@phdthesis{Vranic2019, author = {Vranic, Marija}, title = {3D Structure of the biomarker hepcidin-25 in its native state}, doi = {10.25932/publishup-45929}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-459295}, school = {Universit{\"a}t Potsdam}, pages = {xii, 135}, year = {2019}, abstract = {Hepcidin-25 (Hep-25) plays a crucial role in the control of iron homeostasis. Since the dysfunction of the hepcidin pathway leads to multiple diseases as a result of iron imbalance, hepcidin represents a potential target for the diagnosis and treatment of disorders of iron metabolism. Despite intense research in the last decade targeted at developing a selective immunoassay for iron disorder diagnosis and treatment and better understanding the ferroportin-hepcidin interaction, questions remain. The key to resolving these underlying questions is acquiring exact knowledge of the 3D structure of native Hep-25. Since it was determined that the N-terminus, which is responsible for the bioactivity of Hep-25, contains a small Cu(II)-binding site known as the ATCUN motif, it was assumed that the Hep-25-Cu(II) complex is the native, bioactive form of the hepcidin. This structure has thus far not been elucidated in detail. Owing to the lack of structural information on metal-bound Hep-25, little is known about its possible biological role in iron metabolism. Therefore, this work is focused on structurally characterizing the metal-bound Hep-25 by NMR spectroscopy and molecular dynamics simulations. For the present work, a protocol was developed to prepare and purify properly folded Hep-25 in high quantities. In order to overcome the low solubility of Hep-25 at neutral pH, we introduced the C-terminal DEDEDE solubility tag. The metal binding was investigated through a series of NMR spectroscopic experiments to identify the most affected amino acids that mediate metal coordination. Based on the obtained NMR data, a structural calculation was performed in order to generate a model structure of the Hep-25-Ni(II) complex. The DEDEDE tag was excluded from the structural calculation due to a lack of NMR restraints. The dynamic nature and fast exchange of some of the amide protons with solvent reduced the overall number of NMR restraints needed for a high-quality structure. The NMR data revealed that the 20 Cterminal Hep-25 amino acids experienced no significant conformational changes, compared to published results, as a result of a pH change from pH 3 to pH 7 and metal binding. A 3D model of the Hep-25-Ni(II) complex was constructed from NMR data recorded for the hexapeptideNi(II) complex and Hep-25-DEDEDE-Ni(II) complex in combination with the fixed conformation of 19 C-terminal amino acids. The NMR data of the Hep-25-DEDEDE-Ni(II) complex indicates that the ATCUN motif moves independently from the rest of the structure. The 3D model structure of the metal-bound Hep-25 allows for future works to elucidate hepcidin's interaction with its receptor ferroportin and should serve as a starting point for the development of antibodies with improved selectivity.}, language = {en} } @phdthesis{Krentz2019, author = {Krentz, Konrad-Felix}, title = {A Denial-of-Sleep-Resilient Medium Access Control Layer for IEEE 802.15.4 Networks}, doi = {10.25932/publishup-43930}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-439301}, school = {Universit{\"a}t Potsdam}, pages = {xiv, 187}, year = {2019}, abstract = {With the emergence of the Internet of things (IoT), plenty of battery-powered and energy-harvesting devices are being deployed to fulfill sensing and actuation tasks in a variety of application areas, such as smart homes, precision agriculture, smart cities, and industrial automation. In this context, a critical issue is that of denial-of-sleep attacks. Such attacks temporarily or permanently deprive battery-powered, energy-harvesting, or otherwise energy-constrained devices of entering energy-saving sleep modes, thereby draining their charge. At the very least, a successful denial-of-sleep attack causes a long outage of the victim device. Moreover, to put battery-powered devices back into operation, their batteries have to be replaced. This is tedious and may even be infeasible, e.g., if a battery-powered device is deployed at an inaccessible location. While the research community came up with numerous defenses against denial-of-sleep attacks, most present-day IoT protocols include no denial-of-sleep defenses at all, presumably due to a lack of awareness and unsolved integration problems. After