Klassische und ab initio Molekulardynamik-Untersuchungen zu Germaniumdioxidschmelzen

Germaniumdioxid (GeO2) ist ein Glasbildner, der wie das homologe SiO2 ein ungeordnetes tetraedrisches Netzwerk ausbildet. In dieser Arbeit werden mit Hilfe von Molekulardynamik-Computersimulationen die Struktur und Dynamik von GeO2 in Abhängigkeit von der Temperatur untersucht. Dazu werden sowohl Simulationen mit einem klassischen Paarpotentialmodell von Oeffner und Elliott als auch ab initio-Simulationen gemäß der Car-Parrinello-Molekulardynamik (CPMD), bei der elektronische Freiheitsgrade mittels Dichtefunktionaltheorie beschrieben werden, durchgeführt. In der klassischen Simulation werden dazu ein Temperaturen zwischen 6100 K und 2530 K betrachtet. Darüberhinaus ermöglichen Abkühlläufe auf T=300 K das Studium der Struktur des Glases. Zum Vergleich werden CPMD-Simulationen für kleinere Systeme mit 60 bzw. 120 Teilchen bei den Temperaturen 3760 K und 3000 K durchgeführt. In den klassischen Simulationen kann die im Experiment bis 1700 K nachgewiesene, im Vergleich zu SiO2 starke, Temperaturabhängigkeit der Dichte auch bei höheren Temperaturen beobachtet werden. Gute Übereinstimmungen der Simulationen mit experimentellen Daten zeigen sich bei der Untersuchung verschiedener struktureller Größen, wie z.B. Paarkorrelationsfunktionen, Winkelverteilungen, Koordinationszahlen und Strukturfaktoren. Es können leichte strukturelle Abweichungen der CPMD-Simulationen von den klassischen Simulationen aufgezeigt werden: 1. Die Paarabstände in CPMD sind durchweg etwas kleiner. 2. Es zeigt sich, daß die Bindungen in den ab initio-Simulationen weicher sind, was sich auch in einer etwas stärkeren Temperaturabhängigkeit der strukturellen Größen im Vergleich zu den klassischen Simulationen niederschlägt. 3. Für CPMD kann ein vermehrtes Auftreten von Dreierringstrukturen gezeigt werden. 4. In der CPMD werden temperaturabhängige Defektstrukturen in Form von Sauerstoffpaaren beobachtet, die vor allem bei 3760 K, kaum jedoch bei 3000 K auftreten. Alle strukturellen Unterschiede zwischen klassischer und CPMD-Simulation sind eindeutig nicht auf Finite-Size-Effekte aufgrund der kleinen Systemgrößen in den CPMD-Simulationen zurückzuführen, d.h. sie sind tatsächlich methodisch bedingt. Bei der Dynamik von GeO2 wird in den klassischen Simulationen ebenfalls eine gute Übereinstimmung mit experimentellen Daten beobachtet, was ein Vergleich der Diffusionskonstanten mit Viskositätsmessungen bei hohen Temperaturen belegt. Die Diffusionskonstanten zeigen teilweise ein verschiedenes Verhalten zum homologen SiO2. Sie folgen in GeO2 bei Temperaturen unter 3000 K einem Arrheniusgesetz mit einer deutlich niedrigeren Aktivierungsenergie. Darüberhinaus werden die Möglichkeiten der Parametrisierung eines neuen klassischen Paarpotentials mittels der Kräfte entlang der CPMD-Trajektorien untersucht. Es zeigt sich, daß derartige Parametrisierungen sehr stark von den gewählten Startparametern abhängen. Ferner führen sämtliche an die Schmelze parametrisierten Potentiale zu zu hohen Dichten im Vergleich zum Experiment. Zum einen liegt dies sehr wahrscheinlich daran,daß für das System GeO2 Kraftdaten allein nicht ausreichen, um grundlegende strukturelle Größen, wie z.B. Paarkorrelationen und Winkelverteilungen, der CPMD-Simulationen gut reproduzieren zu können. Zum anderen ist wohl die Beschreibung mittels Paarpotentialen nicht ausreichend und es ist erforderlich, Merkörperwechselwirkungen in Betracht zu ziehen.

