1016/j.cpc.2016.12.007}, pages = {223 -- 234}, year = {2016}, abstract = {WavePacket is an open-source program package for the numerical simulation of quantum-mechanical dynamics. It can be used to solve time-independent or time-dependent linear Schr{\"o}dinger and Liouville-von Neumann-equations in one or more dimensions. Also coupled equations can be treated, which allows to simulate molecular quantum dynamics beyond the Born-Oppenheimer approximation. Optionally accounting for the interaction with external electric fields within the semiclassical dipole approximation, WavePacket can be used to simulate experiments involving tailored light pulses in photo-induced physics or chemistry. The graphical capabilities allow visualization of quantum dynamics 'on the fly', including Wigner phase space representations. Being easy to use and highly versatile, WavePacket is well suited for the teaching of quantum mechanics as well as for research projects in atomic, molecular and optical physics or in physical or theoretical chemistry. The present Part I deals with the description of closed quantum systems in terms of Schr{\"o}dinger equations. The emphasis is on discrete variable representations for spatial discretization as well as various techniques for temporal discretization. The upcoming Part II will focus on open quantum systems and dimension reduction; it also describes the codes for optimal control of quantum dynamics. The present work introduces the MATLAB version of WavePacket 5.2.1 which is hosted at the Sourceforge platform, where extensive Wiki-documentation as well as worked-out demonstration examples can be found.}, language = {en} } @article{SchmidtWolfEhlert2016, author = {Schmidt, Bernd and Wolf, Felix and Ehlert, Christopher}, title = {Systematic Investigation into the Matsuda-Heck Reaction of alpha-Methylene Lactones: How Conformational Constraints Direct the beta-H-Elimination Step}, series = {The journal of organic chemistry}, volume = {81}, journal = {The journal of organic chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {0022-3263}, doi = {10.1021/acs.joc.6b02207}, pages = {11235 -- 11249}, year = {2016}, abstract = {alpha-Methylene-gamma-butyrolactone and alpha-methylene-gamma-valerolactone undergo Pd-catalyzed Matsuda-Heck couplings with arene diazonium salts to alpha-benzyl butenolides or pentenolides, respectively, or to alpha-benzylidene lactones. The observed regioselectivity is strongly ring size dependent, with six-membered rings giving exclusively alpha-benzyl pentenolides, whereas the five-membered alpha-methylene lactone reacts to mixtures of regioisomers with a high proportion of (E)-alpha-benzylidene-gamma-butyrolactones. DFT calculations suggest that the reasons for these differences are not thermodynamic but kinetic in nature. The relative energies of the conformers of the Pd sigma-complexes resulting from insertion into the Pd-aryl bond were correlated with the dihedral angles between Pd and endo-beta-H. This correlation revealed that in the case of the six-membered lactone an energetically favorable conformer adopts a nearly synperiplanar Pd/endo-beta-H arrangement, whereas for the analogous Pd sigma-complex of the five-membered lactone the smallest Pd/endo-beta-H dihedral angle is observed for a conformer with a comparatively high potential energy. The optimized conditions for Matsuda-Heck arylations of exo-methylene lactones were eventually applied to the synthesis of the natural product anemarcoumarin A.}, language = {en} } @article{SchmidtWolfBrunner2016, author = {Schmidt, Bernd and Wolf, Felix and Brunner, Heiko}, title = {Styrylsulfonates and -Sulfonamides through Pd-Catalysed Matsuda-Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts}, series = {European journal of organic chemistry}, journal = {European journal of organic chemistry}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1434-193X}, doi = {10.1002/ejoc.201600469}, pages = {2972 -- 2982}, year = {2016}, abstract = {Arene diazonium salts undergo Matsuda-Heck reactions with vinylsulfonates and -sulfonamides to give styrylsulfonic acid derivatives in high to excellent yields and with high to excellent selectivities. By quantifying the evolution of nitrogen over time in a gas-meter apparatus, the reactivities of ethylvinylsulfonate and the benchmark olefin methyl acrylate were compared for an electron-rich and an -deficient arene diazonium salt. Tertiary sulfonamides react in Matsuda-Heck couplings with high conversions, but require long reaction times, which prevents the determination of kinetic data through the measurement of nitrogen evolution. Secondary sulfonamides were found to be unreactive. From these results, the following order of reactivity could be deduced: H2C=CHCO2Me > H2C=CHSO2OEt > H2C=CHSO2N(Me)Bn >> H2C=CHSO2NHBn. Through the Matsuda-Heck coupling of 5-indolyldiazonium salt and a tertiary vinylsulfonamide, the synthesis of the C-5-substituted indole part of the antimigraine drug naratriptan was accomplished in high yield.}, language = {en} } @article{SchmidtRiemer2016, author = {Schmidt, Bernd and Riemer, Martin}, title = {Microwave-Promoted Deprenylation: Prenyl Ether as a Thermolabile Phenol Protecting Group}, series = {Synthesis}, volume = {48}, journal = {Synthesis}, publisher = {Thieme}, address = {Stuttgart}, issn = {0039-7881}, doi = {10.1055/s-0035-1561366}, pages = {1399 -- 1406}, year = {2016}, abstract = {para-Substituted aryl prenyl ethers undergo a deprenylation reaction upon microwave irradiation. This offers the opportunity to use a prenyl ether as a thermolabile protecting group in the synthesis of natural products with a chromone structure, which proceeds via a tandem deprenylation/6-endo-cyclization sequence.}, language = {en} } @article{SchmidtRiemer2016, author = {Schmidt, Bernd and Riemer, Martin}, title = {Synthesis of Allyl- and Prenylcoumarins via Microwave-Promoted Tandem Claisen Rearrangement/Wittig Olefination}, series = {Synthesis}, volume = {48}, journal = {Synthesis}, publisher = {Thieme}, address = {Stuttgart}, issn = {0039-7881}, doi = {10.1055/s-0035-1560501}, pages = {141 -- 149}, year = {2016}, abstract = {Allyl, dimethylallyl, crotyl, and prenyl ethers of various aromatic ortho-hydroxy carbonyl compounds undergo a tandem sequence of Claisen rearrangement, carbonyl olefination, and cyclization upon microwave irradiation in the presence of a stabilized ylide. The products are multiply substituted 6- or 8-allylated or prenylated coumarins (2H-chromen-2-ones).