all, despite there are many denial-of-sleep defenses, effective defenses against certain kinds of denial-of-sleep attacks are yet to be found. The overall contribution of this dissertation is to propose a denial-of-sleep-resilient medium access control (MAC) layer for IoT devices that communicate over IEEE 802.15.4 links. Internally, our MAC layer comprises two main components. The first main component is a denial-of-sleep-resilient protocol for establishing session keys among neighboring IEEE 802.15.4 nodes. The established session keys serve the dual purpose of implementing (i) basic wireless security and (ii) complementary denial-of-sleep defenses that belong to the second main component. The second main component is a denial-of-sleep-resilient MAC protocol. Notably, this MAC protocol not only incorporates novel denial-of-sleep defenses, but also state-of-the-art mechanisms for achieving low energy consumption, high throughput, and high delivery ratios. Altogether, our MAC layer resists, or at least greatly mitigates, all denial-of-sleep attacks against it we are aware of. Furthermore, our MAC layer is self-contained and thus can act as a drop-in replacement for IEEE 802.15.4-compliant MAC layers. In fact, we implemented our MAC layer in the Contiki-NG operating system, where it seamlessly integrates into an existing protocol stack.}, language = {en} } @phdthesis{Thiede2019, author = {Thiede, Tobias}, title = {A multiscale analysis of additively manufactured lattice structures}, doi = {10.25932/publishup-47041}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-470418}, school = {Universit{\"a}t Potsdam}, pages = {xi, 97, LIII}, year = {2019}, abstract = {Additive Manufacturing (AM) in terms of laser powder-bed fusion (L-PBF) offers new prospects regarding the design of parts and enables therefore the production of lattice structures. These lattice structures shall be implemented in various industrial applications (e.g. gas turbines) for reasons of material savings or cooling channels. However, internal defects, residual stress, and structural deviations from the nominal geometry are unavoidable. In this work, the structural integrity of lattice structures manufactured by means of L-PBF was non-destructively investigated on a multiscale approach. A workflow for quantitative 3D powder analysis in terms of particle size, particle shape, particle porosity, inter-particle distance and packing density was established. Synchrotron computed tomography (CT) was used to correlate the packing density with the particle size and particle shape. It was also observed that at least about 50\% of the powder porosity was released during production of the struts. Struts are the component of lattice structures and were investigated by means of laboratory CT. The focus was on the influence of the build angle on part porosity and surface quality. The surface topography analysis was advanced by the quantitative characterisation of re-entrant surface features. This characterisation was compared with conventional surface parameters showing their complementary information, but also the need for AM specific surface parameters. The mechanical behaviour of the lattice structure was investigated with in-situ CT under compression and successive digital volume correlation (DVC). The deformation was found to be knot-dominated, and therefore the lattice folds unit cell layer wise. The residual stress was determined experimentally for the first time in such lattice structures. Neutron diffraction was used for the non-destructive 3D stress investigation. The principal stress directions and values were determined in dependence of the number of measured directions. While a significant uni-axial stress state was found in the strut, a more hydrostatic stress state was found in the knot. In both cases, strut and knot, seven directions were at least needed to find reliable principal stress directions.