@phdthesis{MartinezGuajardo2024, author = {Mart{\´i}nez Guajardo, Alejandro}, title = {New zwitterionic polymers for antifouling applications}, doi = {10.25932/publishup-62682}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-626820}, school = {Universit{\"a}t Potsdam}, pages = {XIX, 145}, year = {2024}, abstract = {The remarkable antifouling properties of zwitterionic polymers in controlled environments are often counteracted by their delicate mechanical stability. In order to improve the mechanical stabilities of zwitterionic hydrogels, the effect of increased crosslinker densities was thus explored. In a first approach, terpolymers of zwitterionic monomer 3-[N -2(methacryloyloxy)ethyl-N,N-dimethyl]ammonio propane-1-sulfonate (SPE), hydrophobic monomer butyl methacrylate (BMA), and photo-crosslinker 2-(4-benzoylphenoxy)ethyl methacrylate (BPEMA) were synthesized. Thin hydrogel coatings of the copolymers were then produced and photo-crosslinked. Studies of the swollen hydrogel films showed that not only the mechanical stability but also, unexpectedly, the antifouling properties were improved by the presence of hydrophobic BMA units in the terpolymers. Based on the positive results shown by the amphiphilic terpolymers and in order to further test the impact that hydrophobicity has on both the antifouling properties of zwitterionic hydrogels and on their mechanical stability, a new amphiphilic zwitterionic methacrylic monomer, 3-((2-(methacryloyloxy)hexyl)dimethylammonio)propane-1-sulfonate (M1), was synthesized in good yields in a multistep synthesis. Homopolymers of M1 were obtained by free-radical polymerization. Similarly, terpolymers of M1, zwitterionic monomer SPE, and photo-crosslinker BPEMA were synthesized by free-radical copolymerization and thoroughly characterized, including its solubilities in selected solvents. Also, a new family of vinyl amide zwitterionic monomomers, namely 3-(dimethyl(2-(N -vinylacetamido)ethyl)ammonio)propane-1-sulfonate (M2), 4-(dimethyl(2-(N-vinylacetamido)ethyl)ammonio)butane-1-sulfonate (M3), and 3-(dimethyl(2-(N-vinylacetamido)ethyl)ammonio)propyl sulfate (M4), together with the new photo-crosslinker 4-benzoyl-N-vinylbenzamide (M5) that is well-suited for copolymerization with vinylamides, are introduced within the scope of the present work. The monomers are synthesized with good yields developing a multistep synthesis. Homopolymers of the new vinyl amide zwitterionic monomers are obtained by free-radical polymerization and thoroughly characterized. From the solubility tests, it is remarkable that the homopolymers produced are fully soluble in water, evidence of their high hydrophilicity. Copolymerization of the vinyl amide zwitterionic monomers, M2, M3, and M4 with the vinyl amide photo-crosslinker M5 proved to require very specific polymerization conditions. Nevertheless, copolymers were successfully obtained by free-radical copolymerization under appropriate conditions. Moreover, in an attempt to mitigate the intrinsic hydrophobicity introduced in the copolymers by the photo-crosslinkers, and based on the proven affinity of quaternized diallylamines to copolymerize with vinyl amides, a new quaternized diallylamine sulfobetaine photo-crosslinker 3-(diallyl(2-(4-benzoylphenoxy)ethyl)ammonio)propane-1-sulfonate (M6) is synthesized. However, despite a priori promising copolymerization suitability, copolymerization with the vinyl amide zwitterionic monomers could not be achieved.}, language = {en} } @phdthesis{Mostafa2024, author = {Mostafa, Amr}, title = {DNA origami nanoforks: A platform for cytochrome c single molecule surface enhanced Raman spectroscopy}, doi = {10.25932/publishup-63548}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-635482}, school = {Universit{\"a}t Potsdam}, pages = {xi, 90, x}, year = {2024}, abstract = {This thesis presents a comprehensive exploration of the application of DNA origami nanofork antennas (DONAs) in the field of spectroscopy, with a particular focus on the structural analysis of Cytochrome C (CytC) at the single-molecule level. The research encapsulates the design, optimization, and application of DONAs in enhancing the sensitivity and specificity of Raman spectroscopy, thereby offering new insights into protein structures and interactions. The initial phase of the study involved the meticulous optimization of DNA origami structures. This process was pivotal in developing nanoscale tools that could significantly enhance the capabilities of Raman spectroscopy. The optimized DNA