In the frame of submitted diploma thesis dealing with the radical products of the decomposition of different X-H bonds, primary attention was focused on the detection of radical intermediates from decomposed N-H bonds. This access was realized with secondary amines of N-alkylaniline group, as well as with other structures R1-NH-R2. The aim was to confirm the formation of unstable aminyl radicals R1-N•-R2, which is possible by using spin-trapping method. In the series of experiments, where the compounds of lead and cobalt, as well as stable radical DPPH were applied as initiators of the decomposition, the unambiguous evidence for aminyl radicals was found only in the case of N-alkylanilines. With other secondary amines the detection of aminyl radicals is an open problem, because their adducts with nitrosobenzene are in very low concentration. Besides the study of the decomposition of N-H bonds also the products of the decomposition of phenolic O-H bonds, as well as products of the decomposition of C-H bonds in alkylsubstituents in phenols was studied.

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Since the last decade, an increasing number of proteins have been shown to be capable of undergoing reversible liquid-liquid phase separation (LLPS) in response to an external stimulus, and the resulting protein-rich phase (coacervate) is considered as one of the main components of membrane-less organelles. Most of these proteins are intrinsically disordered proteins (IDPs) or contain intrinsically disordered regions. More importantly, LLPS often plays an important role in cellular signaling and development of cells and tissues. However, the molecular mechanisms underlying LLPS of proteins remain poorly understood. Elastin-like proteins (ELPs), a class of IDPs derived from the hydrophobic domains of tropoelastin, are known to undergo LLPS reversibly above a concentration-dependent transition temperature (TT), allowing ELPs to be a promising thermo-responsive drug delivery vector for treating cancer. Previous studies have suggested that, as temperature increases, ELPs experience an increased propensity for type II beta-turns. Our hypothesis is that the interaction is initiated at the beta-turn positions. In this work, integrative approaches including experimental and computational methods were employed to study the early stages of ELP phase separation. Using nuclear magnetic resonance spectroscopy (NMR), and paramagnetic relaxation enhancement (PRE), we have characterized structural properties of self-association in several ELPs. NMR chemical shifts suggest that ELPs adopt a beta-turn conformation even at temperatures below the TT. The intermolecular PRE reveals there is a stronger interaction between the higher beta-turn propensity regions. Building on this observation, a series of structural ensembles were generated for ELP incorporating differing amounts of beta-turn bias, from 1% to 90%. To mimic the early stages of the phase change, two monomers were paired, assuming preferential interaction at beta-turn regions. Following dimerization, the ensemble-averaged hydrodynamic properties were calculated for each degree of beta-turn bias, and results were compared with analytical ultracentrifugation (AUC) experiments at various temperatures. The ensemble calculation reveals that accessible surface area changes dramatically as oligomers are formed from monomers with a high beta-turn content. Together, these observations suggest a model where ELP self-association is initiated at beta-turn positions, where the driving force of phase separation is solvent exclusion due to changes in the hydrophobic accessible surface area.

The modified Fiala model from Westin was implemented with conditions for circulatory shock and hypothermia. The purpose is to model Emergency Preservation and Resuscitation (EPR), a procedure for inducing hypothermia in patients. Cold tissue temperatures reduce metabolism exponentially, greatly extending the window of anaerobic metabolic activity before permanent deoxygenation damage. EPR in patients undergoing hypovolemic shock can preserve the patient until primary surgical care and blood transfusions are attainable., thereby increasing survival rates. The main applications of EPR are military in-situ stabilization for transit to clinical care and extending the survivability of patients requiring prolonged surgery before blood transfusion. The model explored in this paper seeks to model the tissue temperatures of the body while enduring circulatory shock and various options of cooling devices. Calibrating this model with already available data enables its use for getting preliminary results and design parameters for prototype cooling devices. The final objective of this research is to support the design of a cooling device that can induce sustained hypothermia in a field setting, while still being mobile enough for military and ambulance use.

Research in recent years on novel materials in organic solar cells (OSCs) have contributed to a rapid advancement in OSC efficiency. Here, OSCs with the well-studied organic semiconductors poly(3-hexylthiophene):[6,6]-phenyl C60-butyric acid methylester (P3HT:PCBM) in a bulk heterojunction structure were prepared to establish a baseline procedure for fabrication and spin-sensitive spectroscopy. Spin-sensitive spectroscopy can be used to probe the spin-dependent processes and loss mechanism in OSCs. Understanding the microscopic processes enables research targeting loss mechanisms directly, which opens up for higher efficiency OSCs. Measurements with continuous wave electrically detected magnetic resonance (cwEDMR), continuous wave electron paramagnetic resonance (cwEPR) and transient (tr)EDMR were set up and followed by an initial study on the spin-dependent processes and their influence on the photocurrent. Signals from spin-dependent processes in the samples were seen for the three experiment series carried out, and well-functioning OSCs with consistent results were prepared. This thesis and the presented baseline fabrication and experimental setup procedures provide with valuable learnings for future research in the group AG Behrends enabling fabrication and spin-sensitive studies on novel materials in OSCs. It was found that post-processing annealing at 120 C for 5 min reduces S-shape behaviour in current-voltage curves, and over all improves poor current-voltage characteristics of the OSC samples fabricated. Further, influence from PEDOT:PSS was seen in cwEPR spectroscopy, indicating the presence of traps or free radicals in the PEDOT:PSS. In cwEDMR spectroscopy of the OSCs it was shown that the spin processes of bias-induced and photo-induced charge carriers influence the photocurrent in the same way. Finally, the authors suggest that results from spin-sensitive spectroscopy of degraded OSCs cannot be applied to non-degraded OSCs.

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X-ray diffraction (XRD) patterns, electron probe microanalysis(EPMA), electron paramagnetic resonance (EPR) powder spectra (9 and 34 GHz) and the magnetic susceptibility of BaTiO3 + 0.04 BaO + 0.01 V2O5 ceramics were studied to investigate the valence states of V ions and their solubility in the BaTiO3 lattice. In samples sintered at 1400 °C in air, only about 0.1 mol% V is incorporated in the BaTiO3 lattice being in V4+ and V5+ valence state, respectively. 95% of the nominal V dopant content occurs in the secondary phase Ba3(V/Ti)2O8. All BaTiO3 samples investigated are in tetragonal phase at room temperature. In the as-sintered samples V4+ is detected at temperatures T < 20 K by its hyperfine structure (HFS) octet due to the nuclear spin 7/2 of 51V. Samples post annealed in H2/Ar atmosphere at 1200 °C exhibit a further HFS octet occurring at T > 25 K and vanishing at T > 250 K, which is caused by V2+ ions. This spectrum is characterized by a simultaneous HFS and fine structure splitting constituted by allowed and forbidden transitions. Both V4+ and V2+ ions are incorporated at Ti4+ sites of the BaTiO3 lattice

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