}, language = {en} } @phdthesis{Kegelmann2019, author = {Kegelmann, Lukas}, title = {Advancing charge selective contacts for efficient monolithic perovskite-silicon tandem solar cells}, doi = {10.25932/publishup-42642}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-426428}, school = {Universit{\"a}t Potsdam}, pages = {v, 155}, year = {2019}, abstract = {Hybrid organic-inorganic perovskites are one of the most promising material classes for photovoltaic energy conversion. In solar cells, the perovskite absorber is sandwiched between n- and p-type contact layers which selectively transport electrons and holes to the cell's cathode and anode, respectively. This thesis aims to advance contact layers in perovskite solar cells and unravel the impact of interface and contact properties on the device performance. Further, the contact materials are applied in monolithic perovskite-silicon heterojunction (SHJ) tandem solar cells, which can overcome the single junction efficiency limits and attract increasing attention. Therefore, all contact layers must be highly transparent to foster light harvesting in the tandem solar cell design. Besides, the SHJ device restricts processing temperatures for the selective contacts to below 200°C. A comparative study of various electron selective contact materials, all processed below 180°C, in n-i-p type perovskite solar cells highlights that selective contacts and their interfaces to the absorber govern the overall device performance. Combining fullerenes and metal-oxides in a TiO2/PC60BM (phenyl-C60-butyric acid methyl ester) double-layer contact allows to merge good charge extraction with minimized interface recombination. The layer sequence thereby achieved high stabilized solar cell performances up to 18.0\% and negligible current-voltage hysteresis, an otherwise pronounced phenomenon in this device design. Double-layer structures are therefore emphasized as a general concept to establish efficient and highly selective contacts. Based on this success, the concept to combine desired properties of different materials is transferred to the p-type contact. Here, a mixture of the small molecule Spiro-OMeTAD [2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluoren] and the doped polymer PEDOT [poly(3,4-ethylenedioxythiophene)] is presented as a novel hole selective contact. PEDOT thereby remarkably suppresses charge recombination at the perovskite surface, allowing an increase of quasi-Fermi level splitting in the absorber. Further, the addition of Spiro-OMeTAD into the PEDOT layer is shown to enhance charge extraction at the interface and allow high efficiencies up to 16.8\%. Finally, the knowledge on contact properties is applied to monolithic perovskite-SHJ tandem solar cells. The main goal is to optimize the top contact stack of doped Spiro-OMeTAD/molybdenum oxide(MoOx)/ITO towards higher transparency by two different routes. First, fine-tuning of the ITO deposition to mitigate chemical reduction of MoOx and increase the transmittance of MoOx/ITO stacks by 25\%. Second, replacing Spiro-OMeTAD with the alternative hole transport materials PEDOT/Spiro-OMeTAD mixtures, CuSCN or PTAA [poly(triaryl amine)]. Experimental results determine layer thickness constrains and validate optical simulations, which subsequently allow to realistically estimate the respective tandem device performances. As a result, PTAA represents the most promising replacement for Spiro-OMeTAD, with a projected increase of the optimum tandem device efficiency for the herein used architecture by 2.9\% relative to 26.5\% absolute. The results also reveal general guidelines for further performance gains of the technology.}, language = {en} } @phdthesis{Nagel2019, author = {Nagel, Oliver}, title = {Amoeboid cells as a transport system for micro-objects}, doi = {10.25932/publishup-44219}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-442192}, school = {Universit{\"a}t Potsdam}, pages = {x, 84}, year = {2019}, abstract = {Due to advances in science and technology towards smaller and more powerful processing units, the fabrication of micrometer sized machines for different tasks becomes more and more possible. Such micro-robots could revolutionize medical treatment of diseases and shall support to work on other small machines. Nevertheless, scaling down robots and other devices is a challenging task and will probably remain limited in near future. Over the past decade the concept of bio-hybrid systems has proved to be a promising approach in order to advance the further development of micro-robots. Bio-hybrid systems combine biological cells with artificial components, thereby benefiting from the functionality of living biological cells. Cell-driven micro-transport is one of the most prominent applications in the emerging field of these systems. So far, micrometer sized cargo has been successfully transported by means of swimming bacterial cells. The potential of motile adherent cells as transport systems has largely remained unexplored. This thesis concentrates on the social amoeba Dictyostelium discoideum as a potential candidate for an amoeboid bio-hybrid