origami nanoforks, in both dimer and aggregate forms, demonstrated an enhanced ability to detect and analyze molecular vibrations, contributing to a more nuanced understanding of protein dynamics. A key aspect of this research was the comparative analysis between the dimer and aggregate forms of DONAs. This comparison revealed that while both configurations effectively identified oxidation and spin states of CytC, the aggregate form offered a broader range of detectable molecular states due to its prolonged signal emission and increased number of molecules. This extended duration of signal emission in the aggregates was attributed to the collective hotspot area, enhancing overall signal stability and sensitivity. Furthermore, the study delved into the analysis of the Amide III band using the DONA system. Observations included a transient shift in the Amide III band's frequency, suggesting dynamic alterations in the secondary structure of CytC. These shifts, indicative of transitions between different protein structures, were crucial in understanding the protein's functional mechanisms and interactions. The research presented in this thesis not only contributes significantly to the field of spectroscopy but also illustrates the potential of interdisciplinary approaches in biosensing. The use of DNA origami-based systems in spectroscopy has opened new avenues for research, offering a detailed and comprehensive understanding of protein structures and interactions. The insights gained from this research are expected to have lasting implications in scientific fields ranging from drug development to the study of complex biochemical pathways. This thesis thus stands as a testament to the power of integrating nanotechnology, biochemistry, and spectroscopic techniques in addressing complex scientific questions.}, language = {en} } @phdthesis{Eren2024, author = {Eren, Enis Oğuzhan}, title = {Covalent anode materials for high-energy sodium-ion batteries}, doi = {10.25932/publishup-62258}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-622585}, school = {Universit{\"a}t Potsdam}, pages = {xi, 153}, year = {2024}, abstract = {The reliance on fossil fuels has resulted in an abnormal increase in the concentration of greenhouse gases, contributing to the global climate crisis. In response, a rapid transition to renewable energy sources has begun, particularly lithium-ion batteries, playing a crucial role in the green energy transformation. However, concerns regarding the availability and geopolitical implications of lithium have prompted the exploration of alternative rechargeable battery systems, such as sodium-ion batteries. Sodium is significantly abundant and more homogeneously distributed in the crust and seawater, making it easier and less expensive to extract than lithium. However, because of the mysterious nature of its components, sodium-ion batteries are not yet sufficiently advanced to take the place of lithium-ion batteries. Specifically, sodium exhibits a more metallic character and a larger ionic radius, resulting in a different ion storage mechanism utilized in lithium-ion batteries. Innovations in synthetic methods, post-treatments, and interface engineering clearly demonstrate the significance of developing high-performance carbonaceous anode materials for sodium-ion batteries. The objective of this dissertation is to present a systematic approach for fabricating efficient, high-performance, and sustainable carbonaceous anode materials for sodium-ion batteries. This will involve a comprehensive investigation of different chemical environments and post-modification techniques as well. This dissertation focuses on three main objectives. Firstly, it explores the significance of post-synthetic methods in designing interfaces. A conformal carbon nitride coating is deposited through chemical vapor deposition on a carbon electrode as an artificial solid-electrolyte interface layer, resulting in improved electrochemical performance. The interaction between the carbon nitride artificial interface and the carbon electrode enhances initial Coulombic efficiency, rate performance, and total capacity. Secondly, a novel process for preparing sulfur-rich carbon as a high-performing anode material for sodium-ion batteries is presented. The method involves using an oligo-3,4-ethylenedioxythiophene precursor for high sulfur content hard carbon anode to investigate the sulfur heteroatom effect on the electrochemical sodium storage mechanism. By optimizing the condensation