}, language = {en} } @article{SchmidtAudoerschKunz2016, author = {Schmidt, Bernd and Audoersch, Stephan and Kunz, Oliver}, title = {Stereoselective Synthesis of 2Z,4E-Configured Dienoates through Tethered Ring Closing Metathesis}, series = {Synthesis}, volume = {48}, journal = {Synthesis}, publisher = {Thieme}, address = {Stuttgart}, issn = {0039-7881}, doi = {10.1055/s-0035-1562536}, pages = {4509 -- 4518}, year = {2016}, language = {en} } @article{SchildeKellingUmbreenetal.2016, author = {Schilde, Uwe and Kelling, Alexandra and Umbreen, Sumaira and Linker, Torsten}, title = {Crystal structures of three bicyclic carbohydrate derivatives}, series = {Acta crystallographica Section E ; Crystallographic communications}, volume = {72}, journal = {Acta crystallographica Section E ; Crystallographic communications}, number = {12}, publisher = {IUCR}, address = {Chester}, issn = {2056-9890}, doi = {10.1107/S2056989016018727}, pages = {1839 -- 1844}, year = {2016}, abstract = {The title compounds, [(1R,3R,4R,5R,6S)-4,5-bis(acetyloxy)-7-oxo-2-oxabicyclo- [4.2.0]octan-3-yl]methyl acetate, C14H18O8, (I), [(1S,4R,5S,6R)-5-acetyloxy-7- hydroxyimino-2-oxobicyclo[4.2.0]octan-4-yl acetate, C11H15NO6, (II), and [(3aR,5R,6R,7R,7aS)-6,7-bis(acetyloxy)-2-oxooctahydropyrano[3,2-b]pyrrol-5- yl]methyl acetate, C14H19NO8, (III), are stable bicyclic carbohydrate derivatives. They can easily be synthesized in a few steps from commercially available glycals. As a result of the ring strain from the four-membered rings in (I) and (II), the conformations of the carbohydrates deviate strongly from the ideal chair form. Compound (II) occurs in the boat form. In the five-membered lactam (III), on the other hand, the carbohydrate adopts an almost ideal chair conformation. As a result of the distortion of the sugar rings, the configurations of the three bicyclic carbohydrate derivatives could not be determined from their NMR coupling constants. From our three crystal structure determinations, we were able to establish for the first time the absolute configurations of all new stereocenters of the carbohydrate rings.}, language = {en} } @article{SchildeKellingUmbreenetal.2016, author = {Schilde, Uwe and Kelling, Alexandra and Umbreen, Sumaira and Linker, Torsten}, title = {Crystal structures of three bicyclic carbohydrate derivatives}, series = {Acta crystallographica, Section E, Crystallographic communications}, volume = {72}, journal = {Acta crystallographica, Section E, Crystallographic communications}, publisher = {International Union of Crystallography}, address = {Chester}, issn = {2056-9890}, doi = {10.1107/S2056989016018727}, pages = {1839 -- +}, year = {2016}, abstract = {The title compounds, [(1R,3R,4R,5R,6S)-4,5-bis(acetyloxy)-7-oxo-2-oxabicyclo-[4.2.0]octan-3-yl]methyl acetate, C14H18O8, (I), [(1S,4R,5S,6R)-5-acetyloxy-7-hydroxyimino-2-oxobicyclo[4.2.0] octan-4-yl acetate, C11H15NO6, (II), and [(3aR, 5R, 6R, 7R, 7aS)-6,7-bis(acetyloxy)-2-oxooctahydropyrano[3,2-b]pyrrol-5-yl] methyl acetate, C14H19NO8, (III), are stable bicyclic carbohydrate derivatives. They can easily be synthesized in a few steps from commercially available glycals. As a result of the ring strain from the four-membered rings in (I) and (II), the conformations of the carbohydrates deviate strongly from the ideal chair form. Compound (II) occurs in the boat form. In the five-membered lactam (III), on the other hand, the carbohydrate adopts an almost ideal chair conformation. As a result of the distortion of the sugar rings, the configurations of the three bicyclic carbohydrate derivatives could not be determined from their NMR coupling constants. From our three crystal structure determinations, we were able to establish for the first time the absolute configurations of all new stereocenters of the carbohydrate rings.}, language = {en} } @article{RyabchunRaguzinStumpeetal.2016, author = {Ryabchun, Alexander and Raguzin, Ivan and Stumpe, Joachim and Shibaev, Valery and Bobrovsky, Alexey}, title = {Cholesteric Polymer Scaffolds Filled with Azobenzene-Containing Nematic Mixture with Phototunable Optical Properties}, series = {Scientific reports}, volume = {8}, journal = {Scientific reports}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.6b09642}, pages = {27227 -- 27235}, year = {2016}, abstract = {The past two decades witnessed tremendous progress in the field of creation of different types of responsive materials. Cholesteric polymer networks present a very promising class of smart materials due to the combination of the unique optical properties of cholesteric mesophase and high mechanical properties of polymer networks. In the present work we demonstrate the possibility of fast and reversible photocontrol of the optical properties of cholesteric polymer networks. Several cholesteric photopolymerizable mixtures are prepared, and porous cholesteric network films with different helix pitches are produced by polymerization of these mixtures. An effective and simple method of the introduction of photochromic azobenzene-containing nematic mixture capable of isothermal photoinducing the nematic isotropic phase transition into the porous polymer matrix is developed, It is found that cross-linking density and degree of polymer network filling with a photochromic nematic mixture strongly influence the photo-optical behavior of the obtained composite films. In particular, the densely cross-linked films are characterized by a decrease in selective light reflection bandwidth, whereas weakly cross-linked systems display two processes: the shift of selective light reflection peak and decrease of its width. It is noteworthy that the obtained cholesteric materials are shown to be very promising for the variety applications in optoelectronics and photonics.}, language = {en} } @article{RumschoettelKosmellaPrietzeletal.2016, author = {Rumsch{\"o}ttel, Jens and Kosmella, Sabine and Prietzel, Claudia Christina and Appelhans, Dietmar and Koetz, Joachim}, title = {Change in size, morphology and stability of DNA polyplexes with hyperbranched poly(ethyleneimines) containing bulky maltose units}, 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 = {138}, 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.2015.11.061}, pages = {78 -- 85}, year = {2016}, abstract = {Polyplexes between Salmon DNA and non-modified hyperbranched poly(ethyleneimines) of varying molar mass, i.e., PEI(5 k) with 5000 g/mol and PEI(25 k) with 25,000 g/mol, and modified PEI(5 k) with maltose units (PEI-Mal) were investigated in dependence on the molar N/P ratio by using dynamic light scattering (DLS), zeta potential measurements, micro differential scanning calorimetry (mu-DSC), scanning-transmission electron microscopy (STEM), and cryo-scanning electron microscopy (cryo-SEM). A reloading of the polyplexes can be observed by adding the unmodified PEI samples of different molar mass. In excess of PEI a morphological transition from core-shell particles (at N/P 8) to loosely packed onion-like polyplexes (at N/P 40) is observed. The shift of the DSC melting peak from 88 degrees C to 76 degrees C indicates a destabilization of the DNA double helix due to the complexation with the unmodified PEI. Experiments with the maltose-modified PEI show a reloading already at a lower N/P ratio. Due to the presence of the sugar units in the periphery of the polycation electrostatic interactions between DNA become weaker, but cooperative H-bonding forces are reinforced. The resulting less-toxic, more compact polyplexes in excess of the PEI-Mal with two melting points and well distributed DNA segments are of special interest for extended gene delivery experiments. (C) 2015 Elsevier B.V. All rights reserved.