EPR spectroscopy as a tool for the elucidation of non-covalent structuring principles in complex soft matter

This thesis aims at connecting structural and functional changes of complex soft matter systems due to external stimuli with non-covalent molecular interaction profiles. It addresses the problem of elucidating non-covalent forces as structuring principle of mainly polymer-based systems in solution. The structuring principles of a wide variety of complex soft matter types are analyzed. In many cases this is done by exploring conformational changes upon the exertion of external stimuli. The central question throughout this thesis is how a certain non-covalent interaction profile leads to solution condition-dependent structuring of a polymeric system.rnTo answer this question, electron paramagnetic resonance (EPR) spectroscopy is chosen as the main experimental method for the investigation of the structure principles of polymers. With EPR one detects only the local surroundings or environments of molecules that carry an unpaired electron. Non-covalent forces are normally effective on length scales of a few nanometers and below. Thus, EPR is excellently suited for their investigations. It allows for detection of interactions on length scales ranging from approx. 0.1 nm up to 10 nm. However, restriction to only one experimental technique likely leads to only incomplete pictures of complex systems. Therefore, the presented studies are frequently augmented with further experimental and computational methods in order to yield more comprehensive descriptions of the systems chosen for investigation.rnElectrostatic correlation effects in non-covalent interaction profiles as structuring principles in colloid-like ionic clusters and DNA condensation are investigated first. Building on this it is shown how electrostatic structuring principles can be combined with hydrophobic ones, at the example of host-guest interactions in so-called dendronized polymers (denpols).rnSubsequently, the focus is shifted from electrostatics in dendronized polymers to thermoresponsive alkylene oxide-based materials, whose structuring principles are based on hydrogen bonds and counteracting hydrophobic interactions. The collapse mechanism in dependence of hydrophilic-hydrophobic balance and topology of these polymers is elucidated. Complementarily the temperature-dependent phase behavior of elastin-like polypeptides (ELPs) is investigated. ELPs are the first (and so far only) class of compounds that is shown to feature a first-order inverse phase transition on nanoscopic length scales.rnFinally, this thesis addresses complex biological systems, namely intrinsically disordered proteins (IDPs). It is shown that the conformational space of the IDPs Osteopontin (OPN), a cytokine involved in metastasis of several kinds of cancer, and BASP1 (brain acid soluble protein one), a protein associated with neurite outgrowth, is governed by a subtle interplay between electrostatic forces, hydrophobic interaction, system entropy and hydrogen bonds. Such, IDPs can even sample cooperatively folded structures, which have so far only been associated with globular proteins.

Economic Talc Deposits of Montana and Related Firing Problems

This thesis has to do with a study of the produc­tion of talc in Montana, describing the local geology of each deposit, and a description of the laboratory tests that were made on various grades of Montana talc in an attempt to determine why some grades of talc can be burned in solid forms while others must be ground, mixed with a binder and molded.

Temporary zinc oxide-eugenol cement: eugenol quantity in dentin and bond strength of resin composite

Uptake of eugenol from eugenol-containing temporary materials may reduce the adhesion of subsequent resin-based restorations. This study investigated the effect of duration of exposure to zinc oxide–eugenol (ZOE) cement on the quantity of eugenol retained in dentin and on the microtensile bond strength (μTBS) of the resin composite. The ZOE cement (IRM Caps) was applied onto the dentin of human molars (21 per group) for 1, 7, or 28 d. One half of each molar was used to determine the quantity of eugenol (by spectrofluorimetry) and the other half was used for μTBS testing. The ZOE-exposed dentin was treated with either OptiBond FL using phosphoric acid (H3PO4) or with Gluma Classic using ethylenediaminetetraacetic acid (EDTA) conditioning. One group without conditioning (for eugenol quantity) and two groups not exposed to ZOE (for eugenol quantity and μTBS testing) served as controls. The quantity of eugenol ranged between 0.33 and 2.9 nmol mg−1 of dentin (median values). No effect of the duration of exposure to ZOE was found. Conditioning with H3PO4 or EDTA significantly reduced the quantity of eugenol in dentin. Nevertheless, for OptiBond FL, exposure to ZOE significantly decreased the μTBS, regardless of the duration of exposure. For Gluma Classic, the μTBS decreased after exposure to ZOE for 7 and 28 d. OptiBond FL yielded a significantly higher μTBS than did Gluma Classic. Thus, ZOE should be avoided in cavities later to be restored with resin-based materials.

Inference of inhomogeneous clouds in an exoplaent atmosphere

We present new visible and infrared observations of the hot Jupiter Kepler-7b to determine its atmospheric properties. Our analysis allows us to (1) refine Kepler-7b's relatively large geometric albedo of Ag = 0.35 ± 0.02, (2) place upper limits on Kepler-7b thermal emission that remains undetected in both Spitzer bandpasses and (3) report a westward shift in the Kepler optical phase curve. We argue that Kepler-7b's visible flux cannot be due to thermal emission or Rayleigh scattering from H2 molecules. We therefore conclude that high altitude, optically reflective clouds located west from the substellar point are present in its atmosphere. We find that a silicate-based cloud composition is a possible candidate. Kepler-7b exhibits several properties that may make it particularly amenable to cloud formation in its upper atmosphere. These include a hot deep atmosphere that avoids a cloud cold trap, very low surface gravity to suppress cloud sedimentation, and a planetary equilibrium temperature in a range that allows for silicate clouds to potentially form in the visible atmosphere probed by Kepler. Our analysis does not only present evidence of optically thick clouds on Kepler-7b but also yields the first map of clouds in an exoplanet atmosphere.