temperature, a significant transformation in the materials' nanostructure is achieved, leading to improved electrochemical performance. The use of in-operando small-angle X-ray scattering provides valuable insights into the interaction between micropores and sodium ions during the electrochemical processes. Lastly, the development of high-capacity hard carbon, derived from 5-hydroxymethyl furfural, is examined. This carbon material exhibits exceptional performance at both low and high current densities. Extensive electrochemical and physicochemical characterizations shed light on the sodium storage mechanism concerning the chemical environment, establishing the material's stability and potential applications in sodium-ion batteries.}, language = {en} } @phdthesis{Hussein2024, author = {Hussein, Mahmoud}, title = {Solvent engineering for highly-efficiency lead-free perovskite solar cells}, doi = {10.25932/publishup-63037}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-630375}, school = {Universit{\"a}t Potsdam}, pages = {137}, year = {2024}, abstract = {Global warming, driven primarily by the excessive emission of greenhouse gases such as carbon dioxide into the atmosphere, has led to severe and detrimental environmental impacts. Rising global temperatures have triggered a cascade of adverse effects, including melting glaciers and polar ice caps, more frequent and intense heat waves disrupted weather patterns, and the acidification of oceans. These changes adversely affect ecosystems, biodiversity, and human societies, threatening food security, water availability, and livelihoods. One promising solution to mitigate the harmful effects of global warming is the widespread adoption of solar cells, also known as photovoltaic cells. Solar cells harness sunlight to generate electricity without emitting greenhouse gases or other pollutants. By replacing fossil fuel-based energy sources, solar cells can significantly reduce CO2 emissions, a significant contributor to global warming. This transition to clean, renewable energy can help curb the increasing concentration of greenhouse gases in the atmosphere, thereby slowing down the rate of global temperature rise. Solar energy's positive impact extends beyond emission reduction. As solar panels become more efficient and affordable, they empower individuals, communities, and even entire nations to generate electricity and become less dependent on fossil fuels. This decentralized energy generation can enhance resilience in the face of climate-related challenges. Moreover, implementing solar cells creates green jobs and stimulates technological innovation, further promoting sustainable economic growth. As solar technology advances, its integration with energy storage systems and smart grids can ensure a stable and reliable energy supply, reducing the need for backup fossil fuel power plants that exacerbate environmental degradation. The market-dominant solar cell technology is silicon-based, highly matured technology with a highly systematic production procedure. However, it suffers from several drawbacks, such as: 1) Cost: still relatively high due to high energy consumption due to the need to melt and purify silicon, and the use of silver as an electrode, which hinders their widespread availability, especially in low-income countries. 2) Efficiency: theoretically, it should deliver around 29\%; however, the efficiency of most of the commercially available silicon-based solar cells ranges from 18 - 22\%. 3) Temperature sensitivity: The efficiency decreases with the increase in the temperature, affecting their output. 4) Resource constraints: silicon as a raw material is unavailable in all countries, creating supply chain challenges. Perovskite solar cells arose in 2011 and matured very rapidly in the last decade as a highly efficient and versatile solar cell technology. With an efficiency of 26\%, high absorption coefficients, solution processability, and tunable band gap, it attracted the attention of the solar cells community. It represented a hope for cheap, efficient, and easily processable next-generation solar cells. However, lead toxicity might be the block stone hindering perovskite solar cells' market reach. Lead is a heavy and bioavailable element that makes perovskite solar cells environmentally unfriendly technology. As a result, scientists try to replace lead with a more environmentally friendly element. Among several possible alternatives, tin was the most suitable element due to its electronic and atomic