TY - JOUR A1 - Goldhahn, Christian A1 - Schubert, Jonas A1 - Schlaad, Helmut A1 - Ferri, James K. A1 - Fery, Andreas A1 - Chanana, Munish T1 - Synthesis of Metal@Protein@Polymer Nanoparticles with Distinct Interfacial and Phase Transfer Behavior JF - Chemistry of materials : a publication of the American Chemical Society N2 - In this study, we present a novel and facile method for the synthesis of multiresponsive plasmonic nanoparticles with an interesting interfacial behavior. We used thiol-initiated photopolymerization technique to graft poly(N-isopropylacrylamide) onto the surface of protein-coated gold nanoparticles. The combination of the protein bovine serum albumin with the thermoresponsive polymer leads to smart hybrid nanoparticles, which show a stimuli-responsive behavior of their aggregation and a precisely controllable phase transfer behavior. Three interconnected stimuli, namely, temperature, ionic strength, and pH, were identified as property tuning switches. The aggregation was completely reversible and was quantified by determining Smoluchowski’s instability ratios with time-resolved dynamic light scattering. The tunable hydrophobicity via the three stimuli was used to study interfacial activity and phase transfer behavior of the nanoparticles at an octanol/water interface. Depending on the type of coating (i.e., protein or protein/polymer) as well as the three external stimuli, the nanoparticles either remained in the aqueous phase (aggregated or nonaggregated), accumulated at the oil/water interface, wet the glass wall between the glass vial and the octanol phase, or even crossed the oil/water interface. Such smart and interfacially active nanoparticles with external triggers that are capable of crossing oil/water interfaces under physiological conditions open up new avenues for a variety of applications ranging from the development of drug-delivery nanosystems across biological barriers to the preparation of new catalytic materials. Y1 - 2018 U6 - https://doi.org/10.1021/acs.chemmater.8b02314 SN - 0897-4756 SN - 1520-5002 VL - 30 IS - 19 SP - 6717 EP - 6727 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Ehlert, Christopher A1 - Gühr, Markus A1 - Saalfrank, Peter T1 - An efficient first principles method for molecular pump-probe NEXAFS spectra BT - application to thymine and azobenzene JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr N2 - Pump-probe near edge X-ray absorption fine structure (PP-NEXAFS) spectra of molecules offer insight into valence-excited states, even if optically dark. In PP-NEXAFS spectroscopy, the molecule is "pumped" by UV or visible light enforcing a valence excitation, followed by an X-ray "probe" exciting core electrons into (now) partially empty valence orbitals. Calculations of PP-NEXAFS have so far been done by costly, correlated wavefunction methods which are not easily applicable to medium-sized or large molecules. Here we propose an efficient, first principles method based on density functional theory in combination with the transition potential and Delta SCF methodology (TP-DFT/Delta SCF) to compute molecular ground state and PP-NEXAFS spectra. We apply the method to n ->pi* pump/O-K-edge NEXAFS probe spectroscopy of thymine (for which both experimental and other theoretical data exist) and to n -> pi* or pi -> pi* pump/N-K-edge NEXAFS probe spectroscopies of trans-and cis-azobenzene. Published by AIP Publishing. Y1 - 2018 U6 - https://doi.org/10.1063/1.5050488 SN - 0021-9606 SN - 1089-7690 VL - 149 IS - 14 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Sun, Zhiyong A1 - Glebe, Ulrich A1 - Charan, Himanshu A1 - Böker, Alexander A1 - Wu, Changzhu T1 - Enzyme-Polymer Conjugates as Robust Pickering Interfacial Biocatalysts for Efficient Biotransformations and One-Pot Cascade Reactions JF - Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition N2 - Despite the rapid development of Pickering interfacial catalysis (PIC) at liquid-liquid interfaces with chemocatalysts, the use of unstable biocatalysts at emulsion interfaces remains a technical challenge. Herein, we present a Pickering interfacial biocatalysis (PIB) platform based on robust and recyclable enzyme-polymer conjugates that act as both catalytic sites and stabilizers at the interface of Pickering emulsions. The conjugates were prepared by growing poly(N-isopropylacrylamide) on a fragile enzyme, benzaldehyde lyase, under physiological conditions. The mild in situ conjugation process preserved the enzyme structure, and the conjugates were used to emulsify a water-organic two-phase system into a stable Pickering emulsion, leading to a significantly larger interfacial area and a 270-fold improvement in catalytic performance as compared to the unemulsified two-phase system. The PIB system could be reused multiple times. Conjugates of other enzymes were also fabricated and applied for cascade reactions. KW - biphasic catalysis KW - cascade reactions KW - enzyme catalysis KW - enzyme-polymer conjugates KW - Pickering interfacial catalysis Y1 - 2018 U6 - https://doi.org/10.1002/anie.201806049 SN - 1433-7851 SN - 1521-3773 VL - 57 IS - 42 SP - 13810 EP - 13814 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Turrini, Nikolaus G. A1 - Kroepfl, Nina A1 - Jensen, Kenneth Bendix A1 - Reiter, Tamara C. A1 - Francesconi, Kevin A. A1 - Schwerdtle, Tanja A1 - Kroutil, Wolfgang A1 - Kuehnelt, Doris T1 - Biosynthesis and isolation of selenoneine from genetically modified fission yeast JF - Metallomics : integrated biometal science N2 - Selenoneine, a naturally occurring form of selenium, is the selenium analogue of ergothioneine, a sulfur species with health relevance not only as a purported antioxidant but likely also beyond. Selenoneine has been speculated to exhibit similar effects. To study selenoneine's health properties as well as its metabolic transformation, the pure compound is required. Chemical synthesis of selenoneine, however, is challenging and biosynthetic approaches have been sought. We herein report the biosynthesis and isolation of selenoneine from genetically modified fission yeast Schizosaccharomyces pombe grown in a medium containing sodium selenate. After cell lysis and extraction with methanol, selenoneine was purified by three consecutive preparative reversed-phase HPLC steps. The product obtained at the mg level was characterised by high resolution mass spectrometry, NMR and HPLC/ICPMS. Biosynthesis was found to be a promising alternative to chemical synthesis, and should be suitable for upscaling to produce higher amounts of this important selenium species in the future. Y1 - 2018 U6 - https://doi.org/10.1039/c8mt00200b SN - 1756-5901 SN - 1756-591X VL - 10 IS - 10 SP - 1532 EP - 1538 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Tadjoung Waffo, Armel Franklin A1 - Yesildag, Cigdem A1 - Caserta, Giorgio A1 - Katz, Sagie A1 - Zebger, Ingo A1 - Lensen, Marga C. A1 - Wollenberger, Ulla A1 - Scheller, Frieder W. A1 - Altintas, Zeynep T1 - Fully electrochemical MIP sensor for artemisinin JF - Sensors and actuators : B, Chemical N2 - This study aims to develop a rapid, sensitive and cost-effective biomimetic electrochemical sensor for artemisinin determination in plant extracts and for pharmacokinetic studies. A novel molecularly imprinted polymer (MIP)based electrochemical sensor was developed by electropolymerization of o-phenylenediamine (o-PD) in the presence of artemisinin on gold wire surface for sensitive detection of artemisinin. The experimental parameters, including selection of functional monomer, polymerization conditions, template extraction after polymerization, influence of pH and buffer were all optimized. Every step of imprinted film synthesis were evaluated by employing voltammetry techniques, surface-enhanced infrared absorption spectroscopy (SEIRAS) and atomic force microscopy (AFM). The specificity was further evaluated by investigating non-specific artemisinin binding on non-imprinted polymer (NIP) surfaces and an imprinting factor of 6.8 was achieved. The artemisinin imprinted polymers using o-PD as functional monomer have provided highly stable and effective binding cavities for artemisinin. Cross-reactivity studies with drug molecules showed that the MIPs are highly specific for artemisinin. The influence of matrix effect was further investigated both in artificial plant matrix and diluted human serum. The results revealed a high affinity of artemisinin-MIP with dissociation constant of 7.3 x 10(-9) M and with a detection limit of 0.01 mu M and 0.02 mu M in buffer and plant matrix, respectively. KW - Electro-synthesized molecularly imprinted polymer KW - o-Phenylenediamine KW - Artemisinin KW - Antimalarial drug detection KW - Electrochemical sensor Y1 - 2018 U6 - https://doi.org/10.1016/j.snb.2018.08.018 SN - 0925-4005 VL - 275 SP - 163 EP - 173 PB - Elsevier CY - Lausanne ER - TY - JOUR A1 - Büchner, Dörthe A1 - John, Leonard A1 - Mertens, Monique A1 - Wessig, Pablo T1 - Detection of dsDNA with [1,3]Dioxolo[4,5-f]benzodioxol (DBD) Dyes JF - Chemistry - a European journal N2 - DBD fluorescent dyes have proven to be useful in numerous applications. To widen the range of biological applications, we propose three different types of DBD molecules that have been modified in such a way that DNA interaction becomes probable. After the successful synthesis of all three compounds, we tested their fluorescent properties and their DNA binding abilities. Two of the three probes exhibit an interaction with dsDNA with subsequent fluorescence enhancement. The determined binding constants of the two new DNA dyes are comparable to other minorgroove-binding dyes. Their large Stokes shifts and their long fluorescent lifetimes are outstanding features of these dyes. KW - DNA recognition KW - dyes/pigments KW - fluorescent probes KW - heterocycles KW - scatchard plot Y1 - 2018 U6 - https://doi.org/10.1002/chem.201804057 SN - 0947-6539 SN - 1521-3765 VL - 24 IS - 60 SP - 16183 EP - 16190 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Schulz, Eike C. A1 - Mehrabi, Pedram A1 - Müller-Werkmeister, Henrike A1 - Tellkamp, Friedjof A1 - Jha, Ajay A1 - Stuart, William A1 - Persch, Elke A1 - De Gasparo, Raoul A1 - Diederich, François A1 - Pai, Emil F. A1 - Miller, R. J. Dwayne T1 - The hit-and-return system enables efficient time-resolved serial synchrotron crystallography JF - Nature methods : techniques for life scientists and chemists N2 - We present a ‘hit-and-return’ (HARE) method for time-resolved serial synchrotron crystallography with time resolution from milliseconds to seconds or longer. Timing delays are set mechanically, using the regular pattern in fixed-target crystallography chips and a translation stage system. Optical pump-probe experiments to capture intermediate structures of fluoroacetate dehalogenase binding to its ligand demonstrated that data can be collected at short (30 ms), medium (752 ms) and long (2,052 ms) intervals. KW - Biophysical chemistry KW - Enzymes KW - Molecular biophysics KW - X-ray crystallography Y1 - 2018 U6 - https://doi.org/10.1038/s41592-018-0180-2 SN - 1548-7091 SN - 1548-7105 VL - 15 IS - 11 SP - 901 EP - 904 PB - Nature Publishing Group (London) CY - London ER - TY - JOUR A1 - Riemer, Nastja A1 - Coswig, Christin A1 - Shipman, Michael A1 - Schmidt, Bernd T1 - Palladium-catalyzed cross-coupling of arenediazonium salts with organoindium or organobismuth reagents JF - Synlett : accounts and rapid communications in synthetic organic chemistry N2 - Arylindium and isolated triarylbismuth compounds generated in situ react as nucleophiles with arenediazonium salts in palladium-catalyzed cross-coupling reactions to give substituted biphenyls. KW - Palladium-catalyzed cross-coupling of arenediazonium salts with organoindium or organobismuth reagents Y1 - 2018 U6 - https://doi.org/10.1055/s-0037-1611001 SN - 0936-5214 SN - 1437-2096 VL - 29 IS - 18 SP - 2427 EP - 2431 PB - Georg Thieme Verlag KG CY - Stuttgart ER - TY - JOUR A1 - Hardy, John G. A1 - Bertin, Annabelle A1 - Torres-Rendon, Jose Guillermo A1 - Leal-Egana, Aldo A1 - Humenik, Martin A1 - Bauer, Felix A1 - Walther, Andreas A1 - Cölfen, Helmut A1 - Schlaad, Helmut A1 - Scheibel, Thomas R. T1 - Facile photochemical modification of silk protein-based biomaterials JF - Macromolecular bioscience N2 - Silk protein-based materials show promise for application as biomaterials for tissue engineering. The simple and rapid photochemical modification of silk protein-based materials composed of either Bombyx mori silkworm silk or engineered spider silk proteins (eADF4(C16)) is reported. Radicals formed on the silk-based materials initiate the polymerization of monomers (acrylic acid, methacrylic acid, or allylamine) which functionalize the surface of the silk materials with poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), or poly(allylamine) (PAAm). To demonstrate potential applications of this type of modification, the polymer-modified silks are mineralized. The PAA- and PMAA-functionalized silks are mineralized with calcium carbonate, whereas the PAAm-functionalized silks are mineralized with silica, both of which provide a coating on the materials that may be useful for bone tissue engineering, which will be the subject of future investigations. KW - biomaterials KW - chemical modification KW - photochemistry KW - silkworm silk KW - spider silk Y1 - 2018 U6 - https://doi.org/10.1002/mabi.201800216 SN - 1616-5187 SN - 1616-5195 VL - 18 IS - 11 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Zheng, Botuo A1 - Bai, Tianwen A1 - Tao, Xinfeng A1 - Schlaad, Helmut A1 - Ling, Jun T1 - Identifying the Hydrolysis of Carbonyl Sulfide as a Side Reaction Impeding the Polymerization of N-Substituted Glycine N-Thiocarboxyanhydride JF - Biomacromolecules : an interdisciplinary journal focused at the interface of polymer science and the biological sciences N2 - Polypeptoids are noticeable biological materials due to their versatile properties and various applications in drug delivery, surface modification, self-assembly, etc. N-Substituted glycine N-thiocarboxyanhydrides (NNTAs) are more stable monomers than the corresponding N-carboxyanhydrides (NNCAs) and enable one to prepare polypeptoids via ring-opening polymerization even in the presence of water. However, larger amounts of water (>10,000 ppm) cause inhibition of the polymerization. Herein, we discover that during polymerization hydrogen sulfide evolves from the hydrolysis of carbonyl sulfide, which is the byproduct of ring-opening reaction, and reacts with NNTA to produce cyclic oligopeptoids. The capture of N-ethylethanethioic acid as an intermediate product confirms the reaction mechanism together with density functional theory quantum computational results. By bubbling the polymerization solution with argon, the side reaction can be suppressed to allow the synthesis of polysarcosine with high molar mass (M-n = 11,200 g/mol, D = 1.25) even in the presence of similar to 10,000 ppm of water. Y1 - 2018 U6 - https://doi.org/10.1021/acs.biomac.8b01119 SN - 1525-7797 SN - 1526-4602 VL - 19 IS - 11 SP - 4263 EP - 4269 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kutlug, Oezgür A1 - Hass, Roland A1 - Reck, Stephan A1 - Hartwig, Andreas T1 - Inline characterization of dispersion formation of a solvent-borne acrylic copolymer by Photon Density Wave spectroscopy JF - Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects N2 - Most investigations on phase inversion (PI) of resins upon addition of water have been carried out by dynamic light scattering (DLS), torque, and viscosity measurements. The main problem, however, is analytic discontinuity due to sample removal and a changing matrix due to dilution during the preparation of the aqueous resin dispersions. This work presents Photon Density Wave (PDW) spectroscopy as a tool for the inline characterization of the acetone process for an acrylic copolymer with high acrylic acid (AA) content. PDW spectroscopy revealed different trends for optical properties compared to torque during water feed. Also the absence of PI due to dissolution of copolymer in the solvent/water mixture is observed by PDW spectroscopy. PI for the investigated copolymer did not occour during water feed but during removal of solvent. Different feeding rates of water gave similar trends while a change in temperature and degree of AA neutralization led to changes in optical properties and torque. Thermal processing showed that the optical properties of mixtures prior and after removal of solvent were completely different caused by changes of solubility. KW - Acetone process KW - Dispersion KW - Photon Density Wave spectroscopy KW - Radical polymerization KW - Torque KW - Turbid media Y1 - 2018 U6 - https://doi.org/10.1016/j.colsurfa.2018.08.011 SN - 0927-7757 SN - 1873-4359 VL - 556 SP - 113 EP - 119 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Burek, Katja A1 - Krause, Felix A1 - Schwotzer, Matthias A1 - Nefedov, Alexei A1 - Süssmuth, Julia A1 - Haubitz, Toni A1 - Kumke, Michael Uwe A1 - Thissen, Peter T1 - Hydrophobic Properties of Calcium-Silicate Hydrates Doped with Rare-Earth Elements JF - ACS sustainable chemistry & engineering N2 - In this study, the