transport system. The use of this model organism comes with several advantages. Due to the unspecific properties of Dictyostelium adhesion, a wide range of different cargo materials can be used for transport. As amoeboid cells exceed bacterial cells in size by one order of magnitude, also the size of an object carried by a single cell can also be much larger for an amoeba. Finally it is possible to guide the cell-driven transport based on the chemotactic behavior of the amoeba. Since cells undergo a developmentally induced chemotactic aggregation, cargo could be assembled in a self-organized manner into a cluster. It is also possible to impose an external chemical gradient to guide the amoeboid transport system to a desired location. To establish Dictyostelium discoideum as a possible candidate for bio-hybrid transport systems, this thesis will first investigate the movement of single cells. Secondly, the interaction of cargo and cells will be studied. Eventually, a conceptional proof will be conducted, that the cheomtactic behavior can be exploited either to transport a cargo self-organized or through an external chemical source.}, language = {en} } @phdthesis{Grafe2019, author = {Grafe, Marianne Erika}, title = {Analysis of supramolecular assemblies of NE81, the first lamin protein in a non-metazoan organism}, doi = {10.25932/publishup-44180}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-441802}, school = {Universit{\"a}t Potsdam}, pages = {V, 94}, year = {2019}, abstract = {Lamine sind Proteine an der inneren Kernh{\"u}lle und bilden zusammen mit verbundenen Proteinen die nukle{\"a}re Lamina. Dieses Netzwerk sorgt f{\"u}r die Stabilit{\"a}t des Zellkerns und unterst{\"u}tzt die Organisation des Zell-Zytoskeletts. Zus{\"a}tzlich sind Lamine und ihre verbundenen Proteine in viele Prozesse wie Genregulation und Zelldifferenzierung involviert. Bis 2012 war der Stand der Forschung, dass nur bei mehrzelligen Organismen eine nukle{\"a}re Lamina zu finden ist. NE81 ist das erste lamin-{\"a}hnliche Protein, das in einem nicht-mehrzelligen Organismus (Dictyostelium discoideum) entdeckt wurde. Es hat viele Eigenschaften und Strukturmerkmale mit Laminen gemeinsam. Dazu z{\"a}hlt der dreiteilige Aufbau des Proteins, eine Phosphorylierungsstelle f{\"u}r ein Zellzyklus-abh{\"a}ngiges Enzym, ein Kernlokalisationssignal, wodurch das Protein in den Kern transportiert wird, sowie eine C-terminale Sequenz zur Verankerung des Proteins in der Kernh{\"u}lle. In dieser Arbeit wurden verschiedene Methoden zur vereinfachten Untersuchung von Laminstrukturen getestet, um zu zeigen, dass sich NE81 wie bereits bekannte Lamin-Proteine verh{\"a}lt und supramolekulare Netzwerke aus Laminfilamenten bildet. Zur Analyse der Struktur supramolekularer Anordnungen wurde das Protein durch Entfernen des Kernlokalisationssignals auf der {\"a}ußeren Kernh{\"u}lle von Dictyostelium gebildet. Die anschließende Untersuchung der Oberfl{\"a}che der Kerne mit einem Rasterelektronenmikroskop zeigte, dass NE81 Strukturen in der Gr{\"o}ße von Laminen bildet, allerdings nicht in regelm{\"a}ßigen filament{\"o}sen Anordnungen. Um die Entstehung der Laminfilamente zu untersuchen, wurde l{\"o}sliches NE81 aus Dictyostelium aufgereinigt und mit verschiedenen mikroskopischen Methoden untersucht. Dabei wurde festgestellt, dass NE81 unter Niedrigsalz-Bedingungen d{\"u}nne, fadenf{\"o}rmige Strukturen und Netzwerke ausbildet, die denen von S{\"a}ugetier-Laminen sehr {\"a}hnlich sind. Die Mutation der Phosphorylierungsstelle von NE81 zu einer imitierenden dauerhaften Phosphorylierung von NE81 in der Zelle, zeigte zun{\"a}chst ein gel{\"o}stes Protein, das {\"u}berraschenderweise unter Blaulichtbestrahlung der Zelle wieder lamin-{\"a}hnliche Anordnungen formte. Die Ergebnisse dieser Arbeit zeigen, dass NE81 echte Laminstrukturen ausbilden kann und hebt Dictyostelium als Nicht-S{\"a}ugetier-Modellorganismus mit einer gut charakterisierten Kernh{\"u}lle, mit allen relevanten, aus tierischen Zellen bekannten Proteinen, hervor.