structure similarity to lead. Tin perovskites were developed to alleviate the challenge of lead toxicity. Theoretically, it shows very high absorption coefficients, an optimum band gap of 1.35 eV for FASnI3, and a very high short circuit current, which nominates it to deliver the highest possible efficiency of a single junction solar cell, which is around 30.1\% according to Schockly-Quisser limit. However, tin perovskites' efficiency still lags below 15\% and is irreproducible, especially from lab to lab. This humble performance could be attributed to three reasons: 1) Tin (II) oxidation to tin (IV), which would happen due to oxygen, water, or even by the effect of the solvent, as was discovered recently. 2) fast crystallization dynamics, which occurs due to the lateral exposure of the P-orbitals of the tin atom, which enhances its reactivity and increases the crystallization pace. 3) Energy band misalignment: The energy bands at the interfaces between the perovskite absorber material and the charge selective layers are not aligned, leading to high interfacial charge recombination, which devastates the photovoltaic performance. To solve these issues, we implemented several techniques and approaches that enhanced the efficiency of tin halide perovskites, providing new chemically safe solvents and antisolvents. In addition, we studied the energy band alignment between the charge transport layers and the tin perovskite absorber. Recent research has shown that the principal source of tin oxidation is the solvent known as dimethylsulfoxide, which also happens to be one of the most effective solvents for processing perovskite. The search for a stable solvent might prove to be the factor that makes all the difference in the stability of tin-based perovskites. We started with a database of over 2,000 solvents and narrowed it down to a series of 12 new solvents that are suitable for processing FASnI3 experimentally. This was accomplished by looking into 1) the solubility of the precursor chemicals FAI and SnI2, 2) the thermal stability of the precursor solution, and 3) the potential to form perovskite. Finally, we show that it is possible to manufacture solar cells using a novel solvent system that outperforms those produced using DMSO. The results of our research give some suggestions that may be used in the search for novel solvents or mixes of solvents that can be used to manufacture stable tin-based perovskites. Due to the quick crystallization of tin, it is more difficult to deposit tin-based perovskite films from a solution than manufacturing lead-based perovskite films since lead perovskite is more often utilized. The most efficient way to get high efficiencies is to deposit perovskite from dimethyl sulfoxide (DMSO), which slows down the quick construction of the tin-iodine network that is responsible for perovskite synthesis. This is the most successful approach for achieving high efficiencies. Dimethyl sulfoxide, which is used in the processing, is responsible for the oxidation of tin, which is a disadvantage of this method. This research presents a potentially fruitful alternative in which 4-(tert-butyl) pyridine can substitute dimethyl sulfoxide in the process of regulating crystallization without causing tin oxidation to take place. Perovskite films that have been formed from pyridine have been shown to have a much-reduced defect density. This has resulted in increased charge mobility and better photovoltaic performance, making pyridine a desirable alternative for use in the deposition of tin perovskite films. The precise control of perovskite precursor crystallization inside a thin film is of utmost importance for optimizing the efficiency and manufacturing of solar cells. The deposition process of tin-based perovskite films from a solution presents difficulties due to the quick crystallization of tin compared to the more often employed lead perovskite. The optimal approach for attaining elevated efficiencies entails using dimethyl sulfoxide (DMSO) as a medium for depositing perovskite. This choice of solvent impedes the tin-iodine network's fast aggregation, which plays a crucial role in the production of perovskite. Nevertheless, this methodology is limited since the utilization of dimethyl sulfoxide leads to the oxidation of tin throughout the processing stage. In this thesis, we present a potentially advantageous alternative approach wherein 4-(tert-butyl) pyridine is proposed as a substitute for dimethyl sulfoxide in regulating crystallization processes