TY - JOUR A1 - Piekarczyk, Andreas A1 - Heitmann, Ulrike A1 - Weiß, Karl-Anders A1 - Köhl, Michael A1 - Bald, Ilko T1 - Development of a simple setup for temperature dependent mass spectrometric measurements for the investigation of outgassing effects in polymeric materials for solar application JF - Polymer testing N2 - A simple experimental setup for temperature dependent mass spectrometric measurements has been constructed. It consists of a heated sample chamber and a mass spectrometer and allows for measurements under inert gas and ambient air. Based on initial measurements on two extruded polystyrene (XPS) samples a methodology for the data analysis has been developed. With this methodology the outgassing temperature of volatile compounds, which were used as blowing agents, has been identified. Furthermore, the composition of the blowing agents has been analyzed by temperature dependent mass spectra. The results indicate the use of ambient air in one material and a mixture of the banned blowing agents R142b and R22, both hydrochlorofluorocarbons (HCFC), in the other material. The here described methodology provides an easy to use approach to identify such compounds, for example as part of environmental or quality control. Y1 - 2019 U6 - https://doi.org/10.1016/j.polymertesting.2019.106164 SN - 0142-9418 SN - 1873-2348 VL - 81 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Liebig, Ferenc A1 - Sarhan, Radwan Mohamed A1 - Schmitt, Clemens Nikolaus Zeno A1 - Thünemann, Andreas F. A1 - Prietzel, Claudia Christina A1 - Bargheer, Matias A1 - Koetz, Joachim T1 - Gold nanotriangles with crumble topping and their influence on catalysis and surface-enhanced raman spectroscopy JF - ChemPlusChem N2 - By adding hyaluronic acid (HA) to dioctyl sodium sulfosuccinate (AOT)-stabilized gold nanotriangles (AuNTs) with an average thickness of 7.5 +/- 1 nm and an edge length of about 175 +/- 17 nm, the AOT bilayer is replaced by a polymeric HA-layer leading to biocompatible nanoplatelets. The subsequent reduction process of tetrachloroauric acid in the HA-shell surrounding the AuNTs leads to the formation of spherical gold nanoparticles on the platelet surface. With increasing tetrachloroauric acid concentration, the decoration with gold nanoparticles can be tuned. SAXS measurements reveal an increase of the platelet thickness up to around 14.5 nm, twice the initial value of bare AuNTs. HRTEM micrographs show welding phenomena between densely packed particles on the platelet surface, leading to a crumble formation while preserving the original crystal structure. Crumbles crystallized on top of the platelets enhance the Raman signal by a factor of around 20, and intensify the plasmon-driven dimerization of 4-nitrothiophenol (4-NTP) to 4,4 '-dimercaptoazobenzene in a yield of up to 50 %. The resulting crumbled nanotriangles, with a biopolymer shell and the absorption maximum in the second window for in vivo imaging, are promising candidates for biomedical sensing. KW - gold nanostructures KW - HRTEM KW - hyaluronic acid KW - monolayer formation KW - SERS Y1 - 2020 U6 - https://doi.org/10.1002/cplu.201900745 SN - 2192-6506 VL - 85 IS - 3 SP - 519 EP - 526 PB - Wiley-VCH CY - Weinheim ER - TY - GEN A1 - Mayer, Dennis A1 - Lever, Fabiano A1 - Picconi, David A1 - Metje, Jan A1 - Ališauskas, Skirmantas A1 - Calegari, Francesca A1 - Düsterer, Stefan A1 - Ehlert, Christopher A1 - Feifel, Raimund A1 - Niebuhr, Mario A1 - Manschwetus, Bastian A1 - Kuhlmann, Marion A1 - Mazza, Tommaso A1 - Robinson, Matthew Scott A1 - Squibb, Richard James A1 - Trabattoni, Andrea A1 - Wallner, Måns A1 - Saalfrank, Peter A1 - Wolf, Thomas J. A. A1 - Gühr, Markus T1 - Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1301 Y1 - 2022 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-577442 SN - 1866-8372 IS - 1301 ER - TY - JOUR A1 - Mayer, Dennis A1 - Lever, Fabiano A1 - Picconi, David A1 - Metje, Jan