}, language = {en} } @article{RottkeSchulzRichauetal.2016, author = {Rottke, Falko O. and Schulz, Burkhard and Richau, Klaus and Kratz, Karl and Lendlein, Andreas}, title = {An ellipsometric approach towards the description of inhomogeneous polymer-based Langmuir layers}, series = {Beilstein journal of nanotechnology}, volume = {7}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\~A}\Prderung der Chemischen Wissenschaften}, address = {Frankfurt, Main}, issn = {2190-4286}, doi = {10.3762/bjnano.7.107}, pages = {1156 -- 1165}, year = {2016}, abstract = {The applicability of nulling-based ellipsometric mapping as a complementary method next to Brewster angle microscopy (BAM) and imaging ellipsometry (IE) is presented for the characterization of ultrathin films at the air-water interface. First, the methodology is demonstrated for a vertically nonmoving Langmuir layer of star-shaped, 4-arm poly(omega-pentadecalactone) (PPDL-D4). Using nulling-based ellipsometric mapping, PPDL-D4-based inhomogeneously structured morphologies with a vertical dimension in the lower nm range could be mapped. In addition to the identification of these structures, the differentiation between a monolayer and bare water was possible. Second, the potential and limitations of this method were verified by applying it to more versatile Langmuir layers of telechelic poly[(rac-lactide)-co-glycolide]-diol (PLGA). All ellipsometric maps were converted into thickness maps by introduction of the refractive index that was derived from independent ellipsometric experiments, and the result was additionally evaluated in terms of the root mean square roughness, R-q. Thereby, a three-dimensional view into the layers was enabled and morphological inhomogeneity could be quantified.}, language = {en} } @article{RossbergRottkeSchulzetal.2016, author = {Rossberg, Joana and Rottke, Falko O. and Schulz, Burkhard and Lendlein, Andreas}, title = {Enzymatic Degradation of Oligo(epsilon-caprolactone)s End-Capped with Phenylboronic Acid Derivatives at the Air-Water Interface}, series = {Macromolecular rapid communications}, volume = {37}, journal = {Macromolecular rapid communications}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1022-1336}, doi = {10.1002/marc.201600471}, pages = {1966 -- 1971}, year = {2016}, abstract = {The influence of terminal functionalization of oligo(epsilon-caprolactone)s (OCL) with phenylboronic acid pinacol ester or phenylboronic acid on the enzymatic degradation behavior at the air-water interface is investigated by the Langmuir monolayer degradation technique. While the unsubstituted OCL immediately degrades after injection of the enzyme lipase from Pseudomonas cepacia, enzyme molecules are incorporated into the films based on end-capped OCL before degradation. This incorporation of enzymes does not inhibit or suppress the film degradation, but retards it significantly. A specific binding of lipase to the polymer monolayer allows studying the enzymatic activity of bound proteins and the influence on the degradation process. The functionalization of a macromolecule with phenyl boronic acid groups is an approach to investigate their interactions with diol-containing biomolecules like sugars and to monitor their specified impact on the enzymatic degradation behavior at the air-water interface.}, language = {en} } @article{RiebeEderRitscheletal.2016, author = {Riebe, Daniel and Eder, Alexander and Ritschel, Thomas and Beitz, Toralf and L{\"o}hmannsr{\"o}ben, Hans-Gerd and Beil, Andreas and Blaschke, Michael and Ludwig, Thomas}, title = {Atmospheric pressure chemical ionization of explosives induced by soft X-radiation in ion mobility spectrometry: mass spectrometric investigation of the ionization reactions of drift gasses, dopants and alkyl nitrates}, series = {Journal of mass spectrometr}, volume = {51}, journal = {Journal of mass spectrometr}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {1076-5174}, doi = {10.1002/jms.3784}, pages = {566 -- 577}, year = {2016}, abstract = {A promising replacement for the radioactive sources commonly encountered in ion mobility spectrometers is a miniaturized, energy-efficient photoionization source that produce the reactant ions via soft X-radiation (2.8 keV). In order to successfully apply the photoionization source, it is imperative to know the spectrum of reactant ions and the subsequent ionization reactions leading to the detection of analytes. To that end, an ionization chamber based on the photoionization source that reproduces the ionization processes in the ion mobility spectrometer and facilitates efficient transfer of the product ions into a mass spectrometer was developed. Photoionization of pure gasses and gas mixtures containing air, N-2, CO2 and N2O and the dopant CH2Cl2 is discussed. The main product ions of photoionization are identified and compared with the spectrum of reactant ions formed by radioactive and corona discharge sources on the basis of literature data. The results suggest that photoionization by soft X-radiation in the negative mode is more selective than the other sources. In air, adduct ions of O-2 - with H2O and CO2 were exclusively detected. Traces of CO2 impact the formation of adduct ions of O-2 - and Cl -(upon addition of dopant) and are capable of suppressing them almost completely at high CO2 concentrations. Additionally, the ionization products of four alkyl nitrates (ethylene glycol dinitrate, nitroglycerin, erythritol tetranitrate and pentaerythritol tetranitrate) formed by atmospheric pressure chemical ionization induced by X-ray photoionization in different gasses (air, N-2 and N2O) and dopants (CH2Cl2, C2H5Br and CH3I) are investigated. The experimental studies are complemented by density functional theory calculations of the most important adduct ions of the alkyl nitrates (M) used for their spectrometric identification. In addition to the adduct ions [M + NO3](-) and [M + Cl](-), adduct ions such as [M + N2O2](-), [M + Br](-) and [M+ I](-) were detected, and their gas-phase structures and energetics are investigated by density functional theory calculations. Copyright (C) 2016 John Wiley \& Sons, Ltd.}, language = {en} } @article{RichterSchulzSubkowskietal.2016, author = {Richter, Marina Juliane and Schulz, Alexander and Subkowski, Thomas and B{\"o}ker, Alexander}, title = {Adsorption and rheological behavior of an amphiphilic protein at oil/water interfaces}, series = {Journal of colloid and interface science}, volume = {479}, journal = {Journal of colloid and interface science}, publisher = {Elsevier}, address = {San Diego}, issn = {0021-9797}, doi = {10.1016/j.jcis.2016.06.062}, pages = {199 -- 206}, year = {2016}, abstract = {Hydrophobins are highly surface active proteins which self-assemble at hydrophilic-hydrophobic interfaces into amphipathic membranes. We investigate hydrophobin self-assembly at oil/water interfaces to deepen the understanding of protein behavior in order to improve our biomimetic synthesis. Therefore, we carried out pendant drop measurements of hydrophobin stabilized oil/water systems determining the time-dependent IFT and the dilatational rheology with additional adaptation to the Serrien protein model. We show that the class I hydrophobin H*Protein B adsorbs at an oil/water interface where it forms a densely-packed interfacial protein layer, which dissipates energy during droplet oscillation. Furthermore, the interfacial protein layer exhibits shear thinning behavior. (C) 2016 Elsevier Inc. All rights reserved.