while avoiding the undesired consequence of tin oxidation. Films of perovskite formed using pyridine as a solvent have a notably reduced density of defects, resulting in higher mobility of charges and improved performance in solar applications. Consequently, the utilization of pyridine for the deposition of tin perovskite films is considered advantageous. Tin perovskites are suffering from an apparent energy band misalignment. However, the band diagrams published in the current body of research display contradictions, resulting in a dearth of unanimity. Moreover, comprehensive information about the dynamics connected with charge extraction is lacking. This thesis aims to ascertain the energy band locations of tin perovskites by employing the kelvin probe and Photoelectron yield spectroscopy methods. This thesis aims to construct a precise band diagram for the often-utilized device stack. Moreover, a comprehensive analysis is performed to assess the energy deficits inherent in the current energetic structure of tin halide perovskites. In addition, we investigate the influence of BCP on the improvement of electron extraction in C60/BCP systems, with a specific emphasis on the energy factors involved. Furthermore, transient surface photovoltage was utilized to investigate the charge extraction kinetics of frequently studied charge transport layers, such as NiOx and PEDOT as hole transport layers and C60, ICBA, and PCBM as electron transport layers. The Hall effect, KP, and TRPL approaches accurately ascertain the p-doping concentration in FASnI3. The results consistently demonstrated a value of 1.5 * 1017 cm-3. Our research findings highlight the imperative nature of autonomously constructing the charge extraction layers for tin halide perovskites, apart from those used for lead perovskites. The crystallization of perovskite precursors relies mainly on the utilization of two solvents. The first one dissolves the perovskite powder to form the precursor solution, usually called the solvent. The second one precipitates the perovskite precursor, forming the wet film, which is a supersaturated solution of perovskite precursor and in the remains of the solvent and the antisolvent. Later, this wet film crystallizes upon annealing into a full perovskite crystallized film. In our research context, we proposed new solvents to dissolve FASnI3, but when we tried to form a film, most of them did not crystallize. This is attributed to the high coordination strength between the metal halide and the solvent molecules, which is unbreakable by the traditionally used antisolvents such as Toluene and Chlorobenzene. To solve this issue, we introduce a high-throughput antisolvent screening in which we screened around 73 selected antisolvents against 15 solvents that can form a 1M FASnI3 solution. We used for the first time in tin perovskites machine learning algorithm to understand and predict the effect of an antisolvent on the crystallization of a precursor solution in a particular solvent. We relied on film darkness as a primary criterion to judge the efficacy of a solvent-antisolvent pair. We found that the relative polarity between solvent and antisolvent is the primary factor that affects the solvent-antisolvent interaction. Based on our findings, we prepared several high-quality tin perovskite films free from DMSO and achieved an efficiency of 9\%, which is the highest DMSO tin perovskite device so far.}, language = {en} } @phdthesis{Martin2024, author = {Martin, Johannes}, title = {Synthesis of protein-polymer conjugates and block copolymers via sortase-mediated ligation}, doi = {10.25932/publishup-64566}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-645669}, school = {Universit{\"a}t Potsdam}, pages = {XVII, 150}, year = {2024}, abstract = {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 K{\"o}rper ausgeschieden oder abgebaut wird. Um die Zirkulationszeit im Blut signifikant zu verl{\"a}ngern, werden die Proteine mit synthetischen Polymeren modifiziert (Protein-Polymer-Konjugate). Die Proteine aller heute auf dem Markt erh{\"a}ltlichen Medikamente dieser Art tragen eine oder mehrere Polymerketten aus Poly(ethylenglycol) (PEG). Ein Nachteil der PEGylierung ist, dass viele Patienten bei regelm{\"a}ßiger Einnahme dieser Medikamente Antik{\"o}rper gegen PEG entwickeln, die den effizienzsteigernden Effekt der PEGylierung wieder aufheben. Ein weiterer Nachteil der PEGylierung ist die oftmals deutlich verringerte Aktivit{\"a}t der Konjugate im Vergleich zum nativen Protein. Der