Distributed Atomic Polarizabilities of Amino Acids and their Hydrogen-Bonded Aggregates

With the purpose of rational design of optical materials, distributed atomic polarizabilities of amino acid molecules and their hydrogen-bonded aggregates are calculated in order to identify the most efficient functional groups, able to buildup larger electric susceptibilities in crystals. Moreover, we carefully analyze how the atomic polarizabilities depend on the one-electron basis set or the many-electron Hamiltonian, including both wave function and density functional theory methods. This is useful for selecting the level of theory that best combines high accuracy and low computational costs, very important in particular when using the cluster method to estimate susceptibilities of molecular-based materials.

Desarrollo de una nueva técnica de base colorimétrica para una rápida evaluación de la biodegradabilidad de materiales poliméricos

Resumen: La necesidad de reducir el impacto ambiental causado por el uso de plásticos sintéticos obtenidos a partir de fuentes no-renovables ha motivado el desarrollo de nuevos materiales con carácter biodegradable. Sin embargo, los protocolos internacionales comúnmente utilizados para evaluar la biodegradabilidad de un material son laboriosos y suelen demandar elevados tiempos de procesamiento. En este trabajo, se presentan resultados preliminares obtenidos durante la etapa de desarrollo y puesta a punto de un método rápido, sencillo y eficiente para evaluar el potencial biodegradable de un material plástico, formulado a base de proteínas del lactosuero, utilizando un ensayo colorimétrico indirecto basado en la reducción enzimática de sales de tetrazolio durante el metabolismo aeróbico bacteriano.

Seasonally resolved chemical records of six ice cores from the Dronning Maud Land, Antarctica

The ammonium, calcium, and sodium concentrations from three intermediate depth ice cores drilled in the area of Dronning Maud Land, East Antarctica, have been investigated. Since all measurements were performed by a high-resolution Continuous Flow Analysis system, for the first time seasonal signals of chemical trace species could be obtained from the interior of central Antarctica over a period of approximately 2 millennia. Although the elevation as well as the accumulation rate differ between the drilling sites, similar values were obtained by comparing mean concentrations spanning the last 900 years. However, a distinct lack of intersite correlation was found on decadal timescales. Despite a noticeable accumulation change, apparent in one core, no significant concentration change of all three species has occurred. All the measured ions show clear seasonal signals over the whole records. While the sea-salt-related component sodium peaks simultaneously with calcium, the maximum ammonium concentration occurs in the snow with a time lag of 2 months after the sea-salt peak. More than 60% of the calcium concentration can be attributed to an ocean source. Elevated sodium concentrations were found within this millennium compared to mean values of the whole records, but the spatially varying shape of the increase suggests that a possible climatic signal is biased by local deposition effects.

Mineralogy, geochemistry and selected chemical formulas of sediments from ODP Holes 161-986B and 161-977A

Upper Miocene to Pleistocene hemipelagites and resedimented facies recovered at Holes 976B and 977A (Leg 161) in the Alboran Basin consist mainly of biogenic and detrital components, with a minor contribution of neoformed mineral phases. Diagenetic processes have not obliterated the primary deposition signal, and therefore detrital components (quartz, feldspar, detrital dolomite, rock fragments, and clays) provide information about source rocks and provenances. No major bulk or clay mineralogy differences were recognized between resedimented and hemipelagic facies; in fact, similar mineral assemblages in both types of facies suggest common source rocks. However, mineral abundance fluctuations can be related to climate variations and tectonic factors, as the main controls of sediment fill of this basin. A marked increase in smectites in Messinian sediments suggests an extensive development of soils during that time, probably favored by the alternation of wet and dry climate episodes and the relative aridification of the Mediterranean borderlands. A notable increase in detrital components suggests a sea-level fall and/or tectonic uplift during the late Pliocene. The significant increase in detrital dolomite in the uppermost Pliocene deposits suggests the uplift of dolomite-rich rocks as source areas. Mineral components in Pleistocene sediments indicate increasing tectonic stability, and clay-mineral fluctuations during the Pleistocene can be related not only to tectonic events, but also to alternating cooling and warming periods.

Geochemistry of pockmark sediments from the inner Oslofjord

Pockmarks are geological features that are found on the bottom of lakes and oceans all over the globe. Some are active, seeping oil or methane, while others are inactive. Active pockmarks are well studied since they harbor specialized microbial communities that proliferate on the seeping compounds. Such communities are not found in inactive pockmarks. Interestingly, inactive pockmarks are known to have different macrofaunal communities compared to the surrounding sediments. It is undetermined what the microbial composition of inactive pockmarks is and if it shows a similar pattern as the macrofauna. The Norwegian Oslo Fjord contains many inactive pockmarks and they are well suited to study the influence of these geological features on the microbial community in the sediment. Here we present a detailed analysis of the microbial communities found in three inactive pockmarks and two control samples at two core depth intervals. The communities were analyzed using high-throughput amplicon sequencing of the 16S rRNA V3 region. Microbial communities of surface pockmark sediments were indistinguishable from communities found in the surrounding seabed. In contrast, pockmark communities at 40 cm sediment depth had a significantly different community structure from normal sediments at the same depth. Statistical analysis of chemical variables indicated significant differences in the concentrations of total carbon and non-particulate organic carbon between 40 cm pockmark and reference sample sediments. We discuss these results in comparison with the taxonomic classification of the OTUs identified in our samples. Our results indicate that microbial surface sediment communities are affect by the water column, while the 40 cm communities are affect by local conditions within the sediment.