}, language = {en} } @article{ReppertSarhanSteteetal.2016, author = {Reppert, Alexander von and Sarhan, Radwan Mohamed and Stete, Felix and Pudell, Jan-Etienne and Del Fatti, N. and Crut, A. and Koetz, Joachim and Liebig, Ferenc and Prietzel, Claudia Christina and Bargheer, Matias}, title = {Watching the Vibration and Cooling of Ultrathin Gold Nanotriangles by Ultrafast X-ray Diffraction}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {120}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.6b11651}, pages = {28894 -- 28899}, year = {2016}, abstract = {We study the vibrations of ultrathin gold nanotriangles upon optical excitation of the electron gas by ultrafast X-ray diffraction. We quantitatively measure the strain evolution in these highly asymmetric nano-objects, providing a direct estimation of the amplitude and phase of the excited vibrational motion. The maximal strain value is well reproduced by calculations addressing pump absorption by the nanotriangles and their resulting thermal expansion. The amplitude and phase of the out-of-plane vibration mode with 3.6 ps period dominating the observed oscillations are related to two distinct excitation mechanisms. Electronic and phonon pressures impose stresses with different time dependences. The nanosecond relaxation of the expansion yields a direct temperature sensing of the nano-object. The presence of a thin organic molecular layer at the nanotriangle/substrate interfaces drastically reduces the thermal conductance to the substrate.}, language = {en} } @article{RasovicBlagojevicBaranacStojanovicetal.2016, author = {Rasovic, Aleksandar and Blagojevic, Vladimir and Baranac-Stojanovic, Marija and Kleinpeter, Erich and Markovic, Rade and Minic, Dragica M.}, title = {Quantification of the push-pull effect in 2-alkylidene-4-oxothiazolidines by using NMR spectral data and barriers to rotation around the C=C bond}, series = {New journal of chemistry}, volume = {40}, journal = {New journal of chemistry}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1144-0546}, doi = {10.1039/c6nj00901h}, pages = {6364 -- 6373}, year = {2016}, abstract = {Information about the strength of donor-acceptor interactions in push-pull alkenes is valuable, as this so-called "push-pull effect' influences their chemical reactivity and dynamic behaviour. In this paper, we discuss the applicability of NMR spectral data and barriers to rotation around the CQC double bond to quantify the push-pull effect in biologically important 2-alkylidene-4-oxothiazolidines. While olefinic proton chemical shifts and differences in C-13 NMR chemical shifts of the two carbons constituting the CQC double bond fail to give the correct trend in the electron withdrawing ability of the substituents attached to the exocyclic carbon of the double bond, barriers to rotation prove to be a reliable quantity in providing information about the extent of donor-acceptor interactions in the push-pull systems studied. In particular all relevant kinetic data, that is the Arrhenius parameters ( apparent activation energy Ea and frequency factor A) and activation parameters ( Delta S-double dagger, Delta H-double dagger and Delta G(double dagger)), were determined from the data of the experimentally studied configurational isomerization of ( E)-9a. These results were compared to previously published related data for other two compounds, ( Z)-1b and ( 2E, 5Z)-7, showing that experimentally determined Delta G(double dagger) values are a good indicator of the strength of push-pull character. Theoretical calculations of the rotational barriers of eight selected derivatives excellently correlate with the calculated CQC bond lengths and corroborate the applicability of Delta G(double dagger) for estimation of the strength of the push-pull effect in these and related systems.}, language = {en} } @article{RackwitzKopyraDabkowskaetal.2016, author = {Rackwitz, Jenny and Kopyra, Janina and Dabkowska, Iwona and Ebel, Kenny and Rankovic, MiloS Lj. and Milosavljevic, Aleksandar R. and Bald, Ilko}, title = {Sensitizing DNA Towards Low-Energy Electrons with 2-Fluoroadenine}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {55}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201603464}, pages = {10248 -- 10252}, year = {2016}, abstract = {2-Fluoroadenine ((2F)A) is a therapeutic agent, which is suggested for application in cancer radiotherapy. The molecular mechanism of DNA radiation damage can be ascribed to a significant extent to the action of low-energy (<20 eV) electrons (LEEs), which damage DNA by dissociative electron attachment. LEE induced reactions in (2F)A are characterized both isolated in the gas phase and in the condensed phase when it is incorporated into DNA. Information about negative ion resonances and anion-mediated fragmentation reactions is combined with an absolute quantification of DNA strand breaks in (2F)A-containing oligonucleotides upon irradiation with LEEs. The incorporation of (2F)A into DNA results in an enhanced strand breakage. The strand-break cross sections are clearly energy dependent, whereas the strand-break enhancements by (2F)A at 5.5, 10, and 15 eV are very similar. Thus, (2F)A can be considered an effective radiosensitizer operative at a wide range of electron energies.}, language = {en} } @phdthesis{Rackwitz2016, author = {Rackwitz, Jenny}, title = {A novel approach to study low-energy electron-induced damage to DNA oligonucleotides}, school = {Universit{\"a}t Potsdam}, pages = {137}, year = {2016}, language = {en} } @article{PrinzMatkovicPesicetal.2016, author = {Prinz, Julia and Matkovic, Aleksandar and Pesic, Jelena and Gajic, Rados and Bald, Ilko}, title = {Hybrid Structures for Surface-Enhanced Raman Scattering: DNA Origami/Gold Nanoparticle Dimer/Graphene}, series = {Small}, volume = {12}, journal = {Small}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1613-6810}, doi = {10.1002/smll.201601908}, pages = {5458 -- 5467}, year = {2016}, abstract = {A combination of three innovative materials within one hybrid structure to explore the synergistic interaction of their individual properties is presented. The unique electronic, mechanical, and thermal properties of graphene are combined with the plasmonic properties of gold nanoparticle (AuNP) dimers, which are assembled using DNA origami nanostructures. This novel hybrid structure is characterized by means of correlated atomic force microscopy and surface-enhanced Raman scattering (SERS). It is demonstrated that strong interactions between graphene and AuNPs result in superior SERS performance of the hybrid structure compared to their individual components. This is particularly evident in efficient fluorescence quenching, reduced background, and a decrease of the photobleaching rate up to one order of magnitude. The versatility of DNA origami structures to serve as interface for complex and precise arrangements of nanoparticles and other functional entities provides the basis to further exploit the potential of the here presented DNA origami-AuNP dimer-graphene hybrid structures.}, language = {en} } @article{PrinzHeckElleriketal.2016, author = {Prinz, Julia and Heck, Christian and Ellerik, Lisa and Merk, Virginia and Bald, Ilko}, title = {DNA origami based Au-Ag-core-shell nanoparticle dimers with single-molecule SERS sensitivity}, series = {Nanoscale}, volume = {8}, journal = {Nanoscale}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2040-3364}, doi = {10.1039/c5nr08674d}, pages = {5612 -- 5620}, year = {2016}, abstract = {DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 10(10), which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.