Grund daf{\"u}r ist die Herstellungsmethode der Konjugate, bei der meist die prim{\"a}ren Amine der Lysin-Seitenketten und der N-Terminus des Proteins genutzt werden. Da die meisten Proteine mehrere gut zug{\"a}ngliche Lysine aufweisen, werden oft unterschiedliche und teilweise mehrere Lysine mit PEG funktionalisiert, was zu einer Mischung an Regioisomeren f{\"u}hrt. Je nach Position der PEG-Kette kann das aktive Zentrum abgeschirmt oder die 3D-Struktur des Proteins ver{\"a}ndert werden, was zu einem teilweise drastischen Aktivit{\"a}tsabfall f{\"u}hrt. In dieser Arbeit wurde eine neuartige Methode zur Ligation von Makromolek{\"u}len untersucht. Die Verwendung eines Enzyms als Katalysator zur Verbindung zweier Makromolek{\"u}le ist bisher wenig untersucht und ineffizient. Als Enzym wurde Sortase A ausgew{\"a}hlt, 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 {\"U}berschusses von einem Edukt f{\"u}r Makromolek{\"u}le {\"u}berpr{\"u}ft. Zur Durchf{\"u}hrung der Sortase-vermittelten Ligation werden zwei komplement{\"a}re Peptidsequenzen verwendet, die Erkennungssequenz und das Nukleophil. Um eine systematische Untersuchung durchf{\"u}hren zu k{\"o}nnen, wurden alle n{\"o}tigen 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) gew{\"a}hlt, um eine enge Molmassenverteilung zu erreichen. Die Herstellung der Bausteine begann mit der Synthese der Peptide via automatisierter Festphasen-Peptidsynthese, um eine einfache {\"A}nderung der Peptidsequenz zu gew{\"a}hrleisten und um eine Modifizierung der Polymerkette nach der Polymerisation zu umgehen. Um die ben{\"o}tigte unterschiedliche Funktionalit{\"a}t 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 Ketten{\"u}bertr{\"a}ger (chain transfer agent, CTA) zur Kontrolle der Polymerisation mit dem auf dem Harz befindlichen Peptid gekoppelt. Die f{\"u}r die anschließende Polymerisation verwendeten Monomere basierten auf Acrylamiden und Acrylaten und wurden anhand ihrer Eignung als Alternativen zu PEG ausgew{\"a}hlt. Es wurde eine k{\"u}rzlich 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 zun{\"a}chst genutzt, um mittels Sortase-vermittelter Ligation zwei Polymerketten zu einem Blockcopolymer zu verbinden. Unter Verwendung von Ni2+-Ionen in Kombination mit einer Verl{\"a}ngerung der Erkennungssequenz um ein Histidin zur Unterdr{\"u}ckung der R{\"u}ckreaktion konnte ein maximaler Umsatz von 70 \% erreicht werden. Dabei zeigte sich ein oberes Limit von durchschnittlich 100 Wiederholungseinheiten; die Ligation von l{\"a}ngeren Polymeren war nicht erfolgreich. Danach wurden ein Modellprotein und ein Nanobody mit vielversprechenden medizinischen Eigenschaften mit den f{\"u}r die enzymkatalysierte Ligation ben{\"o}tigten Peptidsequenzen f{\"u}r 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 {\"a}hnliche Limitierung in der Polymer-Kettenl{\"a}nge beobachtet wie zuvor. Die auf Ni-Ionen basierte Strategie zur Gleichgewichtsverschiebung hatte hier keinen ausschlaggebenden Effekt, w{\"a}hrend die Verwendung von einem {\"U}berschuss an Polymer zur vollst{\"a}ndigen Umsetzung des Edukt-Nanobody f{\"u}hrte. Die erhaltenen Daten aus diesem Projekt bilden eine gute Basis f{\"u}r weitere Forschung in dem vielversprechenden Feld der enzymkatalysierten Herstellung von Protein-Polymer-Konjugaten und Blockcopolymeren. Langfristig k{\"o}nnte diese Herangehensweise eine vielseitig einsetzbare Herstellungsmethode von ortsspezifischen therapeutischen Protein-Polymer Konjugaten darstellen, welche sowohl eine hohe Aktivit{\"a}t als auch eine lange Zirkulationszeit im Blut aufweisen.}, language = {en} } @article{BrinkmannKoellnerMerketal.2023, author = {Brinkmann, Pia and K{\"o}llner, Nicole and Merk, Sven and Beitz, Toralf and Altenberger, Uwe and L{\"o}hmannsr{\"o}ben, Hans-Gerd}, title = {Comparison of handheld and echelle spectrometer to assess copper in ores by means of laser-induced breakdown spectroscopy (LIBS)}, series = {Minerals}, volume = {13}, journal = {Minerals}, number = {1}, publisher = {MDPI}, address = {Basel}, issn = {2075-163X}, doi = {10.3390/min13010113}, pages = {19}, year = {2023}, abstract = {Its properties make copper one of the world's most important functional metals. Numerous megatrends are increasing the demand for copper. This requires the prospection and exploration of new deposits, as well as the monitoring of copper quality in the various production steps. A promising technique to perform these tasks is Laser Induced Breakdown Spectroscopy (LIBS). Its unique feature, among others, is