A1 - Ališauskas, Skirmantas A1 - Calegari, Francesca A1 - Düsterer, Stefan A1 - Ehlert, Christopher A1 - Feifel, Raimund A1 - Niebuhr, Mario A1 - Manschwetus, Bastian A1 - Kuhlmann, Marion A1 - Mazza, Tommaso A1 - Robinson, Matthew Scott A1 - Squibb, Richard James A1 - Trabattoni, Andrea A1 - Wallner, Måns A1 - Saalfrank, Peter A1 - Wolf, Thomas J. A. A1 - Gühr, Markus T1 - Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy JF - Nature Communications N2 - The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states. Y1 - 2022 U6 - https://doi.org/10.1038/s41467-021-27908-y SN - 2041-1723 VL - 13 PB - Springer Nature CY - Berlin ER - TY - JOUR A1 - Oliver, Sandra N. A1 - Lunn, John Edward A1 - Urbanczyk-Wochniak, Ewa A1 - Lytovchenko, Anna A1 - van Dongen, Joost T. A1 - Faix, Benjamin A1 - Schmälzlin, Elmar A1 - Fernie, Alisdair R. A1 - Schmäelzlin, E. A1 - Geigenberger, Peter T1 - Decreased expression of cytosolic pyruvate kinase in potato tubers leads to a decline in pyruvate resulting in an in vivo repression of the alternative oxidase N2 - The aim of this work was to investigate the effect of decreased cytosolic pyruvate kinase (PKc) on potato (Solanum tuberosum) tuber metabolism. Transgenic potato plants with strongly reduced levels of PKc were generated by RNA interference gene silencing under the control of a tuber-specific promoter. Metabolite profiling showed that decreased PKc activity led to a decrease in the levels of pyruvate and some other organic acids involved in the tricarboxylic acid cycle. Flux analysis showed that this was accompanied by changes in carbon partitioning, with carbon flux being diverted from glycolysis toward starch synthesis. However, this metabolic shift was relatively small and hence did not result in enhanced starch levels in the tubers. Although total respiration rates and the ATP to ADP ratio were largely unchanged, transgenic tubers showed a strong decrease in the levels of alternative oxidase (AOX) protein and a corresponding decrease in the capacity of the alternative pathway of respiration. External feeding of pyruvate to tuber tissue or isolated mitochondria resulted in activation of the AOX pathway, both in the wild type and the PKc transgenic lines, providing direct evidence for the regulation of AOX by changes in pyruvate levels. Overall, these results provide evidence for a crucial role of PKc in the regulation of pyruvate levels as well as the level of the AOX in heterotrophic plant tissue, and furthermore reveal that these parameters are interlinked in vivo. Y1 - 2008 UR - http://www.plantphysiol.org/content/148/3/1640.full U6 - https://doi.org/10.1104/pp.108.126516 ER - TY - JOUR A1 - Reppert, Alexander von A1 - Sarhan, Radwan Mohamed A1 - Stete, Felix A1 - Pudell, Jan-Etienne A1 - Del Fatti, N. A1 - Crut, A. A1 - Koetz, Joachim A1 - Liebig, Ferenc A1 - Prietzel, Claudia Christina A1 - Bargheer, Matias T1 - Watching the Vibration and Cooling of Ultrathin Gold Nanotriangles by Ultrafast X-ray Diffraction JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - We study the vibrations of ultrathin gold nanotriangles upon optical excitation of the electron gas by ultrafast X-ray diffraction. We quantitatively measure the strain evolution in these highly asymmetric nano-objects, providing a direct estimation of the amplitude and phase of the excited vibrational motion. The maximal strain value is well reproduced by calculations addressing pump absorption by the nanotriangles and their resulting thermal expansion. The amplitude and phase of the out-of-plane vibration mode with 3.6 ps period dominating the observed oscillations are related to two distinct excitation mechanisms. Electronic and phonon pressures impose stresses with different time dependences. The nanosecond relaxation of the expansion yields a direct temperature sensing of the nano-object. The presence of a thin organic molecular layer at the