}, language = {en} } @article{PrinzHeckElleriketal.2016, author = {Prinz, Julia and Heck, Christian and Ellerik, Lisa and Merk, Virginia and Bald, Ilko}, title = {DNA origami based Au-Ag-core-shell nanoparticle dimers with single-molecule SERS sensitivity}, series = {Nanoscale}, journal = {Nanoscale}, number = {8}, publisher = {RSC Publishing}, address = {Cambridge}, doi = {10.1039/C5NR08674D}, pages = {5612 -- 5620}, year = {2016}, abstract = {DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.}, language = {en} } @article{PrestelMoeller2016, author = {Prestel, Andreas and M{\"o}ller, Heiko Michael}, title = {Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides}, series = {Chemical communications}, volume = {52}, journal = {Chemical communications}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1359-7345}, doi = {10.1039/c5cc06848g}, pages = {701 -- 704}, year = {2016}, abstract = {The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.}, language = {en} } @article{PoghosyanArsenyanShahinyanetal.2016, author = {Poghosyan, Armen H. and Arsenyan, Levon H. and Shahinyan, Aram A. and Koetz, Joachim}, title = {Polyethyleneimine loaded inverse SDS micelle in pentanol/toluene media}, series = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, volume = {506}, journal = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0927-7757}, doi = {10.1016/j.colsurfa.2016.07.018}, pages = {402 -- 408}, year = {2016}, abstract = {An atomic scale molecular dynamics simulation (100 ns) was carried out to reveal the conformational features of a cationic polyelectrolyte, i.e., hyperbranched polyethyleneimine (PEI), inside of water-in-oil microemulsion droplets stabilized by the anionic sodium dodecyl sulfate surfactant (SDS) layer. Simulations show that the polymer reorients very quickly and is localized at the headgroup region, i.e., the polymer nitrogens are close to SDS sulfur atoms. In spite of the availability of surface roughness caused by the polymer, we track a stable inverse micelle during the production run. In overall, the obtained parameters are well compared with experimental findings. (C) 2016 Elsevier B.V. All rights reserved.}, language = {en} } @article{PinyouRuffPoelleretal.2016, author = {Pinyou, Piyanut and Ruff, Adrian and Poeller, Sascha and Barwe, Stefan and Nebel, Michaela and Alburquerque, Natalia Guerrero and Wischerhoff, Erik and Laschewsky, Andre and Schmaderer, Sebastian and Szeponik, Jan and Plumere, Nicolas and Schuhmann, Wolfgang}, title = {Thermoresponsive amperometric glucose biosensor}, series = {Biointerphases}, volume = {11}, journal = {Biointerphases}, publisher = {American Institute of Physics}, address = {Melville}, issn = {1934-8630}, doi = {10.1116/1.4938382}, pages = {7}, year = {2016}, abstract = {The authors report on the fabrication of a thermoresponsive biosensor for the amperometric detection of glucose. Screen printed electrodes with heatable gold working electrodes were modified by a thermoresponsive statistical copolymer [polymer I: poly(omega-ethoxytriethylenglycol methacrylate-omega-3-(N,N-dimethyl-N-2-methacryloyloxyethyl ammonio) propanesulfonate-co-omega-butoxydiethylenglycol methacrylate-co-2-(4-benzoyl-phenoxy)ethyl methacrylate)] with a lower critical solution temperature of around 28 degrees C in aqueous solution via electrochemically induced codeposition with a pH-responsive redox-polymer [polymer II: poly(glycidyl methacrylate-co-allyl methacrylate-co-poly(ethylene glycol) methacrylate-co-butyl acrylate-co-2-(dimethylamino) ethyl methacrylate)-[Os(bpy)(2)(4-(((2-(2-(2-aminoethoxy) ethoxy) ethyl) amino) methyl)-N,N-dimethylpicolinamide)](2+)] and pyrroloquinoline quinone-soluble glucose dehydrogenase acting as biological recognition element. Polymer II bears covalently bound Os-complexes that act as redox mediators for shuttling electrons between the enzyme and the electrode surface. Polymer I acts as a temperature triggered immobilization matrix. Probing the catalytic current as a function of the working electrode temperature shows that the activity of the biosensor is dramatically reduced above the phase transition temperature of polymer I. Thus, the local modulation of the temperature at the interphase between the electrode and the bioactive layer allows switching the biosensor from an on-to an off-state without heating of the surrounding analyte solution. (C) 2015 American Vacuum Society.}, language = {en} } @article{PazBecerraSilvaetal.2016, author = {Paz, Cristian and Becerra, Jose and Silva, Mario and Cabrera-Pardo, Jaime and Burgos, Viviana and Heydenreich, Matthias and Schmidt, Bernd}, title = {(-)-8-Oxohobartine a New Indole Alkaloid from Aristotelia chilensis (Mol.) Stuntz}, series = {Records of Natural Products}, volume = {10}, journal = {Records of Natural Products}, publisher = {ACG Publications}, address = {Gebze-Kocaeli}, issn = {1307-6167}, pages = {68 -- 73}, year = {2016}, abstract = {The fruit of Aristotelia chilensis is considered a "super fruit" due to its high concentration of polyphenols displaying exceptional antioxidant capacities ORAC. From maqui berries have been reported several anthocyanins and glycosylated flavonoids, those benefits increase the attention to restudy the plant. From the leaves of A. chilensis several indole alkaloids have been reported, we in addition to aristoteline, aristone, aristoquinoline and 3-fromylindole report the spectroscopic elucidation of 8-oxo-9-dehydromakomakine (1), hobartine (2) and a new alkaloid named 8-oxohobartine (3). Compound 1 to 3 did not show bactericidal activity against E. coli and S. aureus till 200 mu g.}, language = {en} } @article{PavasheElamparuthiHettrichetal.2016, author = {Pavashe, Prashant and Elamparuthi, Elangovan and Hettrich, Cornelia and Moeller, Heiko M. and Linker, Torsten}, title = {Synthesis of 2-Thiocarbohydrates and Their Binding to Concanavalin A}, series = {The journal of organic chemistry}, volume = {81}, journal = {The journal of organic chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {0022-3263}, doi = {10.1021/acs.joc.6b00987}, pages = {8595 -- 8603}, year = {2016}, abstract = {A convenient and general synthesis of 2-thiocarbohydrates via cerium ammonium nitrate oxidation of the thiocyanate ion is described. Radical addition to glycals proceeds with excellent regio- and good stereoselectivities in only one step, deprotection affords water-soluble 2-thio saccharides. Binding studies to Con A have been performed by isothermal titration calorimetry (ITC) and saturation transfer difference (STD) NMR spectroscopy. The 2-thiomannose derivative binds even stronger to Con A than the natural substrate, offering opportunities for new lectin or enzyme inhibitors.}, language = {en} } @article{ParkChengBoekeretal.2016, author = {Park, Sungjune and Cheng, Xiao and B{\"o}ker, Alexander and Tsarkova, Larisa}, title = {Hierarchical Manipulation of Block Copolymer Patterns on 3D Topographic Substrates: Beyond Graphoepitaxy}, series = {Advanced materials}, volume = {28}, journal = {Advanced materials}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0935-9648}, doi = {10.1002/adma.201601098}, pages = {6900 -- +}, year = {2016}, abstract = {Templates of complex nanopatterns in a form of hierarchically sequenced dots and stripes can be generated in block copolymer films on lithography-free 3D topographic substrates. The approach exploits thickness- and swelling-responsive morphological behavior of block copolymers, and demonstrates novel possibilities of topography-guided registration of nanopatterns due to periodic confinement and spontaneous orthogonal flow-fields.