apparent relationship between the transport process and the surface chemistry of the Calcium-Silicate Hydrate (CSH) phases was investigated. For this purpose, a method was developed to synthesize ultrathin CSH phases to be used as a model substrate with the specific modification of their structure by introducing europium (Eu(III)). The structural and chemical changes during this Eu(III)-doping were observed by means of infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), and time-resolved laser fluorescence spectroscopy (TRLFS). These alterations of the CSH phases led to significant changes in the surface chemistry and consequently to considerable variations in the interaction with water, as evidenced by measurements of the contact angles on the modified model substrates. Our results provide the basis for a more profound molecular understanding of reactive transport processes in cement-based systems. Furthermore, these results broaden the perspective of improving the stability of cement-based materials, which are subjected to the impact of aggressive aqueous environments through targeted modifications of the CSH phases. KW - Rare-earth elements KW - Europium KW - Luminescence KW - Metal-proton exchange reaction KW - Contact angle KW - Infrared spectroscopy KW - X-ray photoelectron spectroscopy Y1 - 2018 U6 - https://doi.org/10.1021/acssuschemeng.8b03244 SN - 2168-0485 VL - 6 IS - 11 SP - 14669 EP - 14678 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Hänsel, Marc A1 - Barta, Christoph A1 - Rietze, Clemens A1 - Utecht, Manuel Martin A1 - Rueck-Braun, Karola A1 - Saalfrank, Peter A1 - Tegeder, Petra T1 - Two-Dimensional Nonlinear Optical Switching Materials BT - Molecular Engineering toward High Nonlinear Optical Contrasts JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Combining photochromism and nonlinear optical (NLO) properties of molecular switches-functionalized self-assembled monolayers (SAMs) represents a promising concept toward novel photonic and optoelectronic devices. Using second harmonic generation, density functional theory, and correlated wave function methods, we studied the switching abilities as well as the NLO contrasts between different molecular states of various fulgimide-containing SAMs on Si(111). Controlled variations of the linker systems as well as of the fulgimides enabled us to demonstrate very efficient reversible photoinduced ring-opening/closure reactions between the open and closed forms of the fulgimides. Thus, effective cross sections on the order of 10(-18) cm(-2) are observed. Moreover, the reversible switching is accompanied by pronounced NLO contrasts up to 32%. Further molecular engineering of the photochromic switches and the linker systems may even increase the NLO contrast upon switching. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpcc.8b08212 SN - 1932-7447 SN - 1932-7455 VL - 122 IS - 44 SP - 25555 EP - 25564 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Xiong, Tao A1 - Wlodarczyk, Radoslaw A1 - Saalfrank, Peter T1 - Vibrationally resolved absorption and fluorescence spectra of perylene and N-substituted derivatives from autocorrelation function approaches JF - Chemical physics : a journal devoted to experimental and theoretical research involving problems of both a chemical and physical nature N2 - Vibrationally resolved absorption and emission (fluorescence) spectra of perylene and its N-derivatives in gas phase and in solution (acetonitrile) were simulated using a time-dependent approach based on correlation functions determined by density functional theory. By systematically varying the number and position of N atoms, it is shown that the presence of nitrogen heteroatoms has a negligible effect on the molecular structure and geometric distortions upon electronic transitions, while spectral properties change: in particular the number of N atoms is important while their position is less decisive. Thus, the N-substitution can be used to fine-tune the optical properties of perylene-based molecules. KW - Perylene KW - Vibronic spectrum KW - Correlation function KW - Dimer KW - Excimer KW - PCM Y1 - 2018 U6 - https://doi.org/10.1016/j.chemphys.2018.06.011 SN - 0301-0104 SN - 1873-4421 VL - 515 SP - 728 EP - 736 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Utecht, Manuel Martin A1 - Gaebel, Tina A1 - Klamroth, Tillmann T1 - Desorption induced by low energy charge carriers on Si(111)-7 x 7 BT - first principles molecular dynamics for benzene derivates JF - Journal of computational chemistry : organic, inorganic, physical, biological N2 - We use clusters for the modeling of local ion resonances caused by low energy charge carriers in STM-induced desorption of benzene derivates from Si(111)-7 x 7. We perform Born-Oppenheimer molecular dynamics for the charged systems assuming vertical transitions to the charged states at zero temperature, to rationalize the low temperature activation energies, which are found in experiment for chlorobenzene. Our calculations suggest very similar low temperature activation energies for toluene and benzene. For the cationic resonance transitions to physisorption are found even at 0 K, while the anion remains chemisorbed during the propagations. Further, we also extend our previous static quantum chemical investigations to toluene and benzene. In addition, an in depth analysis of the ionization potentials and electron affinities, which are used to estimate resonance energies, is given. KW - Born-Oppenheimer MD KW - STM-induced reactions KW - cluster models KW - Si(111)-7x7 Y1 - 2018 U6 - https://doi.org/10.1002/jcc.25607 SN - 0192-8651 SN - 1096-987X VL - 39 IS - 30 SP - 2517 EP - 2525 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Tan, Li A1 - Liu, Bing A1 - Glebe, Ulrich A1 - Böker, Alexander T1 - Magnetic Field-Induced Assembly of Superparamagnetic Cobalt Nanoparticles on Substrates and at Liquid-Air Interface JF - Langmuir N2 - Superparamagnetic cobalt nanoparticles (Co NPs) are an interesting material for self-assembly processes because of their magnetic properties. We investigated the magnetic field-induced assembly of superparamagnetic cobalt nanoparticles and compared three different approaches, namely, the assembly on solid substrates, at water-air, and ethylene glycol-air interfaces. Oleic acid- and trioctylphosphine oxide-coated Co NPs were synthesized via a thermolysis of cobalt carbonyl and dispersed into either hexane or toluene. The Co NP dispersion was dropped onto different substrates (e.g., transmission electron microscopy (TEM) grid, silicon wafer) and onto liquid surfaces. Transmission electron microscopy (TEM), scanning force microscopy, optical microscopy, as well as scanning electron microscopy showed that superparamagnetic Co NPs assembled into one-dimensional chains in an external magnetic field. By varying the concentration of the Co NP dispersion (1-5 mg/mL) and the strength of the magnetic field (4-54 mT), the morphology of the chains changed. Short, thin, and flexible chain structures were obtained at low NP concentration and low strength of magnetic field, whereas they became long, thick and straight when the NP concentration and the magnetic field strength increased. In comparison, the assembly of Co NPs from hexane dispersion at ethylene glycol-air interface showed the most regular and homogeneous alignment, since a more efficient spreading could be achieved on ethylene glycol than on water and solid substrates. Y1 - 2018 U6 - https://doi.org/10.1021/acs.langmuir.8b02673 SN - 0743-7463 VL - 34 IS - 46 SP - 13993 EP - 14002 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Yalcinkaya, Hacer A1 - Bressel, Katharina A1 - Lindner, Peter A1 - Gradzielski, Michael T1 - Controlled formation of vesicles with added styrene and their fixation by polymerization JF - Journal of colloid and interface science N2 - Hypothesis: An effective way for fixating vesicle structures is the insertion of monomers and cross-linking agents into their bilayer, and their subsequent polymerization can lead to the formation of polymeric nanocapsules. Particularly attractive here are vesicle systems that form spontaneously well-defined small vesicles, as obtaining such small nanocapsules with sizes below 100 nm is still challenging. Experiments: A spontaneously forming well-defined vesicle system composed of the surfactants TDMAO (tetradecyldimethylamine oxide), Pluronic L35, and LiPFOS (lithium perfluorooctylsulfonate) mixture was used as template for fixation by polymerization. Therefore, styrene monomer was incorporated into the vesicle bilayer and ultimately these structures were fixated by UV induced radical polymerization. Structural alteration of the vesicles upon loading with monomer and the cross-linker as well as the effect of subsequent polymerization in the membrane were investigated in detail by turbidity measurements, dynamic and static light scattering, (DLS, SLS), and small angle neutron scattering (SANS). Findings: The analysis showed the changes on vesicle structures due to the monomer loading, and that these structures can become permanently fixed by the polymerization process. The potential of this approach to produce well-defined nanocapsules starting from a self-assembled system and following polymerization is critically evaluated. (C) 2018 Elsevier Inc. All rights reserved. KW - Template reaction KW - Zwitterionic surfactant KW - Anionic surfactant KW - Styrene KW - Vesicle KW - Small angle neutron scattering KW - Polymerization Y1 - 2018 U6 - https://doi.org/10.1016/j.jcis.2018.07.097 SN - 0021-9797 SN - 1095-7103 VL - 531 SP - 672 EP - 680 PB - Elsevier CY - San Diego ER - TY - JOUR A1 - Peng, Xingzhou A1 - Behl, Marc A1 - Zhang, Pengfei A1 - Mazurek-Budzynska, Magdalena A1 - Feng, Yakai A1 - Lendlein, Andreas T1 - Synthesis of Well-Defined Dihydroxy Telechelics by (Co)polymerization of Morpholine-2,5-Diones Catalyzed by Sn(IV) Alkoxide JF - Macromolecular bioscience N2 - Well-defined dihydroxy telechelic oligodepsipeptides (oDPs), which have a high application potential as building blocks for scaffold materials for tissue engineering applications or particulate carrier systems for drug delivery applications are synthesized by ring-opening polymerization (ROP) of morpholine-2,5-diones (MDs) catalyzed by 1,1,6,6-tetra-n-butyl-1,6-distanna-2,5,7,10-tetraoxacyclodecane (Sn(IV) alkoxide). In contrast to ROP catalyzed by Sn(Oct)(2), the usage of Sn(IV) alkoxide leads to oDPs, with less side products and well-defined end groups, which is crucial for potential pharmaceutical applications. A slightly faster reaction of the ROP catalyzed by Sn(IV) alkoxide compared to the ROP initiated by Sn(Oct)(2)/EG is found. Copolymerization of different MDs resulted in amorphous copolymers with T(g)s between 44 and 54 degrees C depending on the molar comonomer ratios in the range from 25% to 75%. Based on the well-defined telechelic character of the Sn(IV) alkoxide synthesized oDPs as determined by matrix-assisted laser desorption/ionization time of flight measurements, they resemble interesting building blocks for subsequent postfunctionalization or multifunctional materials based on multiblock copolymer systems whereas the amorphous oDP-based copolymers are interesting building blocks for matrices of drug delivery systems. KW - oligodepsipeptides KW - ring-opening polymerization KW - Sn(IV) alkoxide KW - telechelics KW - tin(II) 2-ethylhexanoate Y1 - 2018 U6 - https://doi.org/10.1002/mabi.201800257 SN - 1616-5187 SN - 1616-5195 VL - 18 IS - 12 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Hermanns, Jolanda A1 - Schmidt, Bernd T1 - Developing and Applying Stepped Supporting Tools in Organic Chemistry To Promote Students’ Self-Regulated Learning JF - Journal of chemical education N2 - Stepped supporting tools were developed and used in the university seminar Organic Chemistry taken by nonmajor chemistry students, which supported self-regulated learning. These supporting tools were also used for accompanying homework, which included a QR code that led to additional supporting tools. The application of stepped supporting tools in the seminars was evaluated by a four-item Likert scale. The students assessed the tools as a helpful instrument for solving tasks in chemistry. KW - High School/Introductory Chemistry KW - Organic Chemistry Y1 - 2018 U6 - https://doi.org/10.1021/acs.jchemed.8b00565 SN - 0021-9584 SN - 1938-1328 VL - 96 IS - 1 SP - 47 EP - 52 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Noack, Sebastian A1 - Schanzenbach, Dirk A1 - Koetz, Joachim A1 - Schlaad, Helmut T1 - Polylactide-based amphiphilic block copolymers BT - Crystallization-Induced Self-Assembly and Stereocomplexation JF - Macromolecular rapid communications N2 - The aqueous self-assembly behavior of a series of poly(ethylene glycol)-poly(l-/d-lactide) block copolymers and corresponding stereocomplexes is examined by differential scanning calorimetry, dynamic light scattering, and transmission electron microscopy. Block copolymers assemble into spherical micelles and worm-like aggregates at room temperature, whereby the fraction of the latter seemingly increases with decreasing lactide weight fraction or hydrophobicity. The formation of the worm-like aggregates arises from the crystallization of the polylactide by which the spherical micelles become colloidally unstable and fuse epitaxically with other micelles. The self-assembly behavior of the stereocomplex aggregates is found to be different from that of the block copolymers, resulting in rather irregular-shaped clusters of spherical micelles and pearl-necklace-like structures. KW - crystallization KW - polylactide KW - self-assembly KW - stereocomplexation Y1 - 2018 U6 - https://doi.org/10.1002/marc.201800639 SN - 1022-1336 SN - 1521-3927 VL - 40 IS - 1 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Heck, Christian A1 - Michaeli, Yael A1 - Bald, Ilko A1 - Ebenstein, Yuval T1 - Analytical epigenetics BT - single-molecule optical detection of DNA and histone modifications JF - Current Opinion in Biotechnology N2 - The field of epigenetics describes the relationship between genotype and phenotype, by regulating gene expression without changing the canonical base sequence of DNA. It deals with molecular genomic information that is encoded by a rich repertoire of chemical modifications and molecular interactions. This regulation involves DNA, RNA and proteins that are enzymatically tagged with small molecular groups that alter their physical and chemical properties. It is now clear that epigenetic alterations are involved in development and disease, and thus, are the focus of intensive research. The ability to record epigenetic changes and quantify them in rare medical samples is critical for next generation diagnostics. Optical detection offers the ultimate single-molecule sensitivity and the potential for spectral multiplexing. Here we review recent progress in ultrasensitive optical detection of DNA and histone modifications. Y1 - 2018 U6 - https://doi.org/10.1016/j.copbio.2018.09.006 SN - 0958-1669 SN - 1879-0429 VL - 55 SP - 151 EP - 158 PB - Elsevier CY - London ER - TY - JOUR A1 - Jiang, Yi A1 - Mansfeld, Ulrich A1 - Fang, Liang A1 - Kratz, Karl A1 - Lendlein, Andreas T1 - Temperature-induced evolution of microstructures on poly[ethylene-co-(vinyl acetate)] substrates switches their underwater wettability JF - Materials & design N2 - Material surfaces with tailored aerophobicity are crucial for applications where gas bubble wettability has to be controlled, e.g., gas storage and transport, electrodes, bioreactors or medical devices. Here, we present switchable underwater aerophobicity of hydrophobic polymeric substrates, which respond to heat with multilevel micro-and nanotopographical changes. The cross-linked poly[ethylene-co-(vinyl acetate)] substrates possess arrays of microcylinders with a nanorough top surface. It is hypothesized that the specific micro-/nanotopography of the surface allows trapping of a water film at the micro interspace and in this way generates the aerophobic behavior. The structured substrates were programmed to a temporarily stable, nanoscale flat substrate showing aerophilic behavior. Upon heating, the topographical changes caused a switch in contact angle from aerophilic to aerophobic for approaching air bubbles. In this way, the initial adhesion of air bubbles to the programmed flat substrate could be turned into repellence for the recovered substrate surface. The temperature at which the repellence of air bubbles starts can be adjusted from 58 +/- 3 degrees C to 73 +/- 3 degrees C by varying the deformation temperature applied during the temperature-memory programming procedure. The presented actively switching polymeric substrates are attractive candidates for applications, where an on-demand gas bubble repellence is advantageous. (c) 2018 Helmholtz-Zentrum Geesthacht, Zentrum fur Material- und Kustenforschung. Published by Elsevier Ltd. KW - Aerophobicity KW - Temperature-memory effect KW - Switchable wettability KW - Air bubble repellence KW - Thermo-responsive polymer Y1 - 2018 U6 - https://doi.org/10.1016/j.matdes.2018.12.002 SN - 0264-1275 SN - 1873-4197 VL - 