Weathering of Fe-bearing minerals under extraterrestrial conditions, investigated by Mössbauer spectroscopy

The weathering of Fe-bearing minerals under extraterrestrial conditions was investigated by Mössbauer (MB) spectroscopy to gain insights into the role of water on the planet Mars. The NASA Mars Exploration Rovers Spirit and Opportunity each carry a miniaturized Mössbauer spectrometer MIMOS II for the in situ investigation of Martian soils and rocks as part of their payload. The MER flight instruments had to be modified in order to work over the Martian diurnal temperature range (180 K – 290 K) and within the unique electronic environment of the rovers. The modification required special calibration procedures. The integration time necessary to obtain a good quality Mössbauer spectrum with the MIMOS II flight instruments was reduced by 30 % through the design of a new collimator. The in situ investigation of rocks along the rover Spirit's traverse in Gusev crater revealed weakly altered olivine basalt on the plains and pervasively altered basalt in the Columbia Hills. Correlation plots of primary Fe-bearing minerals identified by MB spectroscopy such as olivine versus secondary Fe-bearing phases such as nanophase Fe oxides showed that olivine is the mineral which is primarily involved in weathering reactions. This argues for a reduced availability of water. Identification of the Fe-oxyhydroxide goethite in the Columbia Hills is unequivocal evidence for aqueous weathering processes in the Columbia Hills. Experiments in which mineral powders were exposed to components of the Martian atmosphere showed that interaction with the atmosphere alone, in the absence of liquid water, is sufficient to oxidize Martian surface materials. The fine-grained dust suspended in the Martian atmosphere may have been altered solely by gas-solid reactions. Fresh and altered specimens of Martian meteorites were investigated with MIMOS II. The study of Martian meteorites in the lab helped to identify in Bounce Rock the first rock on Mars which is similar in composition to basaltic shergottites, a subgroup of the Martian meteorites. The field of astrobiology includes the study of the origin, evolution and distribution of life in the universe. Water is a prerequisite for life. The MER Mössbauer spectrometers identified aqueous minerals such as jarosite and goethite. The identification of jarosite was crucial to evaluate the habitability of Opportunity's landing site at Meridiani Planum during the formation of the sedimentary outcrop rocks, because jarosite puts strong constrains on pH levels. The identification of olivine in rocks and soils on the Gusev crater plains provide evidence for the sparsity of water under current conditions on Mars. Ratios of Fe2+/Fe3+ were obtained with Mössbauer spectroscopy from basaltic glass samples which were exposed at a deep sea hydrothermal vent. The ratios were used as a measure of potential energy for use by a microbial community. Samples from Mars analogue field sites on Earth exhibiting morphological biosignatures were also investigated.

Hypersonic elastic excitations in soft mesoscopic structures

This dissertation is devoted to the experimental exploration of the propagation of elastic waves in soft mesoscopic structures with submicrometer dimensions. A strong motivation of this work is the large technological relevance and the fundamental importance of the subject. Elastic waves are accompanied by time-dependent fluctuations of local stress and strain fields in the medium. As such, the propagation phase velocities are intimately related to the elastic moduli. Knowledge of the elastic wave propagation directly provides information about the mechanical properties of the probed mesoscopic structures, which are not readily accessible experimentally. On the other hand, elastic waves, when propagating in an inhomogeneous medium with spatial inhomogeneities comparable to their wavelength, exhibit rather rich behavior, including the appearance of novel physical phenomena, such as phononic bandgap formation. So far, the experimental work has been restricted to macroscopic structures, which limit wave propagation below the KHz range. It was anticipated that an experimental approach capable of probing the interplay of the wave propagation with the controlled mesoscopic structures would contribute to deeper insights into the fundamental problem of elastic wave propagation in inhomogeneous systems. The mesoscopic nature of the structures to be studied precludes the use of traditional methods, such as sound transmission, for the study of elastic wave propagation. In this work, an optical method utilizing the inelastic scattering of photons by GHz frequency thermally excited elastic waves, known as Brillouin light scattering spectroscopy (BLS), was employed. Two important classes of soft structures were investigated: thin films and colloidal crystals. For the former, the main interest was the effect of the one-dimensional (1D) confinement on the wave propagation due to the presence of the free-surface or interface of the layer and the utilization of these waves to extract relevant material parameters. For the second system, the primary interest was the interaction of the elastic wave and the strong scattering medium with local resonance units in a three-dimensional (3D) periodic arrangement.