nanotriangle/substrate interfaces drastically reduces the thermal conductance to the substrate. Y1 - 2016 U6 - https://doi.org/10.1021/acs.jpcc.6b11651 SN - 1932-7447 VL - 120 SP - 28894 EP - 28899 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Deng, Zijun A1 - Wang, Weiwei A1 - Xua, Xun A1 - Gould, Oliver E. C. A1 - Kratz, Karl A1 - Ma, Nan A1 - Lendlein, Andreas T1 - Polymeric sheet actuators with programmable bioinstructivity JF - PNAS N2 - Stem cells are capable of sensing and processing environmental inputs, converting this information to output a specific cell lineage through signaling cascades. Despite the combinatorial nature of mechanical, thermal, and biochemical signals, these stimuli have typically been decoupled and applied independently, requiring continuous regulation by controlling units. We employ a programmable polymer actuator sheet to autonomously synchronize thermal and mechanical signals applied to mesenchymal stem cells (MSC5). Using a grid on its underside, the shape change of polymer sheet, as well as cell morphology, calcium (Ca2+) influx, and focal adhesion assembly, could be visualized and quantified. This paper gives compelling evidence that the temperature sensing and mechanosensing of MSC5 are interconnected via intracellular Ca2+. Up-regulated Ca2+ levels lead to a remarkable alteration of histone H3K9 acetylation and activation of osteogenic related genes. The interplay of physical, thermal, and biochemical signaling was utilized to accelerate the cell differentiation toward osteogenic lineage. The approach of programmable bioinstructivity provides a fundamental principle for functional biomaterials exhibiting multifaceted stimuli on differentiation programs. Technological impact is expected in the tissue engineering of periosteum for treating bone defects. KW - reversible shape-memory actuator KW - mesenchymal stem cells KW - calcium influx KW - HDAC1 KW - RUNX2 Y1 - 2020 U6 - https://doi.org/10.1073/pnas.1910668117 SN - 1091-6490 VL - 117 IS - 4 SP - 1895 EP - 1901 PB - National Academy of Sciences CY - Washington, DC ER - TY - JOUR A1 - Bouakline, Foudhil A1 - Saalfrank, Peter T1 - Seemingly asymmetric atom-localized electronic densities following laser-dissociation of homonuclear diatomics JF - The journal of chemical physics : bridges a gap between journals of physics and journals of chemistry N2 - Recent experiments on laser-dissociation of aligned homonuclear diatomic molecules show an asymmetric forward-backward (spatial) electron-localization along the laser polarization axis. Most theoretical models attribute this asymmetry to interference effects between gerade and ungerade vibronic states. Presumably due to alignment, these models neglect molecular rotations and hence infer an asymmetric (post-dissociation) charge distribution over the two identical nuclei. In this paper, we question the equivalence that is made between spatial electron-localization, observed in experiments, and atomic electron-localization, alluded by these theoretical models. We show that (seeming) agreement between these models and experiments is due to an unfortunate omission of nuclear permutation symmetry, i.e., quantum statistics. Enforcement of the latter requires mandatory inclusion of the molecular rotational degree of freedom, even for perfectly aligned molecules. Unlike previous interpretations, we ascribe spatial electron-localization to the laser creation of a rovibronic wavepacket that involves field-free molecular eigenstates with opposite space-inversion symmetry i.e., even and odd parity. Space-inversion symmetry breaking would then lead to an asymmetric distribution of the (space-fixed) electronic density over the forward and backward hemisphere. However, owing to the simultaneous coexistence of two indistinguishable molecular orientational isomers, our analytical and computational results show that the post-dissociation