163 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Xu, Xiao A1 - Angioletti-Uberti, Stefano A1 - Lu, Yan A1 - Dzubiella, Joachim A1 - Ballauff, Matthias T1 - Interaction of Proteins with Polyelectrolytes BT - Comparison of Theory to Experiment JF - Langmuir N2 - We discuss recent investigations of the interaction of polyelectrolytes with proteins. In particular, we review our recent studies on the interaction of simple proteins such as human serum albumin (HSA) and lysozyme with linear polyelectrolytes, charged dendrimers, charged networks, and polyelectrolyte brushes. In all cases discussed here, we combined experimental work with molecular dynamics (MD) simulations and mean-field theories. In particular, isothermal titration calorimetry (ITC) has been employed to obtain the respective binding constants K-b and the Gibbs free energy of binding. MD simulations with explicit counterions but implicit water demonstrate that counterion release is the main driving force for the binding of proteins to strongly charged polyelectrolytes: patches of positive charges located on the surface of the protein become multivalent counterions of the polyelectrolyte, thereby releasing a number of counterions condensed on the polyelectrolyte. The binding Gibbs free energy due to counterion release is predicted to scale with the logarithm of the salt concentration in the system, which is verified by both simulations and experiment. In several cases, namely, for the interaction of proteins with linear polyelectrolytes and highly charged hydrophilic dendrimers, the binding constant could be calculated from simulations to very good approximation. This finding demonstrated that in these cases explicit hydration effects do not contribute to the Gibbs free energy of binding. The Gibbs free energy can also be used to predict the kinetics of protein uptake by microgels for a given system by applying dynamic density functional theory. The entire discussion demonstrates that the direct comparison of theory with experiments can lead to a full understanding of the interaction of proteins with charged polymers. Possible implications for applications, such as drug design, are discussed. Y1 - 2018 U6 - https://doi.org/10.1021/acs.langmuir.8b01802 SN - 0743-7463 VL - 35 IS - 16 SP - 5373 EP - 5391 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lützow, Karola A1 - Hommes-Schattmann, Paul J. A1 - Neffe, Axel T. A1 - Ahmad, Bilal A1 - Williams, Gareth R. A1 - Lendlein, Andreas T1 - Perfluorophenyl azide functionalization of electrospun poly(para-dioxanone) JF - Polymers for advanced technologies N2 - Strategies to surface-functionalize scaffolds by covalent binding of biologically active compounds are of fundamental interest to control the interactions between scaffolds and biomolecules or cells. Poly(para-dioxanone) (PPDO) is a clinically established polymer that has shown potential as temporary implant, eg, for the reconstruction of the inferior vena cava, as a nonwoven fiber mesh. However, PPDO lacks suitable chemical groups for covalent functionalization. Furthermore, PPDO is highly sensitive to hydrolysis, reflected by short in vivo half-life times and degradation during storage. Establishing a method for covalent functionalization without degradation of this hydrolyzable polymer is therefore important to enable the surface tailoring for tissue engineering applications. It was hypothesized that treatment of PPDO with an N-hydroxysuccinimide ester group bearing perfluorophenyl azide (PFPA) under UV irradiation would allow efficient surface functionalization of the scaffold. X-ray photoelectron spectroscopy and attenuated total reflectance Fourier-transformed infrared spectroscopy investigation revealed the successful binding, while a gel permeation chromatography study showed that degradation did not occur under these conditions. Coupling of a rhodamine dye to the N-hydroxysuccinimide esters on the surface of a PFPA-functionalized scaffold via its amine linker showed a homogenous staining of the PPDO in laser confocal microscopy. The PFPA method is therefore applicable even to the surface functionalization of hydrolytically labile polymers, and it was demonstrated that PFPA chemistry may serve as a versatile tool for the (bio-)functionalization of PPDO scaffolds. KW - biological applications of polymers KW - fibers KW - functionalization of polymers KW - microstructure Y1 - 2018 U6 - https://doi.org/10.1002/pat.4331 SN - 1042-7147 SN - 1099-1581 VL - 30 IS - 5 SP - 1165 EP - 1172 PB - Wiley CY - Hoboken ER - TY - GEN A1 - Schönemann, Eric A1 - Laschewsky, André A1 - Rosenhahn, Axel T1 - Exploring the long-term hydrolytic behavior of zwitterionic polymethacrylates and polymethacrylamides T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The hydrolytic stability of polymers to be used for coatings in aqueous environments, for example, to confer anti-fouling properties, is crucial. However, long-term exposure studies on such polymers are virtually missing. In this context, we synthesized a set of nine polymers that are typically used for low-fouling coatings, comprising the well-established poly(oligoethylene glycol methylether methacrylate), poly(3-(N-2-methacryloylethyl-N,N-dimethyl) ammoniopropanesulfonate) (“sulfobetaine methacrylate”), and poly(3-(N-3-methacryamidopropyl-N,N-dimethyl)ammoniopropanesulfonate) (“sulfobetaine methacrylamide”) as well as a series of hitherto rarely studied polysulfabetaines, which had been suggested to be particularly hydrolysis-stable. Hydrolysis resistance upon extended storage in aqueous solution is followed by ¹H NMR at ambient temperature in various pH regimes. Whereas the monomers suffered slow (in PBS) to very fast hydrolysis (in 1 M NaOH), the polymers, including the polymethacrylates, proved to be highly stable. No degradation of the carboxyl ester or amide was observed after one year in PBS, 1 M HCl, or in sodium carbonate buffer of pH 10. This demonstrates their basic suitability for anti-fouling applications. Poly(sulfobetaine methacrylamide) proved even to be stable for one year in 1 M NaOH without any signs of degradation. The stability is ascribed to a steric shielding effect. The hemisulfate group in the polysulfabetaines, however, was found to be partially labile. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1091 KW - polyzwitterions KW - stability KW - polymer degradation KW - hydrolysis KW - polysulfobetaine KW - polysulfabetaine KW - anti-fouling materials Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-473052 SN - 1866-8372 IS - 1091 ER - TY - JOUR A1 - Czarnecki, Maciej A1 - Wessig, Pablo T1 - Scaling Up UV-Mediated Intramolecular Photodehydro-Diels-Alder Reactions Using a Homemade High-Performance Annular Continuous-Flow Reactor JF - Organic Process Research & Development N2 - Here we present a self-made annular continuous-flow reactor that can be used in the UV/vis range in an internal numbering-up manner. As a model reaction, we chose a powerful batch-scale-limited benzoannelation method, namely, an intramolecular photodehydro-Diels-Alder (IMPDDA) reaction. The scale-up potential of this particular photochemical benchmark reaction toward the preparation of macrocylic (1,7)naphthalenophanes by variation of selected flow parameters is presented. KW - flow photochemistry KW - photocycloaddition KW - photodehydro-Diels-Alder reaction KW - scale-up Y1 - 2018 U6 - https://doi.org/10.1021/acs.oprd.8b00353 SN - 1083-6160 SN - 1520-586X VL - 22 IS - 12 SP - 1823 EP - 1827 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Hoang, Hoa T. A1 - Mertens, Monique A1 - Wessig, Pablo A1 - Sellrie, Frank A1 - Schenk, Jörg A. A1 - Kumke, Michael Uwe T1 - Antibody Binding at the Liposome-Water Interface BT - a FRET Investigation toward a Liposome-Based Assay JF - ACS Omega N2 - Different signal amplification strategies to improve the detection sensitivity of immunoassays have been applied which utilize enzymatic reactions, nanomaterials, or liposomes. The latter are very attractive materials for signal amplification because liposomes can be loaded with a large amount of signaling molecules, leading to a high sensitivity. In addition, liposomes can be used as a cell-like "bioscaffold" to directly test recognition schemes aiming at cell-related processes. This study demonstrates an easy and fast approach to link the novel hydrophobic optical probe based on [1,3]dioxolo[4,5-f]-[1,3]benzodioxole (DBD dye mm239) with tunable optical properties to hydrophilic recognition elements (e.g., antibodies) using liposomes for signal amplification and as carrier of the hydrophobic dye. The fluorescence properties of mm239 (e.g., long fluorescence lifetime, large Stokes shift, high photostability, and high quantum yield), its high hydrophobicity for efficient anchoring in liposomes, and a maleimide bioreactive group were applied in a unique combination to build a concept for the coupling of antibodies or other protein markers to liposomes (coupling to membranes can be envisaged). The concept further allowed us to avoid multiple dye labeling of the antibody. Here, anti-TAMRA-antibody (DC7-Ab) was attached to the liposomes. In proof-of-concept, steady-state as well as time-resolved fluorescence measurements (e.g., fluorescence depolarization) in combination with single molecule detection (fluorescence correlation spectroscopy, FCS) were used to analyze the binding interaction between DC7-Ab and liposomes as well as the binding of the antigen rhodamine 6G (R6G) to the antibody. Here, the Forster resonance energy transfer (FRET) between mm239 and R6G was monitored. In addition to ensemble FRET data, single-molecule FRET (PIE-FRET) experiments using pulsed interleaved excitation were used to characterize in detail the binding on a single-molecule level to avoid averaging out effects. KW - energy-transfer KW - immunoassay KW - complexes KW - probes Y1 - 2018 U6 - https://doi.org/10.1021/acsomega.8b03016 SN - 2470-1343 VL - 3 IS - 12 SP - 18109 EP - 18116 PB - American Chemical Society CY - Washington ER - TY - GEN A1 - Schulze, Sven A1 - Wehrhold, Michel A1 - Hille, Carsten T1 - Femtosecond-pulsed laser written and etched fiber bragg gratings for fiber-optical biosensing T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - We present the development of a label-free, highly sensitive fiber-optical biosensor for online detection and quantification of biomolecules. Here, the advantages of etched fiber Bragg gratings (eFBG) were used, since they induce a narrowband Bragg wavelength peak in the reflection operation mode. The gratings were fabricated point-by-point via a nonlinear absorption process of a highly focused femtosecond-pulsed laser, without the need of prior coating removal or specific fiber doping. The sensitivity of the Bragg wavelength peak to the surrounding refractive index (SRI), as needed for biochemical sensing, was realized by fiber cladding removal using hydrofluoric acid etching. For evaluation of biosensing capabilities, eFBG fibers were biofunctionalized with a single-stranded DNA aptamer specific for binding the C-reactive protein (CRP). Thus, the CRP-sensitive eFBG fiber-optical biosensor showed a very low limit of detection of 0.82 pg/L, with a dynamic range of CRP detection from approximately 0.8 pg/L to 1.2 µg/L. The biosensor showed a high specificity to CRP even in the presence of interfering substances. These results suggest that the proposed biosensor is capable for quantification of CRP from trace amounts of clinical samples. In addition, the adaption of this eFBG fiber-optical biosensor for detection of other relevant analytes can be easily realized. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1073 KW - fiber Bragg gratings KW - ultra-fast laser inscription KW - fiber etching KW - nanostructure fabrication KW - fiber-optical sensors KW - aptamers KW - C-reactive Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-472692 SN - 1866-8372 IS - 1073 ER - TY - GEN A1 - Schneider, Matthias A1 - Günter, Christina A1 - Taubert, Andreas T1 - Co-deposition of a hydrogel/calcium phosphate hybrid layer on 3D printed poly(lactic acid) scaffolds via dip coating BT - Towards automated biomaterials fabrication T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The article describes the surface modification of 3D printed poly(lactic acid) (PLA) scaffolds with calcium phosphate (CP)/gelatin and CP/chitosan hybrid coating layers. The presence of gelatin or chitosan significantly enhances CP co-deposition and adhesion of the mineral layer on the PLA scaffolds. The hydrogel/CP coating layers are fairly thick and the mineral is a mixture of brushite, octacalcium phosphate, and hydroxyapatite. Mineral formation is uniform throughout the printed architectures and all steps (printing, hydrogel deposition, and mineralization) are in principle amenable to automatization. Overall, the process reported here therefore has a high application potential for the controlled synthesis of biomimetic coatings on polymeric biomaterials. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1057 KW - 3D printing KW - dip-coating KW - poly(lactic acid) KW - PLA KW - calcium phosphate KW - gelatin KW - chitosan KW - hydrogel KW - calcium phosphate hybrid material KW - biomaterials Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-474427 SN - 1866-8372 IS - 1057 ER - TY - JOUR A1 - Sun, Fu A1 - Dong, Kang A1 - Osenberg, Markus A1 - Hilger, Andre A1 - Risse, Sebastian A1 - Lu, Yan A1 - Kamm, Paul H. A1 - Klaus, Manuela A1 - Markoetter, Henning A1 - Garcia-Moreno, Francisco A1 - Arlt, Tobias A1 - Manke, Ingo T1 - Visualizing the morphological and compositional evolution of the interface of InLi-anode|thio-LISION electrolyte in an all-solid-state Li-S cell by in operando synchrotron X-ray tomography and energy dispersive diffraction JF - Journal of materials chemistry : A, Materials for energy and sustainability N2 - Dynamic and direct visualization of interfacial evolution is helpful in gaining fundamental knowledge of all-solid-state-lithium battery working/degradation mechanisms and clarifying future research directions for constructing next-generation batteries. Herein, in situ and in operando synchrotron X-ray tomography and energy dispersive diffraction were simultaneously employed to record the morphological and compositional evolution of the interface of InLi-anode|sulfide-solid-electrolyte during battery cycling. Compelling morphological evidence of interfacial degradation during all-solid-state-lithium battery operation has been directly visualized by tomographic measurement. The accompanying energy dispersive diffraction results agree well with the observed morphological deterioration and the recorded electrochemical performance. It is concluded from the current investigation that a fundamental understanding of the phenomena occurring at the solid-solid electrode|electrolyte interface during all-solid-state-lithium battery cycling is critical for future progress in cell performance improvement and may determine its final commercial viability. Y1 - 2018 U6 - https://doi.org/10.1039/c8ta08821g SN - 2050-7488 SN - 2050-7496 VL - 6 IS - 45 SP - 22489 EP - 22496 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Zivanovic, Vesna A1 - Kochovski, Zdravko A1 - Arenz, Christoph A1 - Lu, Yan A1 - Kneipp, Janina T1 - SERS and Cryo-EM Directly Reveal Different Liposome Structures during Interaction with Gold Nanoparticles JF - The journal of physical chemistry letters N2 - The combination of gold nanoparticles with liposomes is important for nano- and biotechnology. Here, we present direct, label-free characterization of liposome structure and composition at the site of its interaction with citrate-stabilized gold nanoparticles by surface-enhanced Raman scattering (SERS) and cryogenic electron microscopy (cryo-EM). Evidenced by the vibrational spectra and cryo-EM, the gold nanoparticles destroy the bilayer structure of interacting liposomes in the presence of a high amount of citrate, while at lower citrate concentration the nanoparticles interact with the surface of the intact liposomes. The spectra of phosphatidylcholine and phosphatidylcholine/sphingomyelin liposomes show that at the site of interaction the lipid chains are in the gel phase. The SERS spectra indicate that cholesterol has strong effects on the contacts of the vesicles with the nanoparticles. By combining cryo-EM and SERS, the structure and properties of lipid nanoparticle composites could be tailored for the development of drug delivery systems. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpclett.8b03191 SN - 1948-7185 VL - 9 IS - 23 SP - 6767 EP - 6772 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schultze, Christiane A1 - Schmidt, Bernd T1 - Ring-closing-metathesis-based synthesis of annellated coumarins from 8-allylcoumarins JF - Beilstein journal of organic chemistry N2 - 8-Allylcoumarins are conveniently accessible through a microwave-promoted tandem Claisen rearrangement/Wittig olefination/cyclization sequence. They serve as a versatile platform for the annellation of five- to seven-membered rings using ring-closing olefin metathesis (RCM). Furano-, pyrano-, oxepino- and azepinocoumarins were synthesized from the same set of precursors using Ru-catalyzed double bond isomerizations and RCM in a defined order. One class of products, pyrano[2,3-f]chromene-2,8-diones, were inaccessible through direct RCM of an acrylate, but became available from the analogous allyl ether via an assisted tandem catalytic RCM/allylic oxidation sequence. KW - coumarins KW - heterocycles KW - isomerization KW - olefin metathesis KW - ruthenium Y1 - 2018 U6 - https://doi.org/10.3762/bjoc.14.278 SN - 1860-5397 VL - 14 SP - 2991 EP - 2998 PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften CY - Frankfurt, Main ER - TY - JOUR A1 - Nguyen, Hiep N. A1 - Lee, Hyeunjoo A1 - Audörsch, Stephan A1 - Reznichenko, Alexander L. A1 - Nawara-Hultzsch, Agnieszka J. A1 - Schmidt, Bernd A1 - Hultzsch, Kai C. T1 - Asymmetric Intra- and Intermolecular Hydroamination Catalyzed by 3,3′-Bis(trisarylsilyl)- and 3,3′-Bis(arylalkylsilyl)-Substituted Binaphtholate Rare-Earth-Metal Complexes JF - Organometallics N2 - The series of novel 3,3′-bis(trisarylsilyl)- and 3,3′-bis(arylalkylsilyl)-substituted binaphtholate rare-earth-metal complexes 2a–i (SiR3 = Si(o-biphenylene)Ph (a), SiCyPh2 (b), Si-t-BuPh2 (c), Si(i-Pr)3 (d), SiCy2Ph (e), Si(2-tolyl)Ph2 (f), Si(4-t-Bu-C6H4)3 (g), Si(4-MeO-C6H4)Ph2 (h), SiBnPh2 (i)) have been prepared via arene elimination from [Ln(o-C6H4CH2NMe2)3] (Ln = Y, Lu) and the corresponding 3,3′-bis(silyl)-substituted binaphthol. The complexes exhibit high catalytic activity in the hydroamination/cyclization of aminoalkenes, with activities exceeding 1000 h–1 for (R)-2f-Ln, (R)-2g-Ln, and (R)-2h-Ln in the cyclization of 2,2-diphenylpent-4-enylamine (3a) at 25 °C, while the rigid dibenzosilole-substituted complexes (R)-2a-Ln and the triisopropylsilyl-substituted complexes (R)-2d-Ln exhibited the lowest activity in the range of 150–270 h–1. Catalysts (R)-2b-Lu, (R)-2c-Lu, (R)-2f-Lu, and (R)-2i-Lu provide the highest selectivities for the majority of the substrates, while the yttrium congeners are usually less selective. The highest enantioselectivities of 96% ee were observed using (R)-2a-Lu and (R)-2c-Lu in the cyclization of (4E)-2,2,5-triphenylpent-4-enylamine (9). The reactions show apparently zero-order rate dependence on substrate concentration and first-order rate dependence on catalyst concentration, with some reactions exhibiting a slightly accelerated rate at high conversion due to a shift in the equilibrium between a less active, higher coordinate catalyst species in favor of a more active, lower coordinate species as a result of weaker binding of the hydroamination product in comparison to the aminoalkene substrate. The shift in equilibrium from the higher to the lower coordinate species is also entropically favored at elevated temperatures, which results in an unusual increase in selectivity in the cyclization of 2,2-dimethylpent-4-enylamine (3d), presumably due to a higher selectivity of the lower coordinate catalyst species. All binaphtholate yttrium complexes, except (R)-2a-Y, are catalytically active in the intermolecular hydroamination of benzylamines with terminal alkenes. The highest selectivity of 66% ee was observed for the reaction of benzylamine with 4-phenyl-1-butene using (R)-2h-Y at 110 °C. Y1 - 2018 U6 - https://doi.org/10.1021/acs.organomet.8b00510 SN - 0276-7333 SN - 1520-6041 VL - 37 IS - 23 SP - 4358 EP - 4379 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Paramonov, Guennaddi K. A1 - Klamroth, Tillmann A1 - Lu, H. Z. A1 - Bandrauk, Andre D. T1 - Quantum dynamics, isotope effects, and power spectra of H-2(+) and HD+ excited to the continuum by strong one-cycle laser pulses: Three-dimensional non-Born-Oppenheimer simulations JF - Physical review : A, Atomic, molecular, and optical physics N2 - Non-Born-Oppenheimer quantum dynamics of H-2(+) and HD+ excited by single one-cycle laser pulses linearly polarized along the molecular (z) axis have been studied within a three-dimensional model, including the internuclear distance R and electron coordinates z and rho, by means of the numerical solution of the time-dependent Schrodinger equation on the timescale of about 200 fs. Laser carrier frequencies corresponding to the wavelengths of lambda(l) = 400 and 50 nm have been used and the amplitudes of the pulses have been chosen such that the energies of H-2(+) and HD+ are above the dissociation threshold after the ends of the laser pulses. It is shown that excitation of H-2(+) and HD+ above the dissociation threshold is accompanied by formation of vibrationally "hot" and "cold" ensembles of molecules. Dissociation of vibrationally "hot" molecules does not prevent the appearance of post-laser-pulse electronic oscillations, parallel z oscillations, and transversal rho oscillations. Moreover, dissociation of "hot" molecules does not influence characteristic frequencies of electronic z and rho oscillations. The main difference between the laser-induced quantum dynamics of homonuclear H-2(+) and its heteronuclear isotope HD+ is that fast post-laser-pulse electronic z oscillations in H-2(+) are regularly shaped with the period of tau(shp) approximate to 30 fs corresponding to nuclear oscillations in H-2(+), while electronic z oscillations in HD+ arise as "echo pulses" of its initial excitation and appear with the period of tau(echo) approximate to 80 fs corresponding to nuclear motion in HD+. Accordingly, corresponding power spectra of nuclear motion contain strong low-frequency harmonics at omega(shp) = 2 pi/tau(shp) in H2(+) and omega(echo) = 2 pi/tau(echo) in HD+. Power spectra related to both electronic and nuclear motion have been calculated in the acceleration form. Both higher- and lower-order harmonics are generated at the laser wavelength lambda(l) = 400 nm, while only lower-order harmonics are well pronounced at lambda(l) = 50 nm. It is also shown that a rationalized harmonic order, defined in terms of the frequency of the laser-induced electronic z oscillations, agrees with the concept of inversion symmetry for electronic motion in diatomic molecules. Y1 - 2018 U6 - https://doi.org/10.1103/PhysRevA.98.063431 SN - 2469-9926 SN - 2469-9934 VL - 98 IS - 6 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Balderas-Valadez, Ruth Fabiola A1 - Estevez-Espinoza, J. O. A1 - Salazar-Kuri, U. A1 - Pacholski, Claudia A1 - Mochan, Wolf Luis A1 - Agarwal, Vivechana T1 - Fabrication of ordered tubular porous silicon structures by colloidal lithography and metal assisted chemical etching BT - SERS performance of 2D porous silicon structures JF - Applied surface science : a journal devoted to applied physics and chemistry of surfaces and interfaces N2 - Fabrication of well-ordered porous silicon tubular structures using colloidal lithography and metal assisted chemical etching is reported. A continuous hexagonal hole/particle gold pattern was designed over monocrystalline silicon through deposition of polyNIPAM microspheres, followed by the surface decoration with gold nanoparticles and thermal treatment. An etching reaction with HF, ethanol and H2O2 dissolved the silicon in contact with the metal nanoparticles (NP), creating a porous tubular array in the "off-metal area". The morphological characterization revealed the formation of a cylindrical hollow porous tubular shape with external and internal diameter of approx. 900 nm and 400 nm respectively, though it can be tuned to other desired sizes by choosing an appropriate dimension for the microspheres. The porous morphology and optical properties were studied as a function of resistivity of silicon substrates. Compared to two different gold templates on cSi and nontubular porous pillar structures, porous silicon tubular framework revealed a maximum surface enhanced Raman scattering enhancement factor of 10(6) for the detection of 6-mercaptopurine (6-MP). Due to the large surface area available for any surface modification, open nanostructured platforms such as those studied here have potential applications in the field of reflection/photoluminescene and SERS based optical bio-/chemical sensors. KW - SERS KW - Porous silicon KW - MACE KW - Colloidal lithography KW - PolyNIPAM KW - 6-Mercaptopurine Y1 - 2018 U6 - https://doi.org/10.1016/j.apsusc.2018.08.120 SN - 0169-4332 SN - 1873-5584 VL - 462 SP - 783 EP - 790 PB - Elsevier CY - Amsterdam ER - TY - THES A1 - Werner, Peter T1 - Untersuchung stark-streuender Polymersuspensionen mittels optischer Methoden Y1 - 2018 ER - TY - THES A1 - Zimmermann, Marc T1 - Multifunctional patchy silica particles via microcontact printing T1 - Multifunktionale Patchy Silika Partikel mithilfe des Mikrokontaktdruckverfahrens N2 - This research addressed the question, if it is possible to simplify current microcontact printing systems for the production of anisotropic building blocks or patchy particles, by using common chemicals while still maintaining reproducibility, high precision and tunability of the Janus-balance Chapter 2 introduced the microcontact printing materials as well as their defined electrostatic interactions. In particular polydimethylsiloxane stamps, silica particles and high molecular weight polyethylenimine ink were mainly used in this research. All of these components are commercially available in large quantities and affordable, which gives this approach a huge potential for further up-scaling developments. The benefits of polymeric over molecular inks was described including its flexible influence on the printing pressure. With this alteration of the µCP concept, a new method of solvent assisted particle release mechanism enabled the switch from two-dimensional surface modification to three-dimensional structure printing on colloidal silica particles, without changing printing parameters or starting materials. This effect opened the way to use the internal volume of the achieved patches for incorporation of nano additives, introducing additional physical properties into the patches without alteration of the surface chemistry. The success of this system and its achievable range was further investigated in chapter 3 by giving detailed information about patch geometry parameters including diameter, thickness and yield. For this purpose, silica particles in a size range between 1µm and 5µm were printed with different ink concentrations to change the Janus-balance of these single patched particles. A necessary intermediate step, consisting of air-plasma treatment, for the production of trivalent particles using "sandwich" printing was discovered and comparative studies concerning the patch geometry of single and double patched particles were conducted. Additionally, the usage of structured PDMS stamps during printing was described. These results demonstrate the excellent precision of this approach and opens the pathway for even greater accuracy as further parameters can be finely tuned and investigated, e.g. humidity and temperature during stamp loading. The performance of these synthesized anisotropic colloids was further investigated in chapter 4, starting with behaviour studies in alcoholic and aqueous dispersions. Here, the stability of the applied patches was studied in a broad pH range, discovering a release mechanism by disabling the electrostatic bonding between particle surface and polyelectrolyte ink. Furthermore, the absence of strong attractive forces between divalent particles in water was investigated using XPS measurements. These results lead to the conclusion that the transfer of small PDMS oligomers onto the patch surface is shielding charges, preventing colloidal agglomeration. However, based on this knowledge, further patch modifications for particle self-assembly were introduced including physical approaches using magnetic nano additives, chemical patch functionalization with avidin-biotin or the light responsive cyclodextrin-arylazopyrazoles coupling as well as particle surface modification for the synthesis of highly amphiphilic colloids. The successful coupling, its efficiency, stability and behaviour in different solvents were evaluated to find a suitable coupling system for future assembly experiments. Based on these results the possibility of more sophisticated structures by colloidal self-assembly is given. Certain findings needed further analysis to understand their underlying mechanics, including the relatively broad patch diameter distribution and the decreasing patch thickness for smaller silica particles. Mathematical assumptions for both effects are introduced in chapter 5. First, they demonstrate the connection between the naturally occurring particle size distribution and the broadening of the patch diameter, indicating an even higher precision for this µCP approach. Second, explaining the increase of contact area between particle and ink surface due to higher particle packaging, leading to a decrease in printing pressure for smaller particles. These calculations ultimately lead to the development of a new mechanical microcontact printing approach, using centrifugal forces for high pressure control and excellent parallel alignment of printing substrates. First results with this device and the comparison with previously conducted by-hand experiments conclude this research. It furthermore displays the advantages of such a device for future applications using a mechanical printing approach, especially for accessing even smaller nano particles with great precision and excellent yield. In conclusion, this work demonstrates the successful adjustment of the µCP approach using commercially available and affordable silica particles and polyelectrolytes for high flexibility, reduced costs and higher scale-up value. Furthermore, its was possible to increase the modification potential by introducing three-dimensional patches for additional functionalization volume. While keeping a high colloidal stability, different coupling systems showed the self-assembly capabilities of this toolbox for anisotropic particles. N2 - Diese Forschungsarbeit befasste sich mit der Frage, ob es möglich ist, bekannte Mikrokontaktdruckverfahren, zur Herstellung von anisotropen Bausteinen (Patchy Partikel), weiter zu vereinfachen. Dabei sollten gängige Chemikalien verwendet werden ohne einen Verlust in Reproduzierbarkeit, hoher Präzision und Feineinstellung der Janus-Balance zu erleiden. In Kapitel 2 wurden die verwendeten Mikrokontaktdruckmaterialien sowie deren elektrostatische Wechselwirkungen vorgestellt. Insbesondere handelte es sich dabei um Polydimethylsiloxan Stempel, Silikapartikel und hoch molekulare Polyethylenimin Tinte. All diese Produkte sind kommerziel in großen und bezahlbaren Mengen erhältlich. Nicht nur die Vorteile von polymeren Tinten im Gegensatz zu molekularen Tinten wurde beschrieben, sondern auch die hohe Flexibilität dieses Verfahrens bezüglich der verwendeten Druckkraft. Mit dieser Anpassung des Mikrokontaktdrucks, wurde eine neue Methode der Lösungsmittel unterstützten Partikelablösung ermöglicht, mit deren Hilfe ein einfaches Schalten zwischen zwei dimensionaler Oberflächenfunktionalisierung und drei dimensionalem Strukturdrucks möglich war, ohne Druckparameter oder Startchemikalien zu verändern. Dadurch konnte neu erschaffenes internes Volumen verwendet werden um Nanoadditive einzuführen und so zusätzliche physikalische Eigenschaften zu integrieren, ohne die Oberflächenchemie der Patches verändert wurde. Der Erfolg dieses Systems und seine erreichbaren Grenzen wurde gründlichst in Kapitel 3 erforscht, indem detaillierte Geometrieparameter der Patches einschließlich Durchmesser, Dicke und Ausbeute, erworben wurden. Hierfür wurden Silikapartikel in einem Größenbereich von 1µm bis 5µm mit unterschiedlichen Tintenkonzentrationen bedruckt, um Veränderungen erforschen zu können. Ein notwendiger Luftplasma Ätzschritt für die Produktion von trivalenten Partikeln, mit Hilfe des sogenannten ,,Sandwich‘‘-Drucks, wurde erläutert und vergleichende Untersuchen von einfach und zweifach modifizierten Bausteinen wurden durchgeführt. Zusätzlich dazu, wurde die Verwendung von strukturierten Stempel beschrieben. Die Ergebnisse verdeutlichen die exzellente Genauigkeit dieser Methode und öffnet den Weg um eine hoch höhere Präzision zu erreichen da weitere Parametere genau eingestellt und untersucht werden können, z.B. Luftfeuchtigkeit und Temperature während der Stempelbeladung. Die Performance der herstellten anisotropen Partikel wurde in Kapitel 4 mit Verhaltensstudien in alkoholischen und wässrigen Dispersionen getestet. Dabei wurde die Stabilität der Oberflächenfunktionalisierungen in einem breiten pH Bereich untersucht. Dadurch wurde ein Ablösungsmechanismus bei sehr hohen bzw. niedrigen pH-Werten entdeckt, der zur Deaktivierung elektrostatischer Wechselwirkungen zwischen Partikeloberfläche und Polyelektrolyte Tinte führte. Desweitern wurden die Abwesenheit starker Wechselwirkung der divalenten Partikel in Wasser mit Hilfe von XPS untersucht. Das Resultat zeigte, dass der Transfer kleinster PDMS Oligomere auf die Patchoberfläche zu einer Ladungsabschirmung führte. Dadurch konnte Agglomeration verhindert werden. Aufgrund dieser Ergebnisse wurden weitere Modifikationen für Partikelassemblierung durchgeführt. Hierfür wurde die Einführung