Search for K isomers in 252,254 No and 260 Sg and investigation of their nuclear structure

Study of K isomerism in the transfermium region around the deformed shells at N=152, Z=102, and N=162, Z=108 provides important information on the structure of heavy nuclei. Recent calculations suggest that the K-isomerism can enhance the stability of such nuclei against alpha emission and spontaneous fission. Nuclei showing K isomerism have neutron and proton orbitals with large spin projections on the symmetry axis which is due to multi quasiparticle states with aligned spins K. Quasi-particle states are formed by breaking pairs of nucleons and raising one or two nucleons in orbitals near the Fermi surface above the gap, forming high K (multi)quasi-particle states mainly at low excitation energies. Experimental examples are the recently studied two quasi-particle K isomers in 250,256-Fm, 254-No, and 270-Ds. Nuclei in this region, are produced with cross sections ranging from several nb up to µb, which are high enough for a detailed decay study. In this work, K isomerism in Sg and No isotopes was studied at the velocity filter SHIP of GSI, Darmstadt. The data were obtained by using a new data acquisition system which was developed and installed during this work. 252,254-No and 260-Sg were produced in fusion evaporation reactions of 48-Ca and 54-Cr projectiles with 206,208-Pb targets at beam energies close to the Coulomb barrier. A new K isomer was discovered in 252-No at excitation energy of 1.25 MeV, which decays to the ground state rotational band via gamma emission. It has a half-life of about 100 ms. The population of the isomeric state was about 20% of the ground state population. Detailed investigations were performed on 254-No in which two isomeric states (275 ms and 198 µs) were already discovered by R.-D. Herzberg, but due to the higher number of observed gamma decays more detailed information about the decay path of the isomers was obtained in the present work. In 260-Sg, we observed no statistically significant component with a half life different from that of the ground state. A comparison between experimental results and theoretical calculations of the single particle energies shows a fair agreement. The structure of the here studied nuclei is in particular important as single particle levels are involved which are relevant for the next shell closure expected to form the region of the shell stabilized superheavy elements at proton numbers 114, 120, or 126 and neutron number 184. K isomers, in particular, could be an ideal tool for the synthesis and study of these isotopes due to enhanced spontaneous fission life times which could result in higher alpha to spontaneous fission branching ratios and longer half lifes.

Chimäre Archonta?: vergleichend-morphologische Studien zur Hyolaryngealregion

Chimäre Archonta? Vergleichend-morphologische Studien zur Hyolaryngealregion. Mit Brevia zur Dental- und Tarsalmorphologie. Die Dissertation greift aus phylogenetisch-systematischer Perspektive das Problem des Primatenursprungs auf. Traditionell wurde die Überordnung Archonta (= Primates + Scandentia + Dermoptera + Chiroptera) angenommen, die aufgrund molekularer Befunde nicht mehr als valide eingestuft wird. Eine Klassifikation anhand der Superordo Euarchontoglires (= Primates + Scandentia + Dermoptera + Glires) wird derzeit bevorzugt. Beide Verwandtschaftshypothesen werden in den taxonomischen Analysen berücksichtigt, um den potentiellen Einfluss der Außengruppenwahl auf die Konstellation der Euarchonta (= Primates + Dermoptera + Scandentia) zu bestimmen. Der Schwerpunkt der Untersuchung liegt in der 3D-Rekonstruktion ontogenetischer Stadien der Hyolaryngealregion diverser Spezies der Ordnungen Artiodactyla, Chiroptera, Dermoptera, Primates, Rodentia, Scandentia und Soricomorpha. Mit AMIRA® 3.1.1 konnten basierend auf histologischen Schnittserien 18 dreidimensionale Modelle der überwiegend spätfetalen Zungenbein- und Kehlkopfregion dargestellt werden. Durch das Studium der Knorpelmorphologie und der Larynx-Myologie wurden 150 Merkmale definiert und in eine MacClade®-Datenmatrix überführt. Die auf dem Parsimonie-Prinzip basierenden PAUP®-Analysen sprechen für eine Schwestergruppenbeziehung der Primates und der Dermoptera (= Primatomorpha). Die als Chimäre titulierte Überordnung Archonta wurde als Vehikel verwendet, um die Integration der Chiropteren zu ermöglichen und die Hyolaryngealforschung zu intensivieren, da auch Echolot-Peilung verwendende Taxa Bestandteil der Untersuchung waren. Die morphologischen Ähnlichkeiten des Zungenbein- und Kehlkopfapparates zwischen der basalen Form Rousettus (Pteropodidae) und dem Dermoptera-Vertreter Cynocephalus wurden als symplesiomorphe Merkmale gedeutet. Bei der Außengruppenwahl eines Rodentia-Repräsentanten hingegen konnte in Übereinstimmung mit den molekularen Befunden und nach dem Gros der Lehrmeinung die Schwestergruppenbeziehung der Primates und der Sundatheria bestätigt werden. Zwecks eines umfassenderen Ansatzes wurden im Rahmen einer „total evidence“-Methodik dental- und tarsalmorphologische Merkmale integriert. Das Resultat der Clusteranalyse, basierend auf 263 Merkmalen, modifiziert das Zwischenergebnis und befürwortet in Übereinstimmung mit molekularen Daten als Schwestergruppe der Primaten das Taxon Sundatheria (= Dermoptera + Scandentia). Damit konnte erstmals mittels eines konsequenten phylogenetisch-systematischen Ansatzes der Primaten-Grundplan hinsichtlich der Merkmalsausstattung der Hyolaryngealregion mit 27 Merkmalen rekonstruiert werden. Der Primatenursprung kann mit dem Euarchonta-Grundplan rekonstruiert werden. Für die Sundatheria wurden 12 Grundplanmerkmale definiert

