@phdthesis{Ibarra2021,
  author    = {Ibarra, Federico},
  title     = {The thermal and rheological state of the Central Andes and its relationship to active deformation processes},
  doi       = {10.25932/publishup-50622},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-506226},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xvi, 149},
  year      = {2021},
  abstract  = {The Central Andes region in South America is characterized by a complex and heterogeneous deformation system. Recorded seismic activity and mapped neotectonic structures indicate that most of the intraplate deformation is located along the margins of the orogen, in the transitions to the foreland and the forearc. Furthermore, the actively deforming provinces of the foreland exhibit distinct deformation styles that vary along strike, as well as characteristic distributions of seismicity with depth. The style of deformation transitions from thin-skinned in the north to thick-skinned in the south, and the thickness of the seismogenic layer increases to the south. Based on geological/geophysical observations and numerical modelling, the most commonly invoked causes for the observed heterogeneity are the variations in sediment thickness and composition, the presence of inherited structures, and changes in the dip of the subducting Nazca plate. However, there are still no comprehensive investigations on the relationship between the lithospheric composition of the Central Andes, its rheological state and the observed deformation processes. The central aim of this dissertation is therefore to explore the link between the nature of the lithosphere in the region and the location of active deformation. The study of the lithospheric composition by means of independent-data integration establishes a strong base to assess the thermal and rheological state of the Central Andes and its adjacent lowlands, which alternatively provide new foundations to understand the complex deformation of the region. In this line, the general workflow of the dissertation consists in the construction of a 3D data-derived and gravity-constrained density model of the Central Andean lithosphere, followed by the simulation of the steady-state conductive thermal field and the calculation of strength distribution. Additionally, the dynamic response of the orogen-foreland system to intraplate compression is evaluated by means of 3D geodynamic modelling. The results of the modelling approach suggest that the inherited heterogeneous composition of the lithosphere controls the present-day thermal and rheological state of the Central Andes, which in turn influence the location and depth of active deformation processes. Most of the seismic activity and neo--tectonic structures are spatially correlated to regions of modelled high strength gradients, in the transition from the felsic, hot and weak orogenic lithosphere to the more mafic, cooler and stronger lithosphere beneath the forearc and the foreland. Moreover, the results of the dynamic simulation show a strong localization of deviatoric strain rate second invariants in the same region suggesting that shortening is accommodated at the transition zones between weak and strong domains. The vertical distribution of seismic activity appears to be influenced by the rheological state of the lithosphere as well. The depth at which the frequency distribution of hypocenters starts to decrease in the different morphotectonic units correlates with the position of the modelled brittle-ductile transitions; accordingly, a fraction of the seismic activity is located within the ductile part of the crust. An exhaustive analysis shows that practically all the seismicity in the region is restricted above the 600°C isotherm, in coincidence with the upper temperature limit for brittle behavior of olivine. Therefore, the occurrence of earthquakes below the modelled brittle-ductile could be explained by the presence of strong residual mafic rocks from past tectonic events. Another potential cause of deep earthquakes is the existence of inherited shear zones in which brittle behavior is favored through a decrease in the friction coefficient. This hypothesis is particularly suitable for the broken foreland provinces of the Santa Barbara System and the Pampean Ranges, where geological studies indicate successive reactivation of structures through time. Particularly in the Santa Barbara System, the results indicate that both mafic rocks and a reduction in friction are required to account for the observed deep seismic events.},
  language  = {en}
}
@phdthesis{Tunn2020,
  author    = {Tunn, Isabell},
  title     = {From single molecules to bulk materials: tuning the viscoelastic properties of coiled coil cross-linked hydrogels},
  doi       = {10.25932/publishup-47595},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-475955},
  school      = {Universit{\"a}t Potsdam},
  pages     = {XVI, 140},
  year      = {2020},