von magnetischen Nanoadditiven, die Funktionalisierung mit Avidin-Biotin sowie dem Lichtschaltbaren Cyclodextrin-Arylazopyrazol Komplexen und die Partikeloberflächenfunktionalisierung zur Herstellung amphiphiler Teilchen untersucht. Die Effizienz der Kopplung, deren Stabilität sowie das Verhalten in unterschiedlichen Lösungsmittel wurde beschrieben. Basierend auf diesen Ergebnissen können noch anspruchsvollere Strukturen durch kolloidale Selbstassemblierung erzeugt werden. Einige Ergebnisse dieser Arbeit benötigten zusätzlicher Analyse um die zugrundeliegenden Mechaniken verstehen zu können. Dazu gehörte die relative hohe Streuung des Durchmessers für unterschiedliche Partikelsysteme, sowie das Ausdünnen des Patches mit kleineren Silikapartikeln. Mathematische Modelle in Kapitel 5 beschreiben beide Effekte. Dadurch war es möglich einen Zusammenhang zwischen der natürlichen Partikelgrößenverteilung sowie der Verbreitung des Patchdurchmessers festzustellen. Des Weiteren konnte eine Verkleinerung der Druckkraft durch eine Erhöhung der Packungsdichte für kleine Partikel beschrieben werden, wodurch eine Erklärung der Ausdünnung möglich war. All diese Berechnung führten schlussendlich zur Entwicklung eines neuen mechanischen Mikrokontaktdruckverfahrens, welches mit Hilfe von Zentrifugalkräften eine hohe Druckkontrolle und eine exzellente parallele Ausrichtung zwischen den Substraten ermöglicht. Erste Ergebnisse, sowie deren Vergleich mit bisher erhaltenen Resultaten schließen diese Forschung ab. Des Weiteren zeigt es die Vorteile einer solchen Vorrichtung für kommende Applikationen, besonders um noch kleinere Nanopartikel mit einer hohen Präzision modifizieren zu können. Zusammenfassend ist zu sagen, dass diese Forschung die erfolgreiche Anpassung des Mikrokontaktdruckverfahrens mit kommerziell erhältlichen und bezahlbaren Silikapartikeln und Polyelektrolyten demonstriert, um hohe Flexibilität, reduzierte Kosten und ein erweitertes Skalierungspotential zu bieten. Zusätzlich ist es gelungen, die Funktionalisierungsdichte zu erhöhen, indem drei dimensionaler Strukturdruck bisher ungenutztes Volumen schaffen konnte. Während eine hohe kolloidale Stabilität erhalten blieb, ist es gelungen unterschiedliche Kopplungssysteme zu nutzen, um das Selbstorganisationspotential dieser Toolbox für anisotrope Partikel aufzuzeigen. KW - patchy particles KW - microcontact printing KW - silica particles KW - anisotropic colloids KW - polyelectrolytes KW - Patchy Partikel KW - Mikrokontaktdruck KW - Silika Partikel KW - Anisotrope Kolloide KW - Polyelektrolyte Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-427731 ER - TY - JOUR A1 - Abbas, Ioana M. A1 - Vranic, Marija A1 - Hoffmann, Holger A1 - El-Khatib, Ahmed H. A1 - Montes-Bayón, María A1 - Möller, Heiko Michael A1 - Weller, Michael G. T1 - Investigations of the Copper Peptide Hepcidin-25 by LC-MS/MS and NMR⁺ JF - International Journal of Molecular Sciences N2 - Hepcidin-25 was identified as themain iron regulator in the human body, and it by binds to the sole iron-exporter ferroportin. Studies showed that the N-terminus of hepcidin is responsible for this interaction, the same N-terminus that encompasses a small copper(II) binding site known as the ATCUN (amino-terminal Cu(II)- and Ni(II)-binding) motif. Interestingly, this copper-binding property is largely ignored in most papers dealing with hepcidin-25. In this context, detailed investigations of the complex formed between hepcidin-25 and copper could reveal insight into its biological role. The present work focuses on metal-bound hepcidin-25 that can be considered the biologically active form. The first part is devoted to the reversed-phase chromatographic separation of copper-bound and copper-free hepcidin-25 achieved by applying basic mobile phases containing 0.1% ammonia. Further, mass spectrometry (tandemmass spectrometry (MS/MS), high-resolutionmass spectrometry (HRMS)) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize the copper-peptide. Lastly, a three-dimensional (3D)model of hepcidin-25with bound copper(II) is presented. The identification of metal complexes and potential isoforms and isomers, from which the latter usually are left undetected by mass spectrometry, led to the conclusion that complementary analytical methods are needed to characterize a peptide calibrant or referencematerial comprehensively. Quantitative nuclear magnetic resonance (qNMR), inductively-coupled plasma mass spectrometry (ICP-MS), ion-mobility spectrometry (IMS) and chiral amino acid analysis (AAA) should be considered among others. KW - hepcidin-25 KW - copper KW - nickel KW - copper complex KW - ATCUN motif KW - metal complex KW - MS KW - NMR structure KW - metal peptide KW - metalloprotein KW - metallopeptide KW - isomerization KW - racemization KW - purity KW - reference material Y1 - 2018 U6 - https://doi.org/10.3390/ijms19082271 SN - 1422-0067 SN - 1661-6596 VL - 19 IS - 8 PB - Molecular Diversity Preservation International CY - Basel ER - TY - THES A1 - Kumru, Baris T1 - Utilization of graphitic carbon nitride in dispersed media T1 - Anwendung von graphitischem Kohlenstoffnitrid in dispergierten Medien N2 - Utilization of sunlight for energy harvesting has been foreseen as sustainable replacement for fossil fuels, which would also eliminate side effects arising from fossil fuel consumption such as drastic increase of CO2 in Earth atmosphere. Semiconductor materials can be implemented for energy harvesting, and design of ideal energy harvesting devices relies on effective semiconductor with low recombination rate, ease of processing, stability over long period, non-toxicity and synthesis from abundant sources. Aforementioned criteria have attracted broad interest for graphitic carbon nitride (g-CN) materials, metal-free semiconductor which can be synthesized from low cost and abundant precursors. Furthermore, physical properties such as band gap, surface area and absorption can be tuned. g-CN was investigated as heterogeneous catalyst, with diversified applications from water splitting to CO2 reduction and organic coupling reactions. However, low dispersibility of g-CN in water and organic solvents was an obstacle for future improvements. Tissue engineering aims to mimic natural tissues mechanically and biologically, so that synthetic materials can replace natural ones in future. Hydrogels are crosslinked networks with high water content, therefore are prime candidates for tissue engineering. However, the first requirement is synthesis of hydrogels with mechanical properties that are matching to natural tissues. Among different approaches for reinforcement, nanocomposite reinforcement is highly promising. This thesis aims to investigate aqueous and organic dispersions of g-CN materials. Aqueous g-CN dispersions were utilized for visible light induced hydrogel synthesis, where g-CN acts as reinforcer and photoinitiator. Varieties of methodologies were presented for enhancing g-CN dispersibility, from co-solvent method to prepolymer formation, and it was shown that hydrogels with diversified mechanical properties (from skin-like to cartilage-like) are accessible via g-CN utilization. One pot photografting method was introduced for functionalization of g-CN surface which provides functional groups towards enhanced dispersibility in aqueous and organic media. Grafting vinyl thiazole groups yields stable additive-free organodispersions of g-CN which are electrostatically stabilized with increased photophysical properties. Colloidal stability of organic systems provides transparent g-CN coatings and printing g-CN from commercial inkjet printers. Overall, application of g-CN in dispersed media is highly promising, and variety of materials can be accessible via utilization of g-CN and visible light with simple chemicals and synthetic conditions. g-CN in dispersed media will bridge emerging research areas from tissue engineering to energy harvesting in near future. N2 - Sonnenlicht kann fossile Brennstoffe in der Energieerzeugung ersetzen und ermöglicht neben der Nutzung einer nachhaltigen Ressource dabei auch die deutliche Reduktion der Umweltbelastung in der Energieerzeugung. Die Verfügbarkeit geeigneter Energiegewinnungstechnologien hängt entscheidend von der Verfügbarkeit geeigneter Superkondensatoren (SC) ab. Ideale SC sollten sich in diesem Zusammenhang durch eine geringe Rekombinationsrate, gute Verarbeitbarkeit, Langzeitstabilität, Ungiftigkeit und die Verfügbarkeit aus nachhaltigen Ressourcen auszeichnen. Graphitisches Kohlenstoffnitrid (graphitic carbon nitride – g-CN), ein metall-freier Halbleiter, der aus nachhaltigen und in großer Menge verfügbaren Ausgangsstoffen hergestellt werden kann, ist als Material für dieses Eigenschaftsprofil hervorragend geeignet. Darüber hinaus können die Eigenschaften dieses Materials (innere Oberfläche, Bandlücke, Lichtabsorption) eingestellt werden. Daraus ergibt sich ein großes Forschungsinteresse z.B. im Bereich heterogener Katalyse, wie in der Kohlenstoffdioxidreduktion, elektrolytischen Wasserspaltung und verschiedener organischer Kupplungsreaktionen. Unglücklicherweise ist die schlechte Dispergierbarkeit von g-CN in organischen Lösungsmitteln und Wasser ein wesentlicher Hinderungsgrund für die erfolgreiche Nutzbarmachung dieser hervorragenden Eigenschaften. Das Design von Materialien, die biologisches Gewebe in seinen mechanischen und biologischen Eigenschaften nachahmen und ersetzen können, ist das Ziel der Gewebekonstruktion (Tissue Engineering – TE). Hydrogele, also Netzwerke mit hohem Wassergehalt, gelten als die vielversprechendsten Materialen in diesem Forschungsfeld. Die Herstellung von Hydrogelen, die biologischem Gewebe in seinen mechanischen Eigenschaften ähnelt gilt allerdings als äußerst schwierig und erfordert die Stabilisierung der Netzwerke. Besonders der Einsatz von Nanoverbundstrukturen (nanocomposites) erscheint in diesem Zusammenhang vielversprechend. Die vorliegende Arbeit beschäftigt sich mit der Untersuchung von g-CN in sowohl wässrigen, als auch organischen Dispersionen. Im Zuge dessen werden wässrige Dispersionen für die Synthese von Hydrogelen, bei der g-CN sowohl als Photoinitiator für die durch sichtbares Licht ausgelöste Vernetzung, als auch als Strukturverstärker fungiert. Zur Verbesserung der Dispergierbarkeit des g CN werden vielseitige Ansätze präsentiert, welche von der Verwendung von Co-Lösungsmitteln bis zur Präpolymerbildung reichen. Durch die aufgezeigten Ansätze können Hydrogele mit unterschiedlichen mechanischen Eigenschaften hergestellt werden (hautartig bis knorpelig). Darüber hinaus wird eine Ein-Topf Synthese für die Oberflächenfunktionalisierung vorgestellt, durch die die Dispergierbarkeit von g-CN in organischen und wässrigen Medien verbessert werden kann. Beispielsweise erlaubt die Oberflächenfunktionalisierung mit Vinylthiazol die Herstellung von kolloidal dispergiertem g-CN mit verbesserten photophysikalischen Eigenschaften ohne zusätzliche Additive und eröffnet damit die Möglichkeit transparenter g-CN Beschichtungen und ermöglicht die Druckbarkeit von g-CN aus handelsüblichen Tintenstrahldruckern. Die Anwendung von g-CN in dispergierten Medien ist vielversprechend, da eine große Zahl sehr vielfältiger Materialien durch die Kombination von g-CN mit sichtbarem Licht aus günstigen, nachhaltigen Ressourcen verfügbar ist. Daher ist zu erwarten, dass g-CN in dispergierten Medien verschiedene im Entstehen begriffene Forschungsfelder von TE bis zur Energiegewinnung überspannen wird. KW - polymer chemistry KW - Polymerchemie KW - photochemistry KW - Photochemie KW - colloid chemistry KW - kolloidchemie KW - hydrogels KW - Hydrogelen Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-427339 ER - TY - THES A1 - Heiden, Sophia L. T1 - Water at α-alumina surfaces T1 - Wasser auf alpha-Aluminiumoxid-Oberflächen BT - energetics, dynamics and kinetics BT - Energetik, Dynamik und Kinetik N2 - The (0001) surface of α-Al₂O₃ is the most stable surface cut under UHV conditions and was studied by many groups both theoretically and experimentally. Reaction barriers computed with GGA functionals are known to be underestimated. Based on an example reaction at the (0001) surface, this work seeks to improve this rate by applying a hybrid functional method and perturbation theory (LMP2) with an atomic orbital basis, rather than a plane wave basis. In addition to activation barriers, we calculate the stability and vibrational frequencies of water on the surface. Adsorption energies were compared to PW calculations and confirmed PBE+D2/PW stability results. Especially the vibrational frequencies with the B3LYP hybrid functional that have been calculated for the (0001) surface are in good agreement with experimental findings. Concerning the barriers and the reaction rate constant, the expectations are fully met. It could be shown that recalculation of the transition state leads to an increased barrier, and a decreased rate constant when hybrid functionals or LMP2 are applied. Furthermore, the molecular beam scattering of water on (0001) surface was studied. In a previous work by Hass the dissociation was studied by AIMD of molecularly adsorbed water, referring to an equilibrium situation. The experimental method to obtaining this is pinhole dosing. In contrast to this earlier work, the dissociation process of heavy water that is brought onto the surface from a molecular beam source was modeled in this work by periodic ab initio molecular dynamics simulations. This experimental method results in a non-equilibrium situation. The calculations with different surface and beam models allow us to understand the results of the non-equilibrium situation better. In contrast to a more equilibrium situation with pinhole dosing, this gives an increase in the dissociation probability, which could be explained and also understood mechanistically by those calculations. In this work good progress was made in understanding the (1120) surface of α-Al₂O₃ in contact with water in the low-coverage regime. This surface cut is the third most stable one under UHV conditions and has not been studied to a great extent yet. After optimization of the clean, defect free surface, the stability of different adsorbed species could be classified. One molecular minimum and several dissociated species could be detected. Starting from these, reaction rates for various surface reactions were evaluated. A dissociation reaction was shown to be very fast because the molecular minimum is relatively unstable, whereas diffusion reactions cover a wider range from fast to slow. In general, the (112‾0) surface appears to be much more reactive against water than the (0001) surface. In addition to reactivity, harmonic vibrational frequencies were determined for comparison with the findings of the experimental “Interfacial Molecular Spectroscopy” group from Fritz-Haber institute in Berlin. Especially the vibrational frequencies of OD species could be assigned to vibrations from experimental SFG spectra with very good agreement. Also, lattice vibrations were studied in close collaboration with the experimental partners. They perform SFG spectra at very low frequencies to get deep into the lattice vibration region. Correspondingly, a bigger slab model with greater expansion perpendicular to the surface was applied, considering more layers in the bulk. Also with the lattice vibrations we could obtain reasonably good agreement in terms of energy differences between the peaks. N2 - Das wissenschaftliche Interesse an der Untersuchung von Oberflächen hat in den letzten Jahren stark zugenommen. Oberflächen spielen unter anderem in Katalyse, Nanotechnologie und Korrosionsforschung eine wichtige Rolle. Es wurden nicht nur Fortschritte im experimentellen Bereich, sondern auch in der theoretischen, computergestützten Analyse dieser Systeme erzielt. Durch leistungsstärkere Computer und ausgefeiltere Software mit immer besseren Methoden können heutzutage wesentlich größere, komplexere Systeme mit höherer Genauigkeit untersucht werden, als noch vor zehn Jahren. In dieser Arbeit wurden derartige Rechnungen angewandt, um Prozesse der α-Aluminiumoxid-Oberfläche besser zu verstehen. Es wurde in drei Teilprojekten wissenschaftlichen Fragestellungen zu Aufbau, Stabilität, Wasseradsorption, Reaktivität und Schwingungseigenschaften nachgegangen, letztere auch im Vergleich zu experimentellen Befunden. Im ersten Teilprojekt wurde auf ein bekanntes Problem der genutzten Methodik eingegangen. Wie aus der Literatur bekannt ist, werden bei dem Dichtefunktional PBE, das in dieser Arbeit hauptsächlich verwendet wurde, die Reaktionsbarrieren unterschätzt, und somit Raten überschätzt. Mit Hilfe zweier unterschiedlicher Methoden konnte dieses Problem deutlich verbessert werden, sodass die Barrieren erhöht und die Raten verringert wurden, was mehr dem Bild der Realität entspricht. Diese Methoden sind zum einen die sogenannten Hybridfunktionale und zum anderen lokale Møller-Plesset Störungstheorie. Außerdem wurden Adsorptionsenergien und Vibrationen berechnet und mit vorherigen Rechnungen, sowie experimentellen Daten verglichen. In einem zweiten Teilprojekt wurde die Streuung von Wasser an der Oberfläche