the ability to measure on site without sample collection and preparation. In this work, copper-bearing minerals from two different deposits are studied. The first set of field samples come from a volcanogenic massive sulfide (VMS) deposit, the second part from a stratiform sedimentary copper (SSC) deposit. Different approaches are used to analyze the data. First, univariate regression (UVR) is used. However, due to the strong influence of matrix effects, this is not suitable for the quantitative analysis of copper grades. Second, the multivariate method of partial least squares regression (PLSR) is used, which is more suitable for quantification. In addition, the effects of the surrounding matrices on the LIBS data are characterized by principal component analysis (PCA), alternative regression methods to PLSR are tested and the PLSR calibration is validated using field samples.}, language = {en} } @phdthesis{Henschel2023, author = {Henschel, Cristiane}, title = {Thermoresponsive polymers with co-nonsolvency behavior}, doi = {10.25932/publishup-57716}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-577161}, school = {Universit{\"a}t Potsdam}, pages = {xiv, 260}, year = {2023}, abstract = {Despite the popularity of thermoresponsive polymers, much is still unknown about their behavior, how it is triggered, and what factors influence it, hindering the full exploitation of their potential. One particularly puzzling phenomenon is called co-nonsolvency, in which a polymer is soluble in two individual solvents, but counter-intuitively becomes insoluble in mixtures of both. Despite the innumerous potential applications of such systems, including actuators, viscosity regulators and as carrier structures, this field has not yet been extensively studied apart from the classical example of poly(N isopropyl acrylamide) (PNIPAM) in mixtures of water and methanol. Therefore, this thesis focuses on evaluating how changes in the chemical structure of the polymers impact the thermoresponsive, aggregation and co-nonsolvency behaviors of both homopolymers and amphiphilic block copolymers. Within this scope, both the synthesis of the polymers and their characterization in solution is investigated. Homopolymers were synthesized by conventional free radical polymerization, whereas block copolymers were synthesized by consecutive reversible addition fragmentation chain transfer (RAFT) polymerizations. The synthesis of the monomers N isopropyl methacrylamide (NIPMAM) and N vinyl isobutyramide (NVIBAM), as well as a few chain transfer agents is also covered. Through turbidimetry measurements, the thermoresponsive and co-nonsolvency behavior of PNIPMAM and PNVIBAM homopolymers is then compared to the well-known PNIPAM, in aqueous solutions with 9 different organic co-solvents. Additionally, the effects of end-groups, molar mass, and concentration are investigated. Despite the similarity of their chemical structures, the 3 homopolymers show significant differences in transition temperatures and some divergences in their co-nonsolvency behavior. More complex systems are also evaluated, namely amphiphilic di- and triblock copolymers of PNIPAM and PNIPMAM with polystyrene and poly(methyl methacrylate) hydrophobic blocks. Dynamic light scattering is used to evaluate their aggregation behavior in aqueous and mixed aqueous solutions, and how it is affected by the chemical structure of the blocks, the chain architecture, presence of cosolvents and polymer concentration. The results obtained shed light into the thermoresponsive, co-nonsolvency and aggregation behavior of these polymers in solution, providing valuable information for the design of systems with a desired aggregation behavior, and that generate targeted responses to temperature and solvent mixture changes.}, language = {en} } @phdthesis{Esen2023, author = {Esen, Cansu}, title = {Carbon nitride incorporation in polymer networks}, doi = {10.25932/publishup-57625}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-576253}, school = {Universit{\"a}t Potsdam}, pages = {xvi, 175}, year = {2023}, abstract = {The urge of light utilization in fabrication of materials is as encouraging as challenging. Steadily increasing energy consumption in accordance with rapid population growth, is requiring a corresponding solution within the same rate of occurrence speed. Therefore, creating, designing and manufacturing materials that can interact with light and in further be applicable as well as disposable in photo-based applications are very much