}, language = {en} } @article{ParkWaltaRosencrantzetal.2016, author = {Park, H. and Walta, S. and Rosencrantz, Ruben R. and Koerner, A. and Schulte, Christoph and Elling, L. and Richtering, Walter and B{\"o}ker, Alexander}, title = {Micelles from self-assembled double-hydrophilic PHEMA-glycopolymer-diblock copolymers as multivalent scaffolds for lectin binding}, series = {Polymer Chemistry}, volume = {7}, journal = {Polymer Chemistry}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1759-9954}, doi = {10.1039/c5py00797f}, pages = {878 -- 886}, year = {2016}, abstract = {We introduce a novel double-hydrophilic hydroxyethylmethacrylate (HEMA) based diblock glycopolymer which self-assembles into homogeneous spherical micellar structures in water. The micellar structure renders surface-oriented N-acetylglucocosamine (GlcNAc) sugar moieties for strong multivalent glycan-mediated lectin binding. Structural analysis and lectin binding is performed by microscopy methods, dynamic light scattering (DLS) and two-focus fluorescence correlation spectroscopy (2fFCS), revealing a novel micellar type of multivalent sugar binding scaffold with high potential for biomedical applications.}, language = {en} } @article{ParamonovKuehnBandrauk2016, author = {Paramonov, Guennaddi K. and Kuehn, O. and Bandrauk, Andre D.}, title = {Shaped Post-Field Electronic Oscillations in H-2(+) Excited by Two-Cycle Laser Pulses: Three-Dimensional Non-Born-Oppenheimer Simulations}, series = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, volume = {120}, journal = {The journal of physical chemistry : A, Molecules, spectroscopy, kinetics, environment \& general theory}, publisher = {American Chemical Society}, address = {Washington}, issn = {1089-5639}, doi = {10.1021/acs.jpca.5b11599}, pages = {3175 -- 3185}, year = {2016}, abstract = {Quantum dynamics of H-2(+) excited by two-cycle laser pulses with laser carrier frequencies corresponding to the wavelengths lambda(1) = 800 and 200 nm (corresponding to the periods tau(1) = 2.667 and 0.667 fs, respectively) and being linearly polarized along the molecular axis have been studied by the numerical solution of the non-Born-Oppenheimer time-dependent Schrodinger equation within a three-dimensional (3D) model, including the internuclear distance R and electron coordinates z and rho. The amplitudes of the pulses have been chosen such that the energies of H-2(+) after the ends of the laser pulses, < E > approximate to-0.515 au, were close to the dissociation threshold of H-2(+). It is found that there exists a certain characteristic oscillation frequency omega(osc) = 0.2278 au (corresponding to the period tau(osc) = 0.667 fs and the wavelength lambda(osc) = 200 nm) that plays the role of a "carrier" frequency of temporally shaped oscillations of the expectation values <-partial derivative V/partial derivative z) emerging after the ends of the laser pulses, both at lambda(1) = 800 nm and at lambda(1) = 200 nm. Moreover, at lambda(1) = 200 nm, the expectation value < z > also demonstrates temporally shaped oscillations after the end of the laser pulse. In contrast, at lambda(1) = 800 nm, the characteristic oscillation frequency omega(osc) = 0.2278 au appears as the frequency of small-amplitude oscillations of the slowly varying expectation value < z > which makes, after the end of the pulse, an excursion with an amplitude of about 4.5 au along the z axis and returns back to < z > approximate to 0 afterward. It is found that the period of the temporally shaped post-field oscillations of <-partial derivative V/partial derivative z > and < z >, estimated as tau(shp) approximate to 30 fs, correlates with the nuclear motion. It is also shown that vibrational excitation of H-2(+) is accompanied by the formation of "hot" and "cold" vibrational ensembles along the R degree of freedom. Power spectra related to the electron motion in H-2(+) calculated for both the laser-driven z and optically passive rho degrees of freedom in the acceleration form proved to be very interesting. In particular, both odd and even harmonics can be observed.}, language = {en} } @article{PapeWessigBrunner2016, author = {Pape, Simon and Wessig, Pablo and Brunner, Heiko}, title = {Iron Trichloride and Air Mediated Guanylation of Acylthioureas. An Ecological Route to Acylguanidines: Scope and Mechanistic Insights}, series = {The journal of organic chemistry}, volume = {81}, journal = {The journal of organic chemistry}, publisher = {American Chemical Society}, address = {Washington}, issn = {0022-3263}, doi = {10.1021/acs.joc.6b00600}, pages = {4701 -- 4712}, year = {2016}, abstract = {Recently we introduced iron trichloride as an environmentally benign and cost-efficient reagent for the synthesis of N-benzoylguanidines. This highly attractive synthetic approach grants access to a broad spectrum of N-benzoylguanidines under mild conditions in short reaction times. In this work we present an extended scope of Our methodology along with the results obtained from mechanistic studies via in situ IR spectroscopy in combination with LC (liquid chromatography)-MS analyses. On the basis of these new mechanistic insights we were able to optimize the synthetic protocol and to develop an alternative mechanistic proposal. In this context the symbiotic roles of iron trithloride and oxygen in the guanylation process are highlighted.}, language = {en} } @article{OncakWlodarczykSauer2016, author = {Oncak, Milan and Wlodarczyk, Radoslaw and Sauer, Joachim}, title = {Hydration Structures of MgO, CaO, and SrO (001) Surfaces}, series = {The journal of physical chemistry : C, Nanomaterials and interfaces}, volume = {120}, journal = {The journal of physical chemistry : C, Nanomaterials and interfaces}, publisher = {American Chemical Society}, address = {Washington}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.6b07434}, pages = {24762 -- 24769}, year = {2016}, abstract = {Using density functional theory (PBE functional), we show that the degree of surface hydroxylation increases in the MgO, CaO, SrO series, accompanied by an increase in water adsorption energy. Already for water coverage of two monolayers, structures with dissolved M2+. ions are considerably more stable than the intact, nondissolved surface. The dissolved ions above the surface form different patterns including ordered ones (e.g., an infinite stripe) that are preferred for MgO(001) and CaO(001) and disordered ones that are favored for SrO(001). Contrary to previous assignments, an analysis of calculated X-ray photoelectron spectra shows that O(1s) signals arising from OH and H2O groups might coincide in the experimental spectrum.