untersucht. In einem Molekularstrahlexperiment konnte kürzlich nachgewiesen werden, dass sich die Dissoziationswahrscheinlichkeit im Vergleich zur Pinhole-Dosierung erhöht (beides sind Methoden um Wasser auf die Oberfläche aufzubringen). In dieser Arbeit konnte dies durch Simulationen nachgewiesen und mechanistisch aufgeklärt werden. Ein weiteres Teilprojekt befasste sich mit der (112‾0)-Oberfläche, zu der es bislang wenige Untersuchungen gibt. Hier wurde zunächst die Oberfläche ohne Wasser untersucht, um die Beschaffenheit zu erkunden. Anschließend wurde das Verhalten eines Wassermoleküls auf der Oberfläche untersucht. Es kann sowohl molekular adsorbieren, als auch in seine Bestandteile OH und H dissoziiert vorliegen, wobei die dissoziierten Strukturen wesentlich stabiler sind. Die Reaktionsraten für Dissoziation und Diffusion wurden untersucht. Erstere sind sehr schnell (Größenordnung 10¹² pro Sekunde) und letztere können einen weiten Bereich abdecken (10⁻¹³-10⁶s⁻¹). Im Vergleich mit oberflächenspezifischen Schwingungsspektroskopie-Experimenten konnte gute Übereinstimmung gefunden werden. So waren wir in der Lage, die jeweiligen OD Gruppen jeder Schwingung den experimentellen Daten zuzuweisen, wobei D hier Deuterium, also schwerer Wasserstoff ist. KW - surface science KW - alumina KW - water at alumina KW - theoretical chemistry KW - theoretische Chemie KW - Aluminiumoberfläche KW - Wasser auf Aluminiumoxid KW - Oberflächenchemie Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-426366 ER - TY - THES A1 - Cheng, Xiao T1 - Controlled solvent vapor annealing of block copolymer films T1 - Kontrolliertes Lösungsmitteldampfglühen von Blockcopolymerfilmen N2 - This project was focused on exploring the phase behavior of poly(styrene)187000-block-poly(2-vinylpyridine)203000 (SV390) with high molecular weight (390 kg/mol) in thin films, in which the self-assembly of block copolymers (BCPs) was realized via thermo-solvent annealing. The advanced processing technique of solvent vapor treatment provides controlled and stable conditions. In Chapter 3, the factors to influence the annealing process and the swelling behavior of homopolymers are presented and discussed. The swelling behavior of BCP in films is controlled by the temperature of the vapor and of the substrate, on one hand, and variation of the saturation of the solvent vapor atmosphere (different solvents), on the other hand. Additional factors like the geometry and material of the chamber, the type of flow inside the chamber etc. also influence the reproducibility and stability of the processing. The slightly selective solvent vapor of chloroform gives 10% more swelling of P2VP than PS in films with thickness of ~40 nm. The tunable morphology in ultrathin films of high molecular weight BCP (SV390) was investigated in Chapter 4. First, the swelling behavior can be precisely tuned by temperature and/or vapor flow separately, which provided information for exploring the multiple-parameter-influenced segmental chain mobility of polymer films. The equilibrium state of SV390 in thin films influenced by temperature was realized at various temperatures with the same degree of swelling. Various methods including characterization with SFM, metallization and RIE were used to identify the morphology of films as porous half-layer with PS dots and P2VP matrix. The kinetic investigations demonstrate that on substrates with either weak or strong interaction the original morphology of the BCP with high molecular weight is changed very fast within 5 min, and the further annealing serves for annihilation of defects. The morphological development of symmetric BCP in films with thickness increasing from half-layer to one-layer influenced by confinement factors of gradient film thicknesses and various surface properties of substrates was studied in Chapter 5. SV390 and SV99 films show bulk lamella-forming morphology after slightly selective solvent vapor (chloroform) treatment. SV99 films show cylinder-forming morphology under strongly selective solvent vapor (toluene) treatment since the asymmetric structure (caused by toluene uptake in PS blocks only) of SV99 block copolymer during annealing. Both kinds of morphology (lamella and cylinder) are influenced by the film thickness. The annealed morphology of SV390 and SV99 influenced by the combination of confined film and substrate property is similar to the morphology on flat silicon wafers. In this chapter the gradients in the film thickness and surface properties of the substrates with regard to their influence on the morphological development in thin BCP films are presented. Directed self-assembly (graphoepitaxy) of this SV390 was also investigated to compare with systematically reported SV99. In Chapter 6 an approach to induced oriented microphase separation in thick block copolymer films via treatment with the oriented vapor flow using mini-extruder is envisaged to be an alternative to existing methodologies, e.g. via non-solvent-induced phase separation. The preliminary tests performed in this study confirm potential perspective of this method, which alters the structure through the bulk of the film (as revealed by SAXS measurements), but more detailed studies have to be conducted in order to optimize the preparation. N2 - Im Rahmen dieser Arbeit wurde das Phasenverhalten von Poly(styrol)_187000 -block-poly(2-Vinylpyridin)_203000 (SV^390 ) hohen Molekulargewichts (390 kg/mol) in dünnen Filmen untersucht, in denen die Selbstassemblierung der Block-Copolymere durch Lösungsmitteltempern erreicht wurde. Das hochentwickelte Verfahren der Behandlung mit Lösungsmitteldampf bietet kontrollierte und stabile Bedingungen. In *Kapitel 3* werden die Faktoren diskutiert, die den Prozess des Temperns und das Schwellverhalten der dünnen Block-Copolymer Filme beeinflussen. Das Schwellverhalten von Block-Copolymeren in Filmen wird einerseits durch die Temperaturen des Lösungsmitteldampfes und des Substrates sowie andererseits dem Sättigungs-Dampfdruck kontrolliert. Zusätzlich beeinflussen auch Faktoren wie die Geometrie und das Material der Kammer sowie die Art der Strömung in der Kammer die Reproduzierbarkeit und Stabilität der Messungen. Der geringfügig selektive Lösungsmitteldampf von Chloroform führt zu 10% stärkerem Schwellen des P2VP-Blocks im Vergleich zu PS in Filmen mit einer Dicke von ca. 40 nm. Die variable Morphologie ultradünner Filme eines Block-Copolymers hohen Molekulargewichts (SV^390 ) wurde in *Kapitel 4* untersucht. Das Schwellverhalten kann durch die Temperatur und den Dampffluss unabhängig voneinander präzise beeinflusst werden. Die Umgebungstemperatur stellt einen limitierenden Faktor für den Bereich der Annealing-Temperatur aufgrund der möglichen Kondensation des Lösungsmitteldampfes dar. Mehrere Methoden, wie zum Beispiel die Charakterisierung mit Rasterkraftmikroskopie, Metallisierung und reaktives Ionenätzen, wurden verwendet, um die Morphologie der Filme als perforierte Lamellen mit PS-Kugeln und P2VP-Matrix zu bestimmen. Eine Analyse der Kinetik der Strukturbildung zeigt, dass sich die ursprüngliche Morphologie von Block-Copolymeren hohen Molekulargewichts sowohl auf Substraten mit schwacher als auch starker Wechselwirkung innerhalb von 5 min ändert und das weitere Tempern zum Ausheilen von Defekten führt. Die morphologische Veränderung von symmetrischen Block-Copolymeren bei Filmdicken zwischen einer halben Domänendicke und einer ganzen Domänendicke wurde in *Kapitel 5* in Abhängigkeit von Gradienten der Filmdicke und verschiedenen Oberflächeneigenschaften der Substrate untersucht. SV^390 und SV^99 Filme zeigen eine lamellare Bulk-Morphologie nach Behandlung mit geringfügig selektivem Lösungsmitteldampf (Chloroform). SV^99 Filme bilden eine zylindrische Morphologie unter Behandlung mit stark selektivem Lösungsmitteldampf (Toluol) aus, weil das SV^99 Block-Copolymer während des Temperns eine asymmetrische Struktur aufweist (Toluol-Aufnahme ausschließlich im Polystyrol-Block). Beide Morphologien (Lamellen und Zylinder) werden durch die Filmdicke beeinflusst. Die Morphologie von SV^390 und SV^99 nach Tempern ist abhängig von der Filmdicke und den Substrat-Eigenschaften und ähnlich der Morphologie auf flachen Silicium-Wafern. In *Kapitel 6* wird ein Ansatz zur induzierten orientierten Mikrophasenseparation in dicken Block-Copolymer Filmen durch Behandlung mit orientiertem Dampffluss unter Verwendung eines Miniextruders vorgestellt, der als Alternative zu existierenden Verfahren wie Nichtlösungsmittel-induzierter Phasenseparation dienen könnte. Die ersten im Rahmen dieser Arbeit durchgeführten Untersuchungen zeigen das Potential der Methode auf, welche die Struktur im gesamten Volumen des Films durchgehend beeinflusst (durch SAXS-Messungen gezeigt). Jedoch sind detailliertere Studien notwendig, um die Prozedur zu optimieren. KW - block copolymer KW - thin films KW - solvo-thermal annealing KW - Block-copolymer KW - dünne Filme KW - Lösungsmittel-thermisches Tempern Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-424179 ER - TY - THES A1 - Riemer, Nastja T1 - Diazoniumsalze für die Synthese von Pflanzenschutzmitteln BT - Entwicklung neuer PD-katalysierter Kupplungsreaktionen mit Aryldiazoniumtetrafluoroboraten und Synthese von Herbiziden, Fungiziden und anderen biologisch aktiven Verbindungen Y1 - 2018 ER - TY - THES A1 - Homeyer, Marc Sören T1 - Photometrische Bestimmungen mittels eines modifizierten Schülerphotometers und naturwissenschaftliches Arbeiten im Seminarkurs Y1 - 2018 CY - 119, A 203 ER - TY - THES A1 - Grunert, Bianca T1 - Entwicklung von Markierungsreagenzien für die bildgebende Diagnostik T1 - Development of cell labeling probes for diagnostic imaging N2 - Die intrazelluläre Markierung mit geeigneten Reagenzien ermöglicht ihre bildgebende Darstellung in lebenden Organismen. Dieses Verfahren (auch „Zell-Tracking“ genannt) wird in der Grundlagenforschung zur Entwicklung zellulärer Therapien, für die Erforschung pathologischer Prozesse, wie der Metastasierung, sowie für Therapiekontrollen eingesetzt. Besondere Bedeutung haben in den letzten Jahren zelluläre Therapien mit Stammzellen erlangt, da sie großes Potential bei der Regeneration von Geweben bei Krankheiten wie Morbus Parkinson oder Typ-1-Diabetes versprechen. Für die Entwicklung einer zellulären Therapie sind Informationen über den Verbleib der applizierten Zellen in vivo (Homing-Potential), über ihre Zellphysiologie sowie über die Entstehung möglicher Entzündungen notwendig. Das Ziel der vorliegenden Arbeit war daher die Synthese von Markierungsreagenzien, die nicht nur eine effiziente Zellmarkierung ermöglichen, sondern einen synergistischen Effekt hinsichtlich des modalitätsübergreifenden Einsatzes in den bildgebenden Verfahren MRT und Laser-Ablation(LA)-ICP-MS erlauben. Die MRT-Bildgebung ermöglicht die nicht invasive Nachverfolgung markierter Zellen in vivo und die LA-ICP-MS die anschließende ex vivo Analytik zur Darstellung der Elementverteilung (Bioimaging) in einer Biopsieprobe oder in einem Gewebeschnitt. Für diese Zwecke wurden zwei verschiedene Markierungsreagenzien mit dem kontrastgebenden Element Gadolinium synthetisiert. Gadolinium eignet sich aufgrund seines hohen magnetischen Moments hervorragend für die MRT-Bildgebung und da es in Biomolekülen nicht natürlich vorkommt, konnten die Reagenzien gleichermaßen für die Zellmarkierung und das Bioimaging mit der LA-ICP-MS untersucht werden. Für die Synthese eines makromolekularen Reagenzes wurde das kommerziell verfügbare Dendrimer G5-PAMAM über bifunktionelle Linker mit dem Chelator DOTA funktionalisiert, um anschließend Gadolinium zu komplexieren. Ein zweites, nanopartikuläres Reagenz wurde über eine Solvothermal-Synthese erhalten, bei der Ln:GdVO4-Nanokristalle mit einer funktionellen Polyacrylsäure(PAA)-Hülle dargestellt wurden. Die Dotierung der Ln:GdVO4-PAA Nanokristalle mit verschiedenen Lanthanoiden (Ln=Eu, Tb) zeigte ihre prinzipielle Multiplexfähigkeit in der LA-ICP-MS. Beide Markierungsreagenzien zeichneten sich durch gute Bioverträglichkeiten und r1-Relaxivitäten aus, was zudem ihr Potential für Anwendungen als präklinische „blood-pool“ MRT-Kontrastmittel belegte. Die Untersuchung der Zellmarkierung erfolgte anhand einer Tumorzelllinie und einer Stammzelllinie, wobei beide Zellarten erfolgreich intrazellulär mit beiden Reagenzien markiert wurden. Nach der Zellmarkierung veranschaulichte die in vitro MRT-Bildgebung von Zell-Phantomen eine deutlichere Kontrastverstärkung der Zellen nach der Markierung mit den Nanokristallen im Vergleich zum kommerziellen Kontrastmittel Magnevist®. Die hohe Effizienz der Zellmarkierung mit den Nanokristallen und die damit verbundenen hohen Signalintensitäten in einer einzelnen Zelle erlaubten beim Bioimaging mit der LA-ICP-MS, Messungen bis zu einer Auflösung von 4 µm Laser Spot Size. Nach der Zellmarkierung mit den DOTA(Gd3+)-funktionalisierten G5-PAMAM Dendrimeren waren hingegen Aufnahmen mit der LA-ICP-MS nur bis zu einer Auflösung von 12 µm Laser Spot Size möglich. Insgesamt waren die Ln:GdVO4-PAA Nanokristalle mit größerer Ausbeute und kostengünstiger herstellbar als die DOTA(Gd3+)-funktionalisierten G5-PAMAM Dendrimere und zeigten zudem eine effizientere Zellmarkierung. Die Ln:GdVO4-PAA Nanokristalle erscheinen somit für das Zell-Tracking als besonders vielversprechend. Darauf aufbauend wurden die Nanokristalle zur Etablierung der Antikörper-Konjugation ausgewählt, was sie für die molekulare in vivo Bildgebung sowie für die Immuno-Bildgebung von Gewebeschnitten oder Biopsie-Proben mit der LA-ICP-MS anwendbar macht. N2 - Labeling of intracellular structures using appropriate reagents allows diagnostic imaging of such structures in living organisms. This procedure, also known as ‘cell-tracking’, can be applied in various fields of basic research, e.g. for development of cellular therapies, understanding of pathological processes such as metastasis as well as monitoring of therapeutic strategies. In recent years, cellular therapies involving stem cells have gained increasing importance for they promise great potential in the regeneration of damaged tissue associated with various diseases such as Parkinson’s disease or Type 1 diabetes. However, to enable the development of a cell-based therapy, information regarding the in vivo ability of administered cells to migrate to the organ of their origin (homing potential), the cell physiology and the risk of potential inflammation is essential. The objective of the present thesis was the synthesis of labeling reagents that not only enable efficient cell labeling, but also allow tracking of the labeled cells via magnetic resonance imaging (MRI) and laser ablation inductively coupled plasma mass spectroscopy (LA-ICP-MS). MRI offers the ability to non-invasively track the labeled cells in vivo, whereas LA-ICP-MS allows subsequent ex vivo analysis of biopsy samples. To this end, two different types of labeling reagents were synthesized containing the contrast-enhancing element gadolinium (Gd). Gd is perfectly suited for MRI due to its high magnetic moment and, since it does not occur naturally in biomolecules, the Gd-containing labelling reagents could additionally be investigated with regard to their cell labeling and bioimaging efficacy using LA-ICP-MS. Synthesis of a macromolecular labeling reagent was performed by functionalization of the commercially available dendrimer G5-PAMAM with the chelator DOTA, which subsequently allows complexation of Gd3+-ions. A second nanoparticulate labeling reagent was synthesized via a solvothermal route which yielded in Ln:GdVO4 nanocrystals having a functional shell of polyacrylic acid. Doping of these nanocrystals with different lanthanides (Ln=Eu, Tb) demonstrated their fundamental capability for multiple implementation with LA-ICP-MS. All synthesized labeling reagents showed suitable biocompatibility and r1-relativities, indicating their potential for application as in vivo preclinical MR imaging agents. The cell labeling efficacy of the synthesized reagents was investigated in both cancer and stem cell lines, whereby both cell types showed efficient intracellular uptake. After cell labelling, in vitro MRI of cell phantoms indicated that the nanocrystalline-labelled cells portrayed a significantly higher contrast enhancement, in comparison to labelling with the commercially available MRI agent, Magnevist. Bioimaging of the nanocrystalline-labelled cells with LA-ICP-MS enabled resolutions of up to 4 µm laser spot size to be achieved since the high labelling efficacy allowed high signal intensities to be observed. On the other hand, measurements of dendrimer-labelled cells could be performed up to resolutions of 12 µm laser spot size. Evaluation of the different labelling reagents showed that the one based on nanocrystals could be synthesized more cost effectively, with greater yields and resulted in a higher cell labelling efficacy, demonstrating a superior aptitude for cell-tracking applications. Consequently, the nanocrystalline labeling reagent was selected for conjugation with antibodies, which in turn enables in vitro ICP-MS-based immunohistochemistry detection as well as in vivo molecular imaging. KW - Zellmarkierung KW - Magnetresonanztomographie KW - Laserablation-ICP-MS KW - cell labeling probe KW - magnetic resonance imaging Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-422830 ER - TY - THES A1 - Vogel, Stefanie T1 - Sequence dependency of photon and electron induced DNA strand breaks T1 - Sequenzabhängigkeit von photonen-und elektroneninduzierten DNA Strangbrüchen N2 - Deoxyribonucleic acid (DNA) is the carrier of human genetic information and is exposed to environmental influences such as the ultraviolet (UV) fraction of sunlight every day. The photostability of the DNA against UV light is astonishing. Even if the DNA bases have a strong absorption maximum at around 260 nm/4.77 eV, their quantum yield of photoproducts remains very low 1. If the photon energies exceed the ionization energy (IE) of the nucleobases ( ̴ 8-9 eV) 2, the DNA can be severely damaged. Photoexcitation and -ionization reactions occur, which can induce strand breaks in the DNA. The efficiency of the excitation and ionization induced strand breaks in the target DNA sequences are represented by cross sections. If Si as a substrate material is used in the VUV irradiation experiments, secondary electrons with an energy below 3.6 eV are generated from the substrate. This low energy electrons (LEE) are known to induce dissociative electron attachment (DEA) in DNA and with it DNA strand breakage very efficiently. LEEs play an important role in cancer radiation therapy, since they are generated secondarily along the radiation track of ionizing radiation. In the framework of this thesis, different single stranded DNA sequences were irradiated with 8.44 eV vacuum UV (VUV) light and cross sections for single strand breaks (SSB) were determined. Several sequences were also exposed to secondary LEEs, which additionally contributed to the SSBs. First, the cross sections for SSBs depending on the type of nucleobases were determined. Both types of DNA sequences, mono-nucleobase and mixed sequences showed very similar results upon VUV radiation. The additional influence of secondarily generated LEEs resulted in contrast in a clear trend for the SSB cross sections. In this, the polythymine sequence had the highest cross section for SSBs, which can be explained by strong anionic resonances in this energy range. Furthermore, SSB cross sections were determined as a function of sequence length. This resulted in an increase in the strand breaks to the same extent as the increase in the geometrical cross section. The longest DNA sequence (20 nucleotides) investigated in this series, however, showed smaller cross section values for SSBs, which can be explained by conformational changes in the DNA. Moreover, several DNA sequences that included the radiosensitizers 5-Bromouracil (5BrU) and 8-Bromoadenine (8BrA) were investigated and the corresponding SSB cross sections were determined. It was shown that 5BrU reacts very strongly to VUV radiation leading to high strand break yields, which showed in turn a strong sequence-dependency. 8BrA, on the other hand, showed no sensitization to the applied VUV radiation, since almost no increase in strand breakage yield was observed in comparison to non-modified DNA sequences. In order to be able to identify the mechanisms of radiation damage by photons, the IEs of certain DNA sequences were further explored using photoionization tandem mass spectrometry. By varying the DNA sequence, both the IEs depending on the type of nucleobase as well as on the DNA strand length could be identified and correlated to the SSB cross sections. The influence of the IE on the photoinduced reaction in the brominated DNA sequences could be excluded. N2 - Desoxyribonukleinsäure (DNA) ist als Träger der menschlichen Erbinformation täglich vielen Einflüssen ausgesetzt. Diese Einflüsse können Teil unserer Umwelt sein, wie der ultraviolette (UV) Anteil des Sonnenlichts. Die Photostabilität der DNA gegen UV-Licht ist erstaunlich, denn trotz eines starkes Absorptionsmaximum der DNA-Basen bei etwa 260 nm/4,77 eV, bleibt ihre Quantenausbeute an Photoprodukten sehr gering 1. Überschreiten die Photonenenergien die Ionisationsenergie (IE) der Nukleinbasen ( ̴ 8-9 eV) 2, kann die DNA schwer geschädigt werden. Es treten Anregungs- und Ionisierungsreaktionen auf, die zu Strangbrüchen in der DNA führen. Die Effizienz der induzierten Strangbrüche in den untersuchten DNA-Sequenzen wird durch Wirkungsquerschnitte dargestellt. Wird in den Bestrahlungsexperimenten Silizium als Substratmaterial verwendet, werden aus dem Substrat zusätzliche Sekundärelektronen mit einer Energie unter 3,6 eV erzeugt, die weiteren Schaden an der DNA verursachen. Diese niederenergetischen Elektronen (LEE) sind dafür bekannt, dissoziative Elektronenanlagerung (DEA) und damit Strangbrüche in der DNA zu erzeugen. LEEs entstehen sekundär entlang des Strahlungsweges von ionisierender Strahlung im biologischen Gewebe, wenn in der Behandlung der Krankheit Krebs Strahlentherapie eingesetzt wird. Im Rahmen dieser Arbeit wurden verschiedene Einzelstrang-DNA-Sequenzen mit 8.44 eV Vakuum-UV (VUV) Licht bestrahlt und Wirkungsquerschnitte für Einzel-strangbrüche (SSB) bestimmt. Ein Teil der Sequenzen wurde außerdem sekundär erzeugten LEEs ausgesetzt, die einen zusätzlichen Beitrag zu den SSBs liefern. Als erstes wurde der Wirkungsquerschnitt für SSBs in Abhängigkeit der Nukleinbasen bestimmt. Hierbei weisen sowohl die DNA Sequenzen, die nur ein Sorte an Nukleinbasen besitzen als auch die gemischte Sequenzen sehr ähnliche Werte auf. Durch den zusätzlichen Einfluss der LEEs hat sich wiederum für die DNA Sequenzen mit nur einer Sorte an Nukleinbasen ein stark ausgeprägter Trend gezeigt. Die Polythymin-Sequenz weist den höchsten Wirkungsquerschnitt für SSBs auf, was durch ausgeprägte anionische Resonanzen in diesem Energiebereich begründet werden kann. Des Weiteren wurden Wirkungsquerschnitte für SSBs in Abhängigkeit Sequenzlänge ermittelt. Dabei ergab sich eine Erhöhung der SSBs im gleichen Maße wie die Vergrößerung des geometrischen Wirkungsquerschnitts. Die längste DNA Sequenz (20 Nukleotide), die in dieser Reihe untersucht wurde, zeigte hingegen kleinere Werte für den SSB Wirkungsquerschnitt, was durch Konformationsänderungen in der DNA erklärt werden kann. Einige der untersuchten DNA Sequenzen wurden zusätzlich mit den Radiosensibilisatoren 5-Bromouracil (5BrU) und 8-Bromoadenine (8BrA) modifiziert und entsprechende SSB Wirkungsquerschnitte bestimmt. Hierbei hat sich gezeigt, dass 5BrU mittels einer hohen Strangbruchausbeute sehr stark auf VUV Strahlung reagiert, wobei das Ausmaß der Reaktion stark sequenzabhängig ist. 8BrA hingegen, weist keine Sensibilisierung gegenüber der verwendeten VUV Strahlung auf, da keine Erhöhung der Strangbruchausbeute gegenüber unmodifizierten DNA Sequenzen ersichtlich ist. Um die Mechanismen der Strahlenschädigung durch Photonen besser einschätzen zu können, wurden zusätzlich die IEs bestimmter DNA Sequenzen mit Hilfe der Photoionisations-Tandem-Massenspektrometrie untersucht. Durch Variation der DNA-Sequenzen konnte sowohl ein Trend der IEs in Abhängigkeit der Nukleinbasen und der DNA-Stranglänge identifiziert und als auch eine Abhängigkeit der Reaktivität von 5BrU von seinem IE in der entsprechenden DNA Sequenz ausgeschlossen werden. Die IE Trends und die Wirkungsquerschnitte für SSBs wurden abschließend in Korrelation gebracht. KW - DNA KW - photo ionization KW - dissociative electron attachment KW - DNA origami KW - radiosensitizer KW - ionization energy KW - tandem mass spectrometry KW - DNS KW - Photoionisation KW - Dissoziative Elektronenanlagerung KW - DNA Origami KW - Radiosensibilisator KW - Ionisierungsenergie KW - Tandemmassenspektrometrie Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-419669 ER - TY - THES A1 - Choi, Youngeun T1 - DNA origami structures as versatile platforms for nanophotonics T1 - DNA Origami Struktruen als Vielseitige Plattform für Nanophotonik N2 - Nanophotonics is the field of science and engineering aimed at studying the light-matter interactions on the nanoscale. One of the key aspects in studying such optics at the nanoscale is the ability to assemble the material components in a spatially controlled manner. In this work, DNA origami nanostructures were used to self-assemble dye molecules and DNA coated plasmonic nanoparticles. Optical properties of dye nanoarrays, where the dyes were arranged at distances where they can interact by Förster resonance energy transfer (FRET), were systematically studied according to the size and arrangement of the dyes using fluorescein (FAM) as the donor and cyanine 3 (Cy 3) as the acceptor. The optimized design, based on steady-state and time-resolved fluorometry, was utilized in developing a ratiometric pH sensor with pH-inert coumarin 343 (C343) as the donor and pH-sensitive FAM as the acceptor. This design was further applied in developing a ratiometric toxin sensor, where the donor C343 is unresponsive and FAM is responsive to thioacetamide (TAA) which is a well-known hepatotoxin. The results indicate that the sensitivity of the ratiometric sensor can be improved by simply arranging the dyes into a well-defined array. The ability to assemble multiple fluorophores without dye-dye aggregation also provides a strategy to amplify the signal measured from a fluorescent reporter, and was utilized here to develop a reporter for sensing oligonucleotides. By incorporating target capturing sequences and multiple fluorophores (ATTO 647N dye molecules), a reporter for microbead-based assay for non-amplified target oligonucleotide sensing was developed. Analysis of the assay using VideoScan, a fluorescence microscope-based technology capable of conducting multiplex analysis, showed the DNA origami nanostructure based reporter to have a lower limit of detection than a single stranded DNA reporter. Lastly, plasmonic nanostructures were assembled on DNA origami nanostructures as substrates to study interesting optical behaviors of molecules in the near-field. Specifically, DNA coated gold nanoparticles, silver nanoparticles, and gold nanorods, were placed on the DNA origami nanostructure aiming to study surface-enhanced fluorescence (SEF) and surface-enhanced Raman scattering (SERS) of molecules placed in the hotspot of coupled plasmonic structures. N2 - Nanophotonik bezeichnet die Untersuchung von Licht in Wechselwirkung mit Materie im Nanometermaßstab. Die exakte Kontrolle über den Aufbau und die räumliche Anordnung der beteiligten Komponenten ist ein entscheidender Faktor für die Erforschung der Optik nanoskalierter Systeme. Eine mögliche Lösung bietet die selbstorganisatorische Eigenschaft von DNA-Origami-Nanostrukturen, die im Rahmen dieser Dissertation, insbesondere zur Kopplung verschiedener Farbstoffe bzw. plasmonisch aktiver Nanopartikel, verwendet wurden. Im ersten Teil dieser Dissertation wurden unterschiedliche Förster-Resonanzenergietransfer- (FRET) Farbstoff-Matrizen, bestehend aus Fluorescein (FAM) als FRET-Donor und Cyanine 3 (Cy 3) als FRET-Akzeptor, hergestellt und nachfolgend hinsichtlich des Einflusses ihrer Gesamtgröße und ihrer Anordnung via statischer und zeitaufgelöster Fluoreszenzspektroskopie untersucht. Daraufhin erfolgte die Weiterentwicklung der ermittelten optimalen Anordnung der Farbstoffe in einen ratiometrischen pH-Sensor, bestehend aus dem pH stabilen Coumarin 343 (C343) als FRET-Donor und dem pH sensitiven FAM als FRET-Akzeptor. Die erhaltenen Ergebnisse zeigten, dass sich die Sensitivität ratiometrischer Sensoren, insbesondere durch die wohldefinierte Anordnung der beteiligten Farbstoffe in der Matrize, deutlich steigern lassen. Selbige Anordnung konnte auch erfolgreich zur Entwicklung eines Giftstoffsensors, zum Nachweis des Hepatoxins Thioacetamid (TAA), verwendet werden. Die Möglichkeit der Anordnung mehrerer Farbstoffe, unter Vermeidung ungewollter Farbstoff-Aggregation, ermöglicht außerdem die Verstärkung der Signale sogenannter Fluoreszenzreporter. Dies führte, im Rahmen dieser Arbeit, zur erfolgreichen Entwicklung eines auf Mikroperlen basierenden Oligonukleotid-Sensors, welcher ohne die Notwendigkeit einer vorherigen Zielverstärkung (z.B. durch Polymerase-Kettenreaktion) auskommt. Die anschließende Analyse mittels VideoScan, einer Multiplex-Analyse-Technik basierend auf der Fluoreszenzmikroskopie, ergab deutlich niedrigere Nachweisgrenzen für auf DNA-Origami basierende Reporter im Vergleich zu DNA-Einzelstrang basierenden Reportern. Abschließend erfolgte die Verwendung der DNA-Origamis als Substrat für die präzise räumliche Anordnung verschiedener plasmonisch aktiver Nanopartikel zur Untersuchung des optischen Verhaltens von Zielmolekülen im plasmonischen Nahfeld. Die Untersuchung der oberflächenverstärkten Fluoreszenz (SEF) und oberflächenverstärkten Raman-Streuung (SERS) von Molekülen im plasmonischer Hotspots erfolgte insbesondere mit Fokus auf den Einfluss der unterschiedlichen Anordnung von Gold-Nanostäbchen, Gold-Nanopartikel, und Silber-Nanopartikel. KW - DNA origami KW - Förster resonance energy transfer KW - plasmonics KW - DNA Origami KW - Förster-Resonanzenergietransfer KW - Plasmonik Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-421483 ER - TY - THES A1 - Liebig, Ferenc T1 - Synthesis and characterization of superstructures based on gold nanotriangles Y1 - 2018 ER - TY - THES A1 - Schulze, Sven T1 - Entwicklung und Charakterisierung optischer Biosensorplattformen basierend auf photonischen Kristallen und Faser-Bragg-Gitter T1 - Development and characterization of optical biosensor platforms based on photonic crystalls and fiber Bragg gratings N2 - In dieser Arbeit steht die Entwicklung einer Sensorplattform für biochemische Anwendungen, welche auf einem optischen Detektionsprinzips beruht, im Vordergrund. Während der Entwicklung wurden zwei komplementäre Konzeptideen behandelt, zum einen ein Sensor, der auf photonischen Kristallen und Wellenleiterstrukturen basiert und zum anderen einen faserbasierten Sensor, der chemisch modifizierte Faser-Bragg-Gitter enthält. Das optische Detektionsprinzip in beiden Sensorideen ist die resultierende Brechungsindexänderung als messbare physikochemische Kenngröße. Das aus der Natur bekannte Phänomen der photonischen Kristalle, das u. a. bei Opalen und bei Schmetterlingen zu finden ist, wurde bereits 1887 von Lord Rayleigh beschrieben. Er beschrieb die optischen Eigenschaften von periodischen mehrschichtigen Filmen, welche als vereinfachtes Modell eines eindimensionalen photonischen Kristalls verstanden werden können. Die Periodizität der Brechungsindexänderung resultiert in einem optischen Filter für Frequenzen in einem bestimmten spektralen Bereich, weshalb dann dort keine Lichtausbreitung mehr möglich ist. Wird dieses System aber durch eine Defektstelle in der Brechungsindexperiodizität gestört, sodass daraus zwei perfekt periodische Systeme entstehen, ist die Lichtausbreitung für eine bestimmte Frequenz dennoch möglich. In der Folge resultiert daraus ein schmalbandiges Signal im Transmissionsspektrum. Die erlaubte Frequenz ist dabei u. a. abhängig vom Brechungsindexunterschied des periodischen Systems, d.h. Veränderung des Brechungsindexes einer Schicht führt zu einer spektralen Verschiebung der erlaubten Frequenz, dadurch kann dieses Sensorkonzept für biochemische Sensorik ausgenutzt werden [1]. Diese Entwicklung des auf photonischen Kristallen basierenden Sensors war eine Kooperation mit dem Industriepartner „Nanoplus GmbH“. In der Doktorarbeit wurden Simulationen und praktischen Arbeiten zur Designentwicklung des Sensors und die Arbeiten an einem ersten Modellaufbau für die biochemischen Anwendungen durchgeführt. Für den faserbasierten Sensor wurden Faser-Bragg-Gitter in den Faserkern hineingeschrieben. Hill et al. entdeckten 1978, dass solche Gitterstrukturen genau wie photonische Kristalle als optische Filter fungieren [2]. Die Gitter bestehen dabei aus Änderungen des Brechungsindexes im Faserkern. Im Laufe der nächsten vierzig Jahren wurden verschiedene Einschreibetechniken und Gitterstrukturen entwickelt, weshalb die Eigenschaften der jeweiligen Gitterstrukturen variieren. Eine solche Gitterstruktur sind u. a. die Faser-Bragg-Gitter, deren Gitterperiode, d. h. die Abstände der Brechungsindexmodifikationen, sich im Nanometer- bis Mikrometerbereich befinden. Aufgrund der kleinen Gitterperiode wird eine rückwärtsführende Welle im Kern für eine bestimmte Frequenz bzw. Wellenlänge, der Bragg-Wellenlänge, erzeugt. Im Endeffekt resultiert daraus ein schmalbandiges Signal sowohl im Transmissionsspektrum, als auch im Reflexionsspektrum. Die Resonanzwellenlänge ist dabei proportional zu der Gitterperiode und dem effektiven Brechungsindex, welcher vom Brechungsindex des Kerns und des kernumgebenen Materials abhängig ist. Letztlich eignet sich diese Technik für physikochemische Sensorik. Im Rahmen dieser Arbeit wurden die Gitter mit Hilfe einer relativen neuen Herstellungsmethode in die Fasern geschrieben [3]. Anschließend stand die Entwicklung eines Biosensors im Vordergrund, wobei zunächst ein Protokoll zum Ätzen der Faser mit Flusssäure entwickelt worden ist, dass das System sensitiv zum umgebenen Brechungsindex macht. Am Ende wurde ein Modellaufbau realisiert, indem ein Modellsystem, hier die Detektion vom C-reaktiven Protein mittels spezifischen einzelsträngigen DNS-Aptameren, erfolgreich getestet und quantifiziert worden ist. 1 Mandal, S.; Erickson, D. Nanoscale Optofluidic Sensor Arrays. Opt. Express 2008, 16 (3), 1623–1631. 