electronic density along a specified space-fixed axis is equally shared between the two identical nuclei-a result that is in perfect accordance with the principle of the indistinguishability of identical particles. Published under an exclusive license by AIP Publishing. Y1 - 2021 U6 - https://doi.org/10.1063/5.0049710 SN - 0021-9606 SN - 1089-7690 VL - 154 IS - 23 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Bornhorst, Julia A1 - Kipp, Anna Patricia A1 - Haase, Hajo A1 - Meyer, Soeren A1 - Schwerdtle, Tanja T1 - The crux of inept biomarkers for risks and benefits of trace elements JF - Trends in Analytical Chemistry N2 - Nowadays, the role of trace elements (TE) is of growing interest because dyshomeostasis of selenium (Se), manganese (Mn), zinc (Zn), and copper (Cu) is supposed to be a risk factor for several diseases. Thereby, research focuses on identifying new biomarkers for the TE status to allow for a more reliable description of the individual TE and health status. This review mirrors a lack of well-defined, sensitive, and selective biomarkers and summarizes technical limitations to measure them. Thus, the capacity to assess the relationship between dietary TE intake, homeostasis, and health is restricted, which would otherwise provide the basis to define adequate intake levels of single TE in both healthy and diseased humans. Besides that, our knowledge is even more limited with respect to the real life situation of combined TE intake and putative interactions between single TE. KW - Trace elements KW - Copper KW - Zinc KW - Manganese KW - Selenium KW - Biomarker KW - Inductively coupled plasma mass spectrometry KW - Hyphenated techniques KW - Isotope ratios Y1 - 2018 U6 - https://doi.org/10.1016/j.trac.2017.11.007 SN - 0165-9936 SN - 1879-3142 VL - 104 SP - 183 EP - 190 PB - Elsevier CY - Oxford ER - TY - THES A1 - Martin, Johannes T1 - Synthesis of protein-polymer conjugates and block copolymers via sortase-mediated ligation N2 - In den vergangenen Jahrzehnten haben therapeutische Proteine in der pharmazeutischen Industrie mehr und mehr an Bedeutung gewonnen. Werden Proteine nichtmenschlichen Ursprungs verwendet, kann es jedoch zu einer Immunreaktion kommen, sodass das Protein sehr schnell aus dem Körper ausgeschieden oder abgebaut wird. Um die Zirkulationszeit im Blut signifikant zu verlängern, werden die Proteine mit synthetischen Polymeren modifiziert (Protein-Polymer-Konjugate). Die Proteine aller heute auf dem Markt erhältlichen Medikamente dieser Art tragen eine oder mehrere Polymerketten aus Poly(ethylenglycol) (PEG). Ein Nachteil der PEGylierung ist, dass viele Patienten bei regelmäßiger Einnahme dieser Medikamente Antikörper gegen PEG entwickeln, die den effizienzsteigernden Effekt der PEGylierung wieder aufheben. Ein weiterer Nachteil der PEGylierung ist die oftmals deutlich verringerte Aktivität der Konjugate im Vergleich zum nativen Protein. Der Grund dafür ist die Herstellungsmethode der Konjugate, bei der meist die primären Amine der Lysin-Seitenketten und der N-Terminus des Proteins genutzt werden. Da die meisten Proteine mehrere gut zugängliche Lysine aufweisen, werden oft unterschiedliche und teilweise mehrere Lysine mit PEG funktionalisiert, was zu einer Mischung an Regioisomeren führt. Je nach Position der PEG-Kette kann das aktive Zentrum abgeschirmt oder die 3D-Struktur des Proteins verändert werden, was zu einem teilweise drastischen Aktivitätsabfall führt. In dieser Arbeit wurde eine neuartige Methode zur Ligation von Makromolekülen untersucht. Die Verwendung eines Enzyms als Katalysator zur Verbindung zweier Makromoleküle ist bisher wenig untersucht und ineffizient. Als Enzym wurde Sortase A ausgewählt, eine gut untersuchte Ligase aus der Familie der Transpeptidasen, welche die Ligation zweier Peptide katalysieren kann. Ein Nachteil dieser Sortase-vermittelten Ligation ist, dass es sich um eine Gleichgewichtsreaktion