}, language = {en} } @phdthesis{Nikkhoo2019, author = {Nikkhoo, Mehdi}, title = {Analytical and numerical elastic dislocation models of volcano deformation processes}, doi = {10.25932/publishup-42972}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-429720}, school = {Universit{\"a}t Potsdam}, pages = {x, 175}, year = {2019}, abstract = {The advances in modern geodetic techniques such as the global navigation satellite system (GNSS) and synthetic aperture radar (SAR) provide surface deformation measurements with an unprecedented accuracy and temporal and spatial resolutions even at most remote volcanoes on Earth. Modelling of the high-quality geodetic data is crucial for understanding the underlying physics of volcano deformation processes. Among various approaches, mathematical models are the most effective for establishing a quantitative link between the surface displacements and the shape and strength of deformation sources. Advancing the geodetic data analyses and hence, the knowledge on the Earth's interior processes, demands sophisticated and efficient deformation modelling approaches. Yet the majority of these models rely on simplistic assumptions for deformation source geometries and ignore complexities such as the Earth's surface topography and interactions between multiple sources. This thesis addresses this problem in the context of analytical and numerical volcano deformation modelling. In the first part, new analytical solutions for triangular dislocations (TDs) in uniform infinite and semi-infinite elastic media have been developed. Through a comprehensive investigation, the locations and causes of artefact singularities and numerical instabilities associated with TDs have been determined and these long-standing drawbacks have been addressed thoroughly. This approach has then been extended to rectangular dislocations (RDs) with full rotational degrees of freedom. Using this solution in a configuration of three orthogonal RDs a compound dislocation model (CDM) has been developed. The CDM can represent generalized volumetric and planar deformation sources efficiently. Thus, the CDM is relevant for rapid inversions in early warning systems and can also be used for detailed deformation analyses. In order to account for complex source geometries and realistic topography in the deformation models, in this thesis the boundary element method (BEM) has been applied to the new solutions for TDs. In this scheme, complex surfaces are simulated as a continuous mesh of TDs that may possess any displacement or stress boundary conditions in the BEM calculations. In the second part of this thesis, the developed modelling techniques have been applied to five different real-world deformation scenarios. As the first and second case studies the deformation sources associated with the 2015 Calbuco eruption and 2013-2016 Copahue inflation period have been constrained by using the CDM. The highly anisotropic source geometries in these two cases highlight the importance of using generalized deformation models such as the CDM, for geodetic data inversions. The other three case studies in this thesis involve high-resolution dislocation models and BEM calculations. As the third case, the 2013 pre-explosive inflation of Volc{\´a}n de Colima has been simulated by using two ellipsoidal cavities, which locate zones of pressurization in the volcano's lava dome. The fourth case study, which serves as an example for volcanotectonics interactions, the 3-D kinematics of an active ring-fault at Tend{\"u}rek volcano has been investigated through modelling displacement time series over the 2003-2010 time period. As the fifth example, the deformation sources associated with North Korea's underground nuclear test in September 2017 have been constrained. These examples demonstrate the advancement and increasing level of complexity and the general applicability of the developed dislocation modelling techniques. This thesis establishes a unified framework for rapid and high-resolution dislocation modelling, which in addition to volcano deformations can also be applied to tectonic and humanmade deformations.}, language = {en} } @phdthesis{Sterzel2019, author = {Sterzel, Till}, title = {Analyzing global typologies of socio-ecological vulnerability}, doi = {10.25932/publishup-42883}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-428837}, school = {Universit{\"a}t Potsdam}, pages = {137}, year = {2019}, abstract = {On a planetary scale human populations need to adapt to both socio-economic and environmental problems amidst rapid global change. This holds true for coupled human-environment (socio-ecological) systems in rural and urban settings alike. Two examples are drylands and urban coasts. Such socio-ecological systems have a global distribution. Therefore, advancing the knowledge base for identifying socio-ecological adaptation needs with local vulnerability assessments alone is infeasible: The systems cover vast areas, while funding, time, and human resources for local assessments are