Measurement of the oscillation frequency of B s mesons in the hadronic decay mode B s pi D s (phi pi) X with the D0 detector at the Fermilab Tevatron collider

The standard model (SM) of particle physics is a theory, describing three out of four fundamental forces. In this model the Cabibbo-Kobayashi-Maskawa (CKM) matrix describes the transformation between the mass and weak eigenstates of quarks. The matrix properties can be visualized as triangles in the complex plane. A precise measurement of all triangle parameters can be used to verify the validity of the SM. The least precisely measured parameter of the triangle is related to the CKM element |Vtd|, accessible through the mixing frequency (oscillation) of neutral B mesons, where mixing is the transition of a neutral meson into its anti-particle and vice versa. It is possible to calculate the CKM element |Vtd| and a related element |Vts| by measuring the mass differences Dmd (Dms ) between neutral Bd and bar{Bd} (Bs and bar{Bs}) meson mass eigenstates. This measurement is accomplished by tagging the initial and final state of decaying B mesons and determining their lifetime. Currently the Fermilab Tevatron Collider (providing pbar{p} collisions at sqrt{s}=1.96 TeV) is the only place, where Bs oscillations can be studied. The first selection of the "golden", fully hadronic decay mode Bs->Ds pi(phi pi)X at DØ is presented in this thesis. All data, taken between April 2002 and August 2007 with the DØ detector, corresponding to an integrated luminosity of int{L}dt=2.8/fb is used. The oscillation frequency Dms and the ratio |Vtd|/|Vts| are determined as Dms = (16.6 +0.5-0.4(stat) +0.4-0.3(sys)) 1/ps, |Vtd|/|Vts| = 0.213 +0.004-0.003(exp)pm 0.008(theor). These results are consistent with the standard model expectations and no evidence for new physics is observable.

DNA hybrid materials consisting of oligonucleotides and organic molecules: synthesis, characterization and applications

The goal of this thesis was to increase the functionality of pristine DNA scaffolds by functionalizing them with fluorescent dyes and hydrophobic moieties. Two important steps were necessary to realize this aim successfully. First, nucleic acids needed to be synthesized making use of multidisciplinary toolbox for the generation and manipulation of polynucleic acids. The most important techniques were the solid phase synthesis involving the incorporation of standard and modified phosphoramidite building blocks as well as molecular biology procedures like the polymerase chain reaction, the bacterial amplification of plasmids and the enzymatic digestion of circular vectors. Second, and evenly important, was the characterization of the novel bioorganic hybrid structures by a multitude of techniques, especially optical measurements. For studying DNA-dye conjugates methods like UV/Vis and photoluminescence spectroscopy as well as time resolved luminescence spectroscopy were utilized. While these measurements characterized the bulk behavior of an ensemble of DNA-dye hybrids it was necessary for a complete understanding of the systems to look at single structures. This was done by single-molecule fluorescence spectroscopy and fluorescence correlation spectroscopy. For complete analysis the optical experiments were complemented by direct visualization techniques, i.e. high resolution