handelt, wodurch hohe Ausbeuten schwierig zu erreichen sind. Im Rahmen dieser Dissertation wurden zwei zuvor entwickelte Methoden zur Verschiebung des Gleichgewichts ohne Einsatz eines großen Überschusses von einem Edukt für Makromoleküle überprüft. Zur Durchführung der Sortase-vermittelten Ligation werden zwei komplementäre Peptidsequenzen verwendet, die Erkennungssequenz und das Nukleophil. Um eine systematische Untersuchung durchführen zu können, wurden alle nötigen Bausteine (Protein-Erkennungssequenz zur Reaktion mit Nukleophil-Polymer und Polymer-Erkennungssequenz mit Nukleophil-Protein) hergestellt. Als Polymerisationstechnik wurde die radikalische Polymerisation mit reversibler Deaktivierung (im Detail, Atom Transfer Radical Polymerization, ATRP und Reversible Addition-Fragmentation Chain Transfer, RAFT polymerization) gewählt, um eine enge Molmassenverteilung zu erreichen. Die Herstellung der Bausteine begann mit der Synthese der Peptide via automatisierter Festphasen-Peptidsynthese, um eine einfache Änderung der Peptidsequenz zu gewährleisten und um eine Modifizierung der Polymerkette nach der Polymerisation zu umgehen. Um die benötigte unterschiedliche Funktionalität der zwei Peptidsequenzen (freier C-Terminus bei der Erkennungssequenz bzw. freier N-Terminus bei dem Nukleophil) zu erreichen, wurden verschiedene Linker zwischen Harz und Peptid verwendet. Danach wurde der Kettenüberträger (chain transfer agent, CTA) zur Kontrolle der Polymerisation mit dem auf dem Harz befindlichen Peptid gekoppelt. Die für die anschließende Polymerisation verwendeten Monomere basierten auf Acrylamiden und Acrylaten und wurden anhand ihrer Eignung als Alternativen zu PEG ausgewählt. Es wurde eine kürzlich entwickelte Technik basierend auf der RAFT-Polymerisation (xanthate-supported photo-iniferter RAFT, XPI-RAFT) verwendet um eine Reihe an Peptid-Polymeren mit unterschiedlichen Molekulargewichten und engen Molekulargewichtsverteilungen herzustellen. Nach Entfernung der Schutzgruppen der Peptid-Seitenketten wurden die Peptid-Polymere zunächst genutzt, um mittels Sortase-vermittelter Ligation zwei Polymerketten zu einem Blockcopolymer zu verbinden. Unter Verwendung von Ni2+-Ionen in Kombination mit einer Verlängerung der Erkennungssequenz um ein Histidin zur Unterdrückung der Rückreaktion konnte ein maximaler Umsatz von 70 % erreicht werden. Dabei zeigte sich ein oberes Limit von durchschnittlich 100 Wiederholungseinheiten; die Ligation von längeren Polymeren war nicht erfolgreich. Danach wurden ein Modellprotein und ein Nanobody mit vielversprechenden medizinischen Eigenschaften mit den für die enzymkatalysierte Ligation benötigten Peptidsequenzen für die Kopplung mit den zuvor hergestellten Peptid-Polymeren verwendet. Dabei konnte bei Verwendung des Modellproteins keine Bildung von Protein-Polymer-Konjugaten beobachtet werden. Der Nanobody konnte dagegen C-terminal mit einem Polymer funktionalisiert werden. Dabei wurde eine ähnliche Limitierung in der Polymer-Kettenlänge beobachtet wie zuvor. Die auf Ni-Ionen basierte Strategie zur Gleichgewichtsverschiebung hatte hier keinen ausschlaggebenden Effekt, während die Verwendung von einem Überschuss an Polymer zur vollständigen Umsetzung des Edukt-Nanobody führte. Die erhaltenen Daten aus diesem Projekt bilden eine gute Basis für weitere Forschung in dem vielversprechenden Feld der enzymkatalysierten Herstellung von Protein-Polymer-Konjugaten und Blockcopolymeren. Langfristig könnte diese Herangehensweise eine vielseitig einsetzbare Herstellungsmethode von ortsspezifischen therapeutischen Protein-Polymer Konjugaten darstellen, welche sowohl eine hohe Aktivität als auch eine lange Zirkulationszeit im Blut aufweisen. N2 - During the last decades, therapeutical proteins have risen to great significance in the pharmaceutical industry. As non-human proteins that are introduced into the human body cause a distinct immune system reaction