  abstract  = {The development of bioinspired self-assembling materials, such as hydrogels, with promising applications in cell culture, tissue engineering and drug delivery is a current focus in material science. Biogenic or bioinspired proteins and peptides are frequently used as versatile building blocks for extracellular matrix (ECM) mimicking hydrogels. However, precisely controlling and reversibly tuning the properties of these building blocks and the resulting hydrogels remains challenging. Precise control over the viscoelastic properties and self-healing abilities of hydrogels are key factors for developing intelligent materials to investigate cell matrix interactions. Thus, there is a need to develop building blocks that are self-healing, tunable and self-reporting. This thesis aims at the development of α-helical peptide building blocks, called coiled coils (CCs), which integrate these desired properties. Self-healing is a direct result of the fast self-assembly of these building blocks when used as material cross-links. Tunability is realized by means of reversible histidine (His)-metal coordination bonds. Lastly, implementing a fluorescent readout, which indicates the CC assembly state, self-reporting hydrogels are obtained. Coiled coils are abundant protein folding motifs in Nature, which often have mechanical function, such as in myosin or fibrin. Coiled coils are superhelices made up of two or more α-helices wound around each other. The assembly of CCs is based on their repetitive sequence of seven amino acids, so-called heptads (abcdefg). Hydrophobic amino acids in the a and d position of each heptad form the core of the CC, while charged amino acids in the e and g position form ionic interactions. The solvent-exposed positions b, c and f are excellent targets for modifications since they are more variable. His-metal coordination bonds are strong, yet reversible interactions formed between the amino acid histidine and transition metal ions (e.g. Ni2+, Cu2+ or Zn2+). His-metal coordination bonds essentially contribute to the mechanical stability of various high-performance proteinaceous materials, such as spider fangs, Nereis worm jaws and mussel byssal threads. Therefore, I bioengineered reversible His-metal coordination sites into a well-characterized heterodimeric CC that served as tunable material cross-link. Specifically, I took two distinct approaches facilitating either intramolecular (Chapter 4.2) and/or intermolecular (Chapter 4.3) His-metal coordination. Previous research suggested that force-induced CC unfolding in shear geometry starts from the points of force application. In order to tune the stability of a heterodimeric CC in shear geometry, I inserted His in the b and f position at the termini of force application (Chapter 4.2). The spacing of His is such that intra-CC His-metal coordination bonds can form to bridge one helical turn within the same helix, but also inter-CC coordination bonds are not generally excluded. Starting with Ni2+ ions, Raman spectroscopy showed that the CC maintained its helical structure and the His residues were able to coordinate Ni2+. Circular dichroism (CD) spectroscopy revealed that the melting temperature of the CC increased by 4 °C in the presence of Ni2+. Using atomic force microscope (AFM)-based single molecule force spectroscopy, the energy landscape parameters of the CC were characterized in the absence and the presence of Ni2+. His-Ni2+ coordination increased the rupture force by ~10 pN, accompanied by a decrease of the dissociation rate constant. To test if this stabilizing effect can be transferred from the single molecule level to the bulk viscoelastic material properties, the CC building block was used as a non-covalent cross-link for star-shaped poly(ethylene glycol) (star-PEG) hydrogels. Shear rheology revealed a 3-fold higher relaxation time in His-Ni2+ coordinating hydrogels compared to the hydrogel without metal ions. This stabilizing effect was fully reversible when using an excess of the metal chelator ethylenediaminetetraacetate (EDTA). The hydrogel properties were further investigated using different metal ions, i.e. Cu2+, Co2+ and Zn2+. Overall, these results suggest that Ni2+, Cu2+ and Co2+ primarily form intra-CC coordination bonds while Zn2+ also participates in inter-CC coordination bonds. This may be a direct result of its different coordination geometry. Intermolecular His-metal coordination bonds in the terminal regions of the protein building blocks of mussel byssal threads are primarily formed by Zn2+ and were found to be intimately linked to higher-order assembly and self-healing of the thread. In the above example, the contribution of intra-CC and inter-CC His-Zn2+ cannot be disentangled. In Chapter 4.3, I redesigned the CC to prohibit the formation of intra-CC His-Zn2+ coordination bonds, focusing only on inter-CC interactions. Specifically, I inserted His in the solvent-exposed f positions of the CC to focus on the effect of metal-induced higher-order assembly of CC cross-links. Raman and CD spectroscopy revealed that this CC building block forms α-helical Zn2+ cross-linked aggregates. Using this CC as a cross-link for star-PEG hydrogels, I showed that the material properties can be switched from viscoelastic in the absence of Zn2+ to elastic-like in the presence of Zn2+. Moreover, the relaxation time of the hydrogel was tunable over three orders of magnitude when using different Zn2+:His ratios. This tunability is attributed