2 Hill, K. O.; Fujii, Y.; Johnson, D. C.; Kawasaki, B. S. Photosensitivity in Optical Fiber Waveguides: Application to Reflection Filter Fabrication. Appl. Phys. Lett. 1978, 32 (10), 647–649. 3 Martínez, A.; Dubov, M.; Khrushchev, I.; Bennion, I. Direct Writing of Fibre Bragg Gratings by Femtosecond Laser. Electron. Lett. 2004, 40 (19), 1170. N2 - In this thesis, the development of a sensor platform for biochemical applications based on an optical detection principle is in the foreground. Two complementary concept ideas address during development, one based on photonic crystals next to waveguide structures and on the other with a fiber-based sensor containing chemically modified fiber Bragg gratings. The optical detection principle in both sensor ideas is the resulting refractive index change as a measurable physicochemical parameter. Lord Rayleigh described the well-known phenomenon of photonic crystals, which can be found among others in opals and butterflies, already in 1887. He described the optical properties of periodic multilayer films, which can be understood as a simplified model of a one-dimensional photonic crystal. The periodicity of the refractive index change results in an optical filter for frequencies in a certain spectral range, which is why no light propagation is possible there. However, if this is disturbed by a defect point in the refractive index periodicity, resulting in two perfectly periodic systems, the light propagation for a given frequency is still possible. This results in a narrowband signal in the transmission spectrum. The permitted frequency is dependent, inter alia, on the refractive index difference of the periodic system, that is, changing the refractive index of a layer leads to a spectral shift of the permitted frequency, thereby this sensor concept can be exploit for biochemical sensors [1]. This development of the sensor based on photonic crystals was a cooperation with the industrial partner “Nanoplus GmbH“. In the doctoral thesis, simulations and practical work for the design development of the sensor and the work on a first model set-up for the biochemical applications were carried out. For the fiber-based sensor, fiber Bragg gratings were written into the fiber core. Hill et al. discovered in 1978 that such lattice structures act as optical filters just like photonic crystals [2]. The gratings consist of changes in the refractive index in the fiber core. Over the next forty years, various inscription techniques and lattice structures have been developed, which is why the properties of the respective lattice structures vary. Such a lattice structure include the fiber Bragg gratings whose grating period, that is, the distances of the refractive index modifications, are in the nanometer to micrometer range. Due to the small grating period, a backward wave is generated in the core for a particular frequency, the Bragg wavelength. Ultimately, this results in a narrowband signal in both in the transmission spectrum, as well as in the reflection spectrum. The resonant wavelength is proportional to the grating period and the effective refractive index, which depends on the refractive index of the core and the core-surrounded material. Ultimately, this technique is suitable for physicochemical sensors. In this thesis, the gratings were written into the fibers using a relatively new manufacturing method [3]. Subsequently, the development of a biosensor was in the the foreground, whereby first a protocol for the etching of the fiber with hydrofluoric acid was developed, which makes the system sensitive to the surrounded refractive index. In the end, a model design was realized by successfully testing and quantifying a model system, here the detection of the C-reactive protein by means of specific single-stranded DNA aptamers. 1 Mandal, S.; Erickson, D. Nanoscale Optofluidic Sensor Arrays. Opt. Express 2008, 16 (3), 1623–1631. 2 Hill, K. O.; Fujii, Y.; Johnson, D. C.; Kawasaki, B. S. Photosensitivity in Optical Fiber Waveguides: Application to Reflection Filter Fabrication. Appl. Phys. Lett. 1978, 32 (10), 647–649. 3 Martínez, A.; Dubov, M.; Khrushchev, I.; Bennion, I. Direct Writing of Fibre Bragg Gratings by Femtosecond Laser. Electron. Lett. 2004, 40 (19), 1170. KW - Faser-Bragg-Gitter KW - fiber Bragg graiting KW - photonischer Kristall KW - photonic crystall KW - point-by-point-inscription method KW - Punkt-für-Punkt-Einschreibemethode KW - Faserätzen KW - fiber etching KW - optischer Fasersensor KW - fiber optical sensor KW - Aptamere KW - aptamers KW - C-reaktives Protein KW - c-reactive protein KW - Biomarker KW - biomarker Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-422139 ER - TY - THES A1 - Jensen, Anders Christian Solberg T1 - Structure and dynamics of amorphous carbonates related to biomineralization T1 - Struktur und Dynamik amorpher Carbonate im Zusammenhang mit der Biomineralisation BT - a neutron diffraction study N2 - Amorphous calcium carbonate(ACC) is a wide spread biological material found in many organisms, such as sea Urchins and mollusks, where it serves as either a precursor phase for the crystalline biominerals or is stabilized and used in the amorphous state. As ACC readily crystallizes, stabilizers such as anions, cations or macromolecules are often present to avoid or delay unwanted crystallization. Furthermore, additives often control the properties of the materials to suit the specific function needed for the organism. E.g. cystoliths in leaves that scatter light to optimize energy uptake from the sun or calcite/aragonite crystals used in protective shells in mussels and gastropods. Lifetime of the amorphous phase is controlled by the kinetic stability against crystallization. This has often been linked to water which plays a role in the mobility of ions and hence the probability of forming crystalline nuclei to initiate crystallization. However, it is unclear how the water molecules are incorporated within the amorphous phase, either as liquid confined in pores, as structural water binding to the ions or as a mixture of both. It is also unclear how this is perturbed when additives are added, especially Mg2+, one the most common additives found in biogenic samples. Mg2+ are expected to have a strong influence on the water incorporated into ACC, given the high energy barrier to dehydration of magnesium ions compared to calcium ions in solution. During the last 10-15 years, there has been a large effort to understand the local environment of the ions/molecules and how this affects the properties of the amorphous phase. But only a few aspects of the structure have so far been well-described in literature. The reason for this is partly caused by the low stability of ACC if exposed to air, where it tends to crystallize within minutes and by the limited quantities of ACC produced in traditional synthesis routes. A further obstacle has been the difficulty in modeling the local structure based on experimental data. To solve the problem of stability and sample size, a few studies have used stabilizers such as Mg2+ or OH- and severely dehydrated samples so as to stabilize the amorphous state, allowing for combined neutron and x-ray analysis to be performed. However, so far, a clear description of the local environments of water present in the structure has not been reported. In this study we show that ACC can be synthesized without any stabilizing additives in quantities necessary for neutron measurements and that accurate models can be derived with the help of empirical-potential structural refinement. These analyses have shown that there is a wide range of local environments for all of the components in the system suggesting that the amorphous phase is highly inhomogeneous, without any phase separation between ions and water. We also showed that the water in ACC is mainly structural and that there is no confined or liquid-like water present in the system. Analysis of amorphous magnesium carbonate also showed that there is a large difference in the local structure of the two cations and that Mg2+ surprisingly interacts with significantly less water molecules then Ca2+ despite the higher dehydration energy. All in all, this shows that the role of water molecules as a structural component of ACC, with a strong binding to cat- and anions probably retard or prevents the crystallization of the amorphous phase. N2 - Amorphes Calciumcarbonat (ACC) ist ein weit verbreitetes biologisches Material, das in vielen Organismen zu finden ist, beispielsweise in Seeigeln und Mollusken, wo es als Präkursorphase für kristalline Biomaterialien dient oder stabilisiert wird und im amorphen Zustand genutzt wird. Da ACC leicht kristallisiert, sind oft Stabilisatoren wie Anionen, Kationen und Makromoleküle zugegen, die eine ungewollte Kristallisation verzögern oder verhindern können. Zusätzlich kontrollieren Additive oftmals die Materialeigenschaften, um spezielle Funktionen erfüllen zu können, die der Organismus benötigt. Z.B. Zystolithen in Blättern, die das Licht streuen, um die Energieaufnahme durch das Sonnenlicht zu optimieren oder den Calcit-/Aragonitkristallen, die in den schützenden Schalen von Muscheln und Schnecken verwendet werden. Die Lebensdauer der amorphen Phase ist kontrolliert von der kinetischen Stabilität gegenüber der Kristallisation. Dies wurde oft mit Wasser verbunden, welches eine Rolle spielt für die Mobilität der Ionen und demzufolge für die Wahrscheinlichkeit der Bildung von Kristallisationskernen, die eine Kristallisation einleiten. Es ist jedoch unklar, wie die Wassermoleküle in die amorphe Phase integriert sind, ob als Flüssigkeit eingeschlossen in Poren, als strukturiertes Wasser gebunden an Ionen oder als Mischung aus beidem. Es ist ebenfalls unklar, wie dies gestört wird durch die Zugabe von Additiven, insbesondere Mg2+, eines der häufigsten Additive in biogenen Proben. Von Mg2+ wird ein starker Einfluss auf das in ACC integrierte Wasser vermutet, vergleicht man die hohe Energiebarriere gegen Dehydration von Magnesiumionen gegenüber Calciumionen in Lösung. Im Verlauf der letzten 10-15 Jahre wurden große Anstrengungen unternommen, um die lokale Umgebung der Ionen/Moleküle zu verstehen und wie diese die Eigenschaften der amorphen Phase beeinflusst. Jedoch wurden bisher nur wenige Aspekte der Struktur gut in der Literatur beschrieben. Dies wird zum Teil von der geringen Stabilität von ACC verursacht, wenn es der Luft ausgesetzt wird, wo es nach wenigen Minuten zur Kristallisation neigt und zum Teil von den begrenzten Mengen an ACC, welches auf traditionellen Synthesewegen produziert wird. Ein weiteres Hindernis stellte die Schwierigkeit dar, die lokale Struktur anhand von experimentellen Daten zu modellieren. Um das Problem der Stabilität und der Probenmenge zu beheben, haben einige Studien Stabilisatoren wie Mg2+ oder OH- und hochgradig dehydrierte Proben verwendet und dadurch den amorphen Zustand stabilisiert, welches eine kombinierte Neutronen- und Röntgenanalyse ermöglichte. Dennoch liegt bis jetzt keine klare Beschreibung der lokalen Umgebung von Wasser in der Struktur vor. In dieser Arbeit zeigen wir, dass ACC ohne stabilisierende Additive in Mengen hergestellt werden kann, wie sie für Neutronenmessungen benötigt werden und dass akkurate Modelle durch empirical-potential structural refinement abgeleitet werden können. Diese Analysen haben gezeigt, dass es eine große Bandbreite lokaler Umgebungen für alle Systemkomponenten gibt, was zu der Vermutung führt, dass die amorphe Phase hochgradig imhomogen ist ohne Phasentrennung zwischen Wasser und Ionen. Wir konnten ebenfalls zeigen, dass das Wasser in ACC hauptsächlich strukturiert ist und dass kein eingeschlossenes oder flüssigkeitsähnliches Wasser im System vorliegt. Die Analyse von amorphem Magnesiumcarbonat zeigte ebenfalls, dass es große Unterschiede in den lokalen Strukturen der beiden Kationen gibt und dass Mg2+ überraschenderweise mit signifikant weniger Wassermolekülen als Ca2+ interagiert, trotz der höheren Dehydrationsenergie. Zusammenfassend zeigt dies, dass die Wassermoleküle in der Rolle als strukturelle Komponenten von ACC, mit einer starken Bindung zu Kat- und Anionen wahrscheinlich die Kristallisation der amorphen Phase verzögern oder verhindern. KW - ACC KW - amorphes Calciumcarbonat KW - emperical potential structure refinement KW - Biomineralisierung Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-421691 ER - TY - THES A1 - Walther, Sebastian T1 - Funktionalisierung von Ölsäuremethylester und Alkydharzen für die photoinduzierte radikalische Polymerisation im UV Bereich N2 - Die vorliegende Arbeit behandelt die Synthese und Charakterisierung von funktionalisierten Alkydharzen und die photoinduzierte Polymerisation dieser unter Einsatz einer Quecksilberdampflampe oder einer UV LED mit unterschiedlicher Lichtintensität. Der Fokus dieser Arbeit bestand in der gezielten Substitution der internalen Doppelbindungen der Fettsäureester durch reaktivere Gruppen, wie Acrylate oder Methacrylate, welche für Alkydharze in dieser Form so in der Literatur nicht beschrieben sind. Untersuchungen des Polymerisationsverhaltens dieser funktionalisierten Harze wurden mit der Photo DSC durchgeführt, wobei Bis – (4 – methoxybenzoyl) diethylgermanium als Photoinitiator diente. Die Ergebnisse haben gezeigt, dass die Harze radikalisch polymerisiert werden können und eine geringere Abhängigkeit von der Umgebungsatmosphäre (Luftsauerstoff bzw. Stickstoff) vorliegt. Dies ist so in der Literatur für funktionalisierte Alkydharze nicht bekannt. Abmischungen von unterschiedlichen Monomeren und funktionalisierten Harzen bewirkten eine Steigerung der Viskosität sowie eine Verringerung der Sauerstoffinhibierung im Zuge der photoinduzierten Polymerisation unter Luftsauerstoff für die Quecksilberdampflampe und der UV LED. Zur Untersuchung der sauerstoffinhibierenden Wirkung der Harze sind Synthesen unterschiedlicher, funktionalisierter Ölsäuremethylester als Modellsubstanzen durchgeführt worden. Ein verbessertes Polymerisationsverhalten und eine geringe Abhängigkeit von der Umgebungsatmosphäre konnte für die Modelle nachgewiesen werden. Zur Aufklärung des verbesserten Polymerisationsverhaltens sind gezielt Substituenten (Imidazol, Brom, Alkohol, Acetat) in den funktionalisierten Ölsäuremethylester eingebaut worden, um den Einfluss dieser aufzuzeigen. Im Rahmen dieser Synthesen sind neuartige Strukturen synthetisiert worden, welche so in der Literatur nicht beschrieben sind. Die Gegenüberstellung der Polymerisationszeit, der Umsatz der (Meth-)Acrylatgruppen sowie die Zeit zum Erreichen der maximalen Polymerisationsgeschwindigkeit unter Verwendung von unterschiedlichen UV Lichtquellen hat einen Einfluss der Substituenten auf das Polymerisationsverhalten gezeigt. N2 - The present work deals with the synthesis and characterization of functionalized alkyl resins and the photoinduced polymerization of them with different UV light sources. The focus of this work was the targeted substitution of the internal double bonds of fatty acid esters by more reactive groups such as acrylates or methacrylates, which are not described in the literature for alkyd resins in this form. Differences in the basic polymerizability of these functionalized resins were carried out with the Photo DSC, with Bis – (4 – methoxybenzoyl) diethylgermane serving as the photoinitiator. The results showed that the resins could be radically polymerized and also had a lower dependence on the ambient atmosphere. This is not described in the literature for functionalized alkyd resins. Blends of different monomers and the functionalized resins also showed that in addition to the increase in viscosity and the polymerizability of the monomers was improved under atmospheric oxygen. The reference used was methyl oleate, which had been functionalized via the same routes of synthesis and polymerized photochemically. In the context of these syntheses, novel monomers have been synthesized which are thus unknown in the literature.
The reference substances confirmed the behavior of the functionalized resins and showed improved polymerization behavior under atmospheric oxygen. To elucidate these properties, different functionalized methyl oleate have been synthesized to investigate the influence of the substituents on the polymerizability under atmospheric oxygen. In particular, the polymerization time, the conversion of the (meth) acrylate groups and the time to reach the maximum polymerization rate played a decisive role. T2 - Functionalization of methyl oleate and alkyd resins for the photoinduced radical polymerization in the UV region KW - UV KW - Alkydharze KW - Fettsäuren KW - Funktionalisierte Ölsäuremethylester KW - Polymerisation KW - Druckfarben KW - Alkyd resin KW - printing inks KW - fatty acids KW - functionalized methyl oleate KW - polymerization KW - UV Y1 - 2018 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-421467 ER -