under attention of researchers. In the era of sustainability for renewable energy systems, semiconductor-based photoactive materials have received great attention not only based on solar and/or hydrocarbon fuels generation from solar energy, but also successful stimulation of photocatalytic reactions such as water splitting, pollutant degradation and organic molecule synthesisThe turning point had been reached for water splitting with an electrochemical cell consisting of TiO2-Pt electrode illuminated by UV light as energy source rather than an external voltage, that successfully pursued water photolysis by Fujishima and Honda in 1972. Ever since, there has been a great deal of interest in research of semiconductors (e.g. metal oxide, metal-free organic, noble-metal complex) exhibiting effective band gap for photochemical reactions. In the case of environmental friendliness, toxicity of metal-based semiconductors brings some restrictions in possible applications. Regarding this, very robust and 'earth-abundant' organic semiconductor, graphitic carbon nitride has been synthesized and successfully applied in photoinduced applications as novel photocatalyst. Properties such as suitable band gap, low charge carrier recombination and feasibility for scaling up, pave the way of advance combination with other catalysts to gather higher photoactivity based on compatible heterojunction. This dissertation aims to demonstrate a series of combinations between organic semiconductor g-CN and polymer materials that are forged through photochemistry, either in synthesis or in application. Fabrication and design processes as well as applications performed in accordance to the scope of thesis will be elucidated in detail. In addition to UV light, more attention is placed on visible light as energy source with a vision of more sustainability and better scalability in creation of novel materials and solar energy based applications.}, language = {en} } @phdthesis{Hwang2023, author = {Hwang, Jinyeon}, title = {Influence of the pore structure and chemical properties of all-carbon composites on their electrochemical properties in lithium-ion capacitors}, doi = {10.25932/publishup-59168}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-591683}, school = {Universit{\"a}t Potsdam}, pages = {156}, year = {2023}, abstract = {Lithium-ion capacitors (LICs) are promising energy storage devices by asymmetrically combining anode with a high energy density close to lithium-ion batteries and cathode with a high power density and long-term stability close to supercapacitors. For the further improvement of LICs, the development of electrode materials with hierarchical porosity, nitrogen-rich lithiophilic sites, and good electrical conductivity is essential. Nitrogen-rich all-carbon composite hybrids are suitable for these conditions along with high stability and tunability, resulting in a breakthrough to achieve the high performance of LICs. In this thesis, two different all-carbon composites are suggested to unveil how the pore structure of lithiophilic composites influences the properties of LICs. Firstly, the composite with 0-dimensional zinc-templated carbon (ZTC) and hexaazatriphenylene-hexacarbonitrile (HAT) is examined how the pore structure is connected to Li-ion storage property as LIC electrode. As the pore structure of HAT/ZTC composite is easily tunable depending on the synthetic factor and ratio of each component, the results will allow deeper insights into Li-ion dynamics in different porosity, and low-cost synthesis by optimization of the HAT:ZTC ratio. Secondly, the composite with 1-dimensional nanoporous carbon fiber (ACF) and cost-effective melamine is proposed as a promising all-carbon hybrid for large-scale application. Since ACF has ultra-micropores, the numerical structure-property relationships will be calculated out not only from total pore volume but more specifically from ultra-micropore volume. From these results above, it would be possible to understand how hybrid all-carbon composites interact with lithium ions in nanoscale as well as how structural properties affect the energy storage performance. Based on this understanding derived from the simple materials modeling, it will provide a clue to design the practical hybrid materials for efficient electrodes in LICs.}, language = {en} } @phdthesis{Frank2023, author = {Frank, Bradley D.}, title = {Complex and adaptive soft colloids}, school = {Universit{\"a}t Potsdam}, pages = {XIV, 154}, year = {2023}, language = {en} }