limited. They are lacking in low an middle-income countries (LICs and MICs) in particular. But places in a specific socio-ecological system are not only unique and complex - they also exhibit similarities. A global patchwork of local rural drylands vulnerability assessments of human populations to socio-ecological and environmental problems has already been reduced to a limited number of problem structures, which typically cause vulnerability. However, the question arises whether this is also possible in urban socio-ecological systems. The question also arises whether these typologies provide added value in research beyond global change. Finally, the methodology employed for drylands needs refining and standardizing to increase its uptake in the scientific community. In this dissertation, I set out to fill these three gaps in research. The geographical focus in my dissertation is on LICs and MICs, which generally have lower capacities to adapt, and greater adaptation needs, regarding rapid global change. Using a spatially explicit indicator-based methodology, I combine geospatial and clustering methods to identify typical configurations of key factors in case studies causing vulnerability to human populations in two specific socio-ecological systems. Then I use statistical and analytical methods to interpret and appraise both the typical configurations and the global typologies they constitute. First, I improve the indicator-based methodology and then reanalyze typical global problem structures of socio-ecological drylands vulnerability with seven indicator datasets. The reanalysis confirms the key tenets and produces a more realistic and nuanced typology of eight spatially explicit problem structures, or vulnerability profiles: Two new profiles with typically high natural resource endowment emerge, in which overpopulation has led to medium or high soil erosion. Second, I determine whether the new drylands typology and its socio-ecological vulnerability concept advance a thematically linked scientific debate in human security studies: what drives violent conflict in drylands? The typology is a much better predictor for conflict distribution and incidence in drylands than regression models typically used in peace research. Third, I analyze global problem structures typically causing vulnerability in an urban socio-ecological system - the rapidly urbanizing coastal fringe (RUCF) - with eleven indicator datasets. The RUCF also shows a robust typology, and its seven profiles show huge asymmetries in vulnerability and adaptive capacity. The fastest population increase, lowest income, most ineffective governments, most prevalent poverty, and lowest adaptive capacity are all typically stacked in two profiles in LICs. This shows that beyond local case studies tropical cyclones and/or coastal flooding are neither stalling rapid population growth, nor urban expansion, in the RUCF. I propose entry points for scaling up successful vulnerability reduction strategies in coastal cities within the same vulnerability profile. This dissertation shows that patchworks of local vulnerability assessments can be generalized to structure global socio-ecological vulnerabilities in both rural and urban socio-ecological systems according to typical problems. In terms of climate-related extreme events in the RUCF, conflicting problem structures and means to deal with them are threatening to widen the development gap between LICs and high-income countries unless successful vulnerability reduction measures are comprehensively scaled up. The explanatory power for human security in drylands warrants further applications of the methodology beyond global environmental change research in the future. Thus, analyzing spatially explicit global typologies of socio-ecological vulnerability is a useful complement to local assessments: The typologies provide entry points for where to consider which generic measures to reduce typical problem structures - including the countless places without local assessments. This can save limited time and financial resources for adaptation under rapid global change.