to a progressive transformation of single CC cross-links into His-Zn2+ cross-linked aggregates, with inter-CC His-Zn2+ coordination bonds serving as an additional, cross-linking mode. Rheological characterization of the hydrogels with inter-CC His-Zn2+ coordination raised the question whether the His-Zn2+ coordination bonds between CCs or also the CCs themselves rupture when shear strain is applied. In general, the amount of CC cross-links initially formed in the hydrogel as well as the amount of CC cross-links breaking under force remains to be elucidated. In order to more deeply probe these questions and monitor the state of the CC cross-links when force is applied, a fluorescent reporter system based on F{\"o}rster resonance energy transfer (FRET) was introduced into the CC (Chapter 4.4). For this purpose, the donor-acceptor pair carboxyfluorescein and tetramethylrhodamine was used. The resulting self-reporting CC showed a FRET efficiency of 77 \% in solution. Using this fluorescently labeled CC as a self-reporting, reversible cross-link in an otherwise covalently cross-linked star-PEG hydrogel enabled the detection of the FRET efficiency change under compression force. This proof-of-principle result sets the stage for implementing the fluorescently labeled CCs as molecular force sensors in non-covalently cross-linked hydrogels. In summary, this thesis highlights that rationally designed CCs are excellent reversibly tunable, self-healing and self-reporting hydrogel cross-links with high application potential in bioengineering and biomedicine. For the first time, I demonstrated that His-metal coordination-based stabilization can be transferred from the single CC level to the bulk material with clear viscoelastic consequences. Insertion of His in specific sequence positions was used to implement a second non-covalent cross-linking mode via intermolecular His-metal coordination. This His-metal binding induced aggregation of the CCs enabled for reversibly tuning the hydrogel properties from viscoelastic to elastic-like. As a proof-of-principle to establish self-reporting CCs as material cross-links, I labeled a CC with a FRET pair. The fluorescently labelled CC acts as a molecular force sensor and first preliminary results suggest that the CC enables the detection of hydrogel cross-link failure under compression force. In the future, fluorescently labeled CC force sensors will likely not only be used as intelligent cross-links to study the failure of hydrogels but also to investigate cell-matrix interactions in 3D down to the single molecule level.},
  language  = {en}
}
@phdthesis{Kristen2011,
  author    = {Kristen, Juliane Ute},
  title     = {Amphiphilic BAB-triblock copolymers bearing fluorocarbon groups : synthesis and self-organization in aqueous media},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-61782},
  school      = {Universit{\"a}t Potsdam},
  year      = {2011},
  abstract  = {In this work new fluorinated and non-fluorinated mono- and bifunctional trithiocarbonates of the structure Z-C(=S)-S-R and Z-C(=S)-S-R-S-C(=S)-Z were synthesized for the use as chain transfer agents (CTAs) in the RAFT-process. All newly synthesized CTAs were tested for their efficiency to moderate the free radical polymerization process by polymerizing styrene (M3). Besides characterization of the homopolymers by GPC measurements, end- group analysis of the synthesized block copolymers via 1H-, 19F-NMR, and in some cases also UV-vis spectroscopy, were performed attaching suitable fluorinated moieties to the Z- and/or R-groups of the CTAs. Symmetric triblock copolymers of type BAB and non-symmetric fluorine end- capped polymers were accessible using the RAFT process in just two or one polymerization step. In particular, the RAFT-process enabled the controlled polymerization of hydrophilic monomers such as N-isopropylacrylamide (NIPAM) (M1) as well as N-acryloylpyrrolidine (NAP) (M2) for the A-blocks and of the hydrophobic monomers styrene (M3), 2-fluorostyrene (M4), 3-fluorostyrene (M5), 4-fluorostyrene (M6) and 2,3,4,5,6-pentafluorostyrene (M7) for the B-blocks. The properties of the BAB-triblock copolymers were investigated in dilute, concentrated and highly concentrated aqueous solutions using DLS, turbidimetry, 1H- and 19F-NMR, rheology, determination of the CMC, foam height- and surface tension measurements and microscopy. Furthermore, their ability to stabilize emulsions and microemulsions and the wetting behaviour of their aqueous solutions on different substrates was investigated. The behaviour of the fluorine end-functionalized polymers to form micelles was studied applying DLS measurements in diluted organic solution. All investigated BAB-triblock copolymers were able to form micelles and show surface activity at room temperature in dilute aqueous solution. The aqueous solutions displayed moderate foam formation. With different types and concentrations of oils, the formation of emulsions could be detected using a light microscope. A boosting effect in microemulsions could not be found adding BAB-triblock copolymers. At elevated polymer concentrations, the formation of hydrogels was proved applying rheology measurements.},
  language  = {en}
}