that triggers their rapid clearance, most newly approved protein pharmaceuticals are shielded by modification with synthetic polymers to significantly improve their blood circulation time. All such clinically approved protein-polymer conjugates contain polyethylene glycol (PEG) and its conjugation is denoted as PEGylation. However, many patients develop anti-PEG antibodies which cause a rapid clearance of PEGylated molecules upon repeated administration. Therefore, the search for alternative polymers that can replace PEG in therapeutic applications has become important. In addition, although the blood circulation time is significantly prolonged, the therapeutic activity of some conjugates is decreased compared to the unmodified protein. The reason is that these conjugates are formed by the traditional conjugation method that addresses the protein's lysine side chains. As proteins have many solvent exposed lysines, this results in a somewhat uncontrolled attachment of polymer chains, leading to a mixture of regioisomers, with some of them eventually affecting the therapeutic performance. This thesis investigates a novel method for ligating macromolecules in a site-specific manner, using enzymatic catalysis. Sortase A is used as the enzyme: It is a well-studied transpeptidase which is able to catalyze the intermolecular ligation of two peptides. This process is commonly referred to as sortase-mediated ligation (SML). SML constitutes an equilibrium reaction, which limits product yield. Two previously reported methods to overcome this major limitation were tested with polymers without using an excessive amount of one reactant. Specific C- or N-terminal peptide sequences (recognition sequence and nucleophile) as part of the protein are required for SML. The complementary peptide was located at the polymer chain end. Grafting-to was used to avoid damaging the protein during polymerization. To be able to investigate all possible combinations (protein-recognition sequence and nucleophile-protein as well as polymer-recognition sequence and nucleophile-polymer) all necessary building blocks were synthesized. Polymerization via reversible deactivation radical polymerization (RDRP) was used to achieve a narrow molecular weight distribution of the polymers, which is required for therapeutic use. The synthesis of the polymeric building blocks was started by synthesizing the peptide via automated solid-phase peptide synthesis (SPPS) to avoid post-polymerization attachment and to enable easy adaptation of changes in the peptide sequence. To account for the different functionalities (free N- or C-terminus) required for SML, different linker molecules between resin and peptide were used. To facilitate purification, the chain transfer agent (CTA) for reversible addition-fragmentation chain-transfer (RAFT) polymerization was coupled to the resin-immobilized recognition sequence peptide. The acrylamide and acrylate-based monomers used in this thesis were chosen for their potential to replace PEG. Following that, surface-initiated (SI) ATRP and RAFT polymerization were attempted, but failed. As a result, the newly developed method of xanthate-supported photo-iniferter (XPI) RAFT polymerization in solution was used successfully to obtain a library of various peptide-polymer conjugates with different chain lengths and narrow molar mass distributions. After peptide side chain deprotection, these constructs were used first to ligate two polymers via SML, which was successful but revealed a limit in polymer chain length (max. 100 repeat units). When utilizing equimolar amounts of reactants, the use of Ni2+ ions in combination with a histidine after the recognition sequence to remove the cleaved peptide from the equilibrium maximized product formation with conversions of up to 70 %. Finally, a model protein and a nanobody with promising properties for therapeutical use were biotechnologically