}, language = {en} } @phdthesis{Grishina2019, author = {Grishina, Yulia}, title = {Assessing the applicability of annotation projection methods for coreference relations}, doi = {10.25932/publishup-42537}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-425378}, school = {Universit{\"a}t Potsdam}, pages = {viii, 198}, year = {2019}, abstract = {The main goal of this thesis is to explore the feasibility of using cross-lingual annotation projection as a method of alleviating the task of manual coreference annotation. To reach our goal, we build a first trilingual parallel coreference corpus that encompasses multiple genres. For the annotation of the corpus, we develop common coreference annotation guidelines that are applicable to three languages (English, German, Russian) and include a novel domain-independent typology of bridging relations as well as state-of-the-art near-identity categories. Thereafter, we design and perform several annotation projection experiments. In the first experiment, we implement a direct projection method with only one source language. Our results indicate that, already in a knowledge-lean scenario, our projection approach is superior to the most closely related work of Postolache et al. (2006). Since the quality of the resulting annotations is to a high degree dependent on the word alignment, we demonstrate how using limited syntactic information helps to further improve mention extraction on the target side. As a next step, in our second experiment, we show how exploiting two source languages helps to improve the quality of target annotations for both language pairs by concatenating annotations projected from two source languages. Finally, we assess the projection quality in a fully automatic scenario (using automatically produced source annotations), and propose a pilot experiment on manual projection of bridging pairs. For each of the experiments, we carry out an in-depth error analysis, and we conclude that noisy word alignments, translation divergences and morphological and syntactic differences between languages are responsible for projection errors. We systematically compare and evaluate our projection methods, and we investigate the errors both qualitatively and quantitatively in order to identify problematic cases. Finally, we discuss the applicability of our method to coreference annotations and propose several avenues of future research.}, language = {en} } @phdthesis{Debsharma2019, author = {Debsharma, Tapas}, title = {Cellulose derived polymers}, doi = {10.25932/publishup-44131}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-441312}, school = {Universit{\"a}t Potsdam}, pages = {x, 103}, year = {2019}, abstract = {Plastics, such as polyethylene, polypropylene, and polyethylene terephthalate are part of our everyday lives in the form of packaging, household goods, electrical insulation, etc. These polymers are non-degradable and create many environmental problems and public health concerns. Additionally, these polymers are produced from finite fossils resources. With the continuous utilization of these limited resources, it is important to look towards renewable sources along with biodegradation of the produced polymers, ideally. Although many bio-based polymers are known, such as polylactic acid, polybutylene succinate adipate or polybutylene succinate, none have yet shown the promise of replacing conventional polymers like polyethylene, polypropylene and polyethylene terephthalate. Cellulose is one of the most abundant renewable resources produced in nature. It can be transformed into various small molecules, such as sugars, furans, and levoglucosenone. The aim of this research is to use the cellulose derived molecules for the synthesis of polymers. Acid-treated cellulose was subjected to thermal pyrolysis to obtain levoglucosenone, which was reduced to levoglucosenol. Levoglucosenol was polymerized, for the first time, by ring-opening metathesis polymerization (ROMP) yielding high molar mass polymers of up to ~150 kg/mol. The poly(levoglucosenol) is thermally stable up to ~220 ℃, amorphous, and is exhibiting a relatively high glass transition temperature of ~100 ℃. The poly(levoglucosenol) can be converted to a transparent film, resembling common plastic, and was found to degrade in a moist acidic environment. This means that poly(levoglucosenol) may find its use as an alternative to conventional plastic, for instance, polystyrene. Levoglucosenol was also converted into levoglucosenyl methyl ether, which was polymerized by cationic ring-opening metathesis polymerization (CROP). Polymers were obtained with molar masses up to ~36 kg/mol. These polymers are thermally stable up to ~220 ℃ and are semi-crystalline thermoplastics, having a glass transition temperature of ~35 ℃ and melting transition of 70-100 ℃. Additionally, the polymers underwent cross-linking, hydrogenation and thiol-ene click chemistry.}, language = {en} }