}, language = {en} } @article{OmorogieBabalolaUnuabonahetal.2016, author = {Omorogie, Martins O. and Babalola, Jonathan Oyebamiji and Unuabonah, Emmanuel Iyayi and Song, Weiguo and Gong, Jian Ru}, title = {Efficient chromium abstraction from aqueous solution using a low-cost biosorbent: Nauclea diderrichii seed biomass waste}, series = {Journal of Saudi Chemical Society}, volume = {20}, journal = {Journal of Saudi Chemical Society}, publisher = {Elsevier}, address = {Amsterdam}, issn = {1319-6103}, doi = {10.1016/j.jscs.2012.09.017}, pages = {49 -- 57}, year = {2016}, abstract = {Toxic Cr(III) which poses environmental hazard to flora and fauna was efficiently abstracted by low-cost Nauclea diderrichii seed biomass (NDS) with good sequestral capacity for this metal was investigated in this study. The NDS surface analyses showed that it has a specific surface area of 5.36 m(2)/g and pHpzc of 4.90. Thermogravimetric analysis of NDS showed three consecutive weight losses from 50-200 degrees C (ca. 5\%), 200-400 C (ca. 35\%), >400 degrees C (ca. 10\%), corresponding to external water molecules, structural water molecules and heat induced condensation reactions respectively. Differential thermogram of NDS presented a large endothermic peak between 20-510 degrees C suggesting bond breakage and dissociation with the ultimate release of small molecules. The experimental data showed kinetically fast biosorption with increased initial Cr(III) concentrations, indicating the role of external mass transfer mechanism as the rate controlling mechanism in this adsorption process. The Langmuir biosorption capacity of NDS was 483.81 mg/g. The use of the corrected Akaike Information Criterion tool for ranking equilibrium models suggested that the Freundlich model best described the experimental data, which is an indication of the heterogeneous nature of the active sites on the surface of NDS. N. diderrichii seed biomass is an easily sourced, cheap and environmental friendly biosorbent which will serve as a good and cost effective alternative to activated carbon for the treatment of polluted water and industrial effluents. (C) 2012 King Saud University. Production and hosting by Elsevier B.V. All rights reserved.}, language = {en} } @article{OmorogieBabalolaUnuabonahetal.2016, author = {Omorogie, Martins O. and Babalola, Jonathan Oyebamiji and Unuabonah, Emmanuel Iyayi and Gong, Jian R.}, title = {Clean technology approach for the competitive binding of toxic metal ions onto MnO2 nano-bioextractant}, series = {Clean technologies and environmental policy}, volume = {18}, journal = {Clean technologies and environmental policy}, publisher = {Springer}, address = {New York}, issn = {1618-954X}, doi = {10.1007/s10098-015-1004-z}, pages = {171 -- 184}, year = {2016}, abstract = {The competitive extraction of Cr(III) onto Nauclea diderrichii seed epicarp doped with MnO2 nanoparticles (MnO2 nano-bioextractant (MNB)) in a single and binary batch system was studied. For validity of experimental data, chi square test, root mean square error, sum of the square errors, hybrid fractional error function, Marquart's percent standard deviation and standard absolute error were used. Among the kinetic models used, pseudo-second-order and Langmuir equations gave the best fits for the experimental data, with qe (mg g) for the uptake of Cr(III) in single metal system onto MNB, then Cr(III) with Cd(II), Pb(II), Hg(II), KCl and CaCl2 in binary metal systems onto MNB were 2.611, then 1.989, 1.016, 2.208, 1.249 and 1.868 from kinetic standpoint, respectively. The initial sorption rates, h (mg/g/min), and half lives, t1/2 (min), for the uptake of Cr(III) in single metal system onto MNB, then Cr(III) with Cd(II), Pb(II), Hg(II), KCl and CaCl2 in binary metal system onto MNB were 3.497, then 2.311, 2.274, 0.242, 2.956, 45.568 and 0.747, then 5.769, 1.766, 12.144, 1.762, and 2.415, respectively. Physicochemical surface analyses such as pH of point of zero charge, Brunauer-Emmett-Teller single point and multi-point techniques for surface area analyses, scanning electron microscopy and transmission electron microscopy were done on MNB and MnO2 nanoparticles in order to understand their surface microstructures. Desorption study showed that MNB can be recycled and used for future study. Hence, MNB showed good potential to remediate Cr(III) from wastewaters and polluted water.}, language = {en} } @phdthesis{Oliveira2016, author = {Oliveira, Joana Santos Lapa}, title = {Role of different ceramides on the nanostructure of Stratum Corneum models and the influence of selected penetration enhancers}, school = {Universit{\"a}t Potsdam}, pages = {125}, year = {2016}, language = {en} } @article{OlejkoCywińskiBald2016, author = {Olejko, Lydia and Cywiński, Piotr J. and Bald, Ilko}, title = {An ion-controlled four-color fluorescent telomeric switch on DNA origami structures}, series = {Nanoscale}, volume = {8}, journal = {Nanoscale}, publisher = {RSC Publ.}, address = {Cambridge}, issn = {2040-3372}, doi = {10.1039/C6NR00119J}, pages = {10339 -- 10347}, year = {2016}, abstract = {The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using F{\"o}rster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.}, language = {en} } @article{OlejkoCywinskiBald2016, author = {Olejko, Lydia and Cywinski, P. J. and Bald, Ilko}, title = {An ion-controlled four-color fluorescent telomeric switch on DNA origami structures}, series = {Nanoscale}, volume = {8}, journal = {Nanoscale}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2040-3364}, doi = {10.1039/c6nr00119j}, pages = {10339 -- 10347}, year = {2016}, abstract = {The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using Forster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.}, language = {en} } @article{OertelKellerPrinzetal.2016, author = {Oertel, Jana and Keller, Adrian and Prinz, Julia and Schreiber, Benjamin and Huebner, Rene and Kerbusch, Jochen and Bald, Ilko and Fahmy, Karim}, title = {Anisotropic metal growth on phospholipid nanodiscs via lipid bilayer expansion}, series = {Scientific reports}, volume = {6}, journal = {Scientific reports}, publisher = {Nature Publ. Group}, address = {London}, issn = {2045-2322}, doi = {10.1038/srep26718}, pages = {9}, year = {2016}, abstract = {Self-assembling biomolecules provide attractive templates for the preparation of metallic nanostructures. However, the intuitive transfer of the "outer shape" of the assembled macromolecules to the final metallic particle depends on the intermolecular forces among the biomolecules which compete with interactions between template molecules and the metal during metallization. The shape of the bio-template may thus be more dynamic than generally assumed. Here, we have studied the metallization of phospholipid nanodiscs which are discoidal particles of similar to 10 nm diameter containing a lipid bilayer similar to 5 nm thick. Using negatively charged lipids, electrostatic adsorption of amine-coated Au nanoparticles was achieved and followed by electroless gold deposition. Whereas Au nanoparticle adsorption preserves the shape of the bio-template, metallization proceeds via invasion of Au into the hydrophobic core of the nanodisc. Thereby, the lipidic phase induces a lateral growth that increases the diameter but not the original thickness of the template. Infrared spectroscopy reveals lipid expansion and suggests the existence of internal gaps in the metallized nanodiscs, which is confirmed by surface-enhanced Raman scattering from the encapsulated lipids. Interference of metallic growth with non-covalent interactions can thus become itself a shape-determining factor in the metallization of particularly soft and structurally anisotropic biomaterials.