modified to contain the peptide sequences required for SML. Using the model protein for C- or N-terminal SML with various polymers did not result in protein-polymer conjugates. The reason is most likely the lack of accessibility of the protein termini to the enzyme. Using the nanobody for C-terminal SML, on the other hand, was successful. However, a similar polymer chain length limit was observed as in polymer-polymer SML. Furthermore, in case of the synthesis of protein-polymer conjugates, it was more effective to shift the SML equilibrium by using an excess of polymer than by employing the Ni2+ ion strategy. Overall, the experimental data from this work provides a good foundation for future research in this promising field; however, more research is required to fully understand the potential and limitations of using SML for protein-polymer synthesis. In future, the method explored in this dissertation could prove to be a very versatile pathway to obtain therapeutic protein-polymer conjugates that exhibit high activities and long blood circulation times. KW - biohybrid molecules KW - sortaseA KW - polymerization KW - RAFT KW - ATRP KW - peptide synthesis KW - enzymatic conjugation KW - sortagging Y1 - 2024 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-645669 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Banße, Wolfgang A1 - Ludwig, Eberhard A1 - Schilde, Uwe A1 - Weller, Frank A1 - Lehmann, Andreas T1 - Ligandenaustauschreaktionen von Bis(acetylacetonato)dioxo-molybdän(VI). Kristallstrukturen von Salicyl- aldehyd-benzoylhydrazonato(2-)]dioxom ethanol-molybdän(VI) und [Benzoylacetonbenzoylhydrazonato(2)]dioxo- triphenylphosphan-oxidmolybdän(VI) Y1 - 1995 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Banße, Wolfgang A1 - Ludwig, Eberhard A1 - Mickler, Wulfhard A1 - Hahn, Ekkehardt A1 - Lügger, Thomas A1 - Lehmann, Andreas T1 - Mangan(IV)-Komplexe mit dreizähnigen diaciden Liganden : Kristallstruktur von Acetylacetonato- salicylaldehyd-benzoylhydrazonato(2-methanol-mangan(III) Y1 - 1995 ER - TY - JOUR A1 - Uhlemann, Erhard A1 - Banße, Wolfgang A1 - Ludwig, Eberhard A1 - Schilde, Uwe A1 - Weller, Frank A1 - Lehmann, Andreas T1 - Template-Reaktion von Bis(acetylacetonato)-dioxo-molybdän(VI) mit Benzoylhydrazin Y1 - 1994 ER - TY - JOUR A1 - Banße, Wolfgang A1 - Fliegner, Jana Ute A1 - Hennig, H. A1 - Lehmann, Andreas A1 - Uhlemann, Erhard A1 - Tschwatschal, F. T1 - Ligand exchange reactions of molybdenum hexacarbonyl with tridentate diacidic ligands Y1 - 1997 ER - TY - JOUR A1 - Schulze-Makuch, Dirk A1 - Wagner, Dirk A1 - Kounaves, Samuel P. A1 - Mangelsdorf, Kai A1 - Devine, Kevin G. A1 - de Vera, Jean-Pierre A1 - Schmitt-Kopplin, Philippe A1 - Grossart, Hans-Peter A1 - Parro, Victor A1 - Kaupenjohann, Martin A1 - Galy, Albert A1 - Schneider, Beate A1 - Airo, Alessandro A1 - Froesler, Jan A1 - Davila, Alfonso F. A1 - Arens, Felix L. A1 - Caceres, Luis A1 - Cornejo, Francisco Solis A1 - Carrizo, Daniel A1 - Dartnell, Lewis A1 - DiRuggiero, Jocelyne A1 - Flury, Markus A1 - Ganzert, Lars A1 - Gessner, Mark O. A1 - Grathwohl, Peter A1 - Guan, Lisa A1 - Heinz, Jacob A1 - Hess, Matthias A1 - Keppler, Frank A1 - Maus, Deborah A1 - McKay, Christopher P. A1 - Meckenstock, Rainer U. A1 - Montgomery, Wren A1 - Oberlin, Elizabeth A. A1 - Probst, Alexander J. A1 - Saenz, Johan S. A1 - Sattler, Tobias A1 - Schirmack, Janosch A1 - Sephton, Mark A. A1 - Schloter, Michael A1 - Uhl, Jenny A1 - Valenzuela, Bernardita A1 - Vestergaard, Gisle A1 - Woermer, Lars A1 - Zamorano, Pedro T1 - Transitory microbial habitat in the hyperarid Atacama Desert JF - Proceedings of the National Academy of Sciences of the United States of America KW - habitat KW - aridity KW - microbial activity KW - biomarker KW - Mars Y1 - 2018 U6 - https://doi.org/10.1073/pnas.1714341115 SN - 0027-8424 VL - 115 IS - 11 SP - 2670 EP - 2675 PB - National Acad. of Sciences CY - Washington ER -