}, language = {en} } @article{NiedlBerensteinBeta2016, author = {Niedl, Robert Raimund and Berenstein, Igal and Beta, Carsten}, title = {How imperfect mixing and differential diffusion accelerate the rate of nonlinear reactions in microfluidic channels}, series = {Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies}, volume = {18}, journal = {Physical chemistry, chemical physics : PCCP ; a journal of European Chemical Societies}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1463-9076}, doi = {10.1039/c6cp00224b}, pages = {6451 -- 6457}, year = {2016}, abstract = {In this paper, we show experimentally that inside a microfluidic device, where the reactants are segregated, the reaction rate of an autocatalytic clock reaction is accelerated in comparison to the case where all the reactants are well mixed. We also find that, when mixing is enhanced inside the microfluidic device by introducing obstacles into the flow, the clock reaction becomes slower in comparison to the device where mixing is less efficient. Based on numerical simulations, we show that this effect can be explained by the interplay of nonlinear reaction kinetics (cubic autocatalysis) and differential diffusion, where the autocatalytic species diffuses slower than the substrate.}, language = {en} } @article{NaolouLendleinNeffe2016, author = {Naolou, Toufik and Lendlein, Andreas and Neffe, Axel T.}, title = {Influence of metal softness on the metal-organic catalyzed polymerization of inorpholin-2,5-diones to oligodepsipeptides}, series = {European polymer journal}, volume = {85}, journal = {European polymer journal}, publisher = {Elsevier}, address = {Oxford}, issn = {0014-3057}, doi = {10.1016/j.eurpolymj.2016.10.011}, pages = {139 -- 149}, year = {2016}, language = {en} } @article{MondalMarquardtJaniaketal.2016, author = {Mondal, Suvendu Sekhar and Marquardt, Dorothea and Janiak, Christoph and Holdt, Hans-J{\"u}rgen}, title = {Use of a 4,5-dicyanoimidazolate anion based ionic liquid for the synthesis of iron and silver nanoparticles}, series = {Dalton transactions : an international journal of inorganic chemistry}, journal = {Dalton transactions : an international journal of inorganic chemistry}, number = {45}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-9226}, doi = {10.1039/C6DT00225K}, pages = {5476 -- 5483}, year = {2016}, abstract = {Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N′-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of -22 to -71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures.}, language = {en} } @article{MondalMarquardtJaniaketal.2016, author = {Mondal, Suvendu Sekhar and Marquardt, Dorothea and Janiak, Christoph and Holdt, Hans-J{\"u}rgen}, title = {Use of a 4,5-dicyanoimidazolate anion based ionic liquid for the synthesis of iron and silver nanoparticles}, series = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, volume = {45}, journal = {Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1477-9226}, doi = {10.1039/c6dt00225k}, pages = {5476 -- 5483}, year = {2016}, abstract = {Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N\&\#8242;-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of \&\#8722;22 to \&\#8722;71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures.}, language = {en} } @misc{MondalHoldt2016, author = {Mondal, Suvendu Sekhar and Holdt, Hans-J{\"u}rgen}, title = {Breaking Down Chemical Weapons by Metal-Organic Frameworks}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {55}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201508407}, pages = {42 -- 44}, year = {2016}, abstract = {Seek and destroy: Filtration schemes and self-detoxifying protective fabrics based on the ZrIV-containing metal—organic frameworks (MOFs) MOF-808 and UiO-66 doped with LiOtBu have been developed that capture and hydrolytically detoxify simulants of nerve agents and mustard gas. Both MOFs function as highly catalytic elements in these applications.}, language = {en} } @article{MondalBhuniaAttallahetal.2016, author = {Mondal, Suvendu Sekhar and Bhunia, Asamanjoy and Attallah, Ahmed G. and Matthes, Philipp R. and Kelling, Alexandra and Schilde, Uwe and M{\"u}ller-Buschbaum, Klaus and Krause-Rehberg, Reinhard and Janiak, Christoph and Holdt, Hans-J{\"u}rgen}, title = {Study of the Discrepancies between Crystallographic Porosity and Guest Access into Cadmium-Imidazolate Frameworks and Tunable Luminescence Properties by Incorporation of Lanthanides}, series = {Chemistry - a European journal}, volume = {22}, journal = {Chemistry - a European journal}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201504757}, pages = {6905 -- 6913}, year = {2016}, abstract = {An extended member of the isoreticular family of metal-imidazolate framework structures, IFP-6 (IFP=imidazolate framework Potsdam), based on cadmium metal and an in situ functionalized 2-methylimidazolate-4-amide-5-imidate linker is reported. A porous 3D framework with 1D hexagonal channels with accessible pore windows of 0.52nm has been synthesized by using an ionic liquid (IL) linker precursor. IFP-6 shows significant gas uptake capacity only for CO2 and CH4 at elevated pressure, whereas it does not adsorb N-2, H-2, and CH4 under atmospheric conditions. IFP-6 is assumed to deteriorate at the outside of the material during the activation process. This closing of the metal-organic framework (MOF) pores is proven by positron annihilation lifetime spectroscopy (PALS), which revealed inherent crystal defects. PALS results support the conservation of the inner pores of IFP-6. IFP-6 has also been successfully loaded with luminescent trivalent lanthanide ions (Ln(III)=Tb, Eu, and Sm) in a bottom-up one-pot reaction through the in situ generation of the linker ligand and in situ incorporation of photoluminescent Ln ions into the constituting network. The results of photoluminescence investigations and powder XRD provide evidence that the Ln ions are not doped as connectivity centers into the frameworks, but are instead located within the pores of the MOFs. Under UV light irradiation, Tb@IFP-6 and Eu@IFP-6 ((exc)=365nm) exhibit observable emission changes to a greenish and reddish color, respectively, as a result of strong Ln 4f emissions.}, language = {en} } @article{MeilingCywińskiBald2016, author = {Meiling, Till Thomas and Cywiński, Piotr J. and Bald, Ilko}, title = {White carbon: Fluorescent carbon nanoparticles with tunable quantum yield in a reproducible green synthesis}, series = {Scientific reports}, volume = {6}, journal = {Scientific reports}, publisher = {Nature Publishing Group}, address = {London}, doi = {10.1038/srep28557}, pages = {9}, year = {2016}, abstract = {In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (>1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1\% up to 28\% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.}, language = {en} } @article{MeilingCywinskiBald2016, author = {Meiling, Till T. and Cywinski, Piotr J. and Bald, Ilko}, title = {White carbon: Fluorescent carbon nanoparticles with tunable quantum yield in a reproducible green synthesis}, series = {Scientific reports}, volume = {6}, journal = {Scientific reports}, publisher = {Nature Publ. Group}, address = {London}, issn = {2045-2322}, doi = {10.1038/srep28557}, pages = {9}, year = {2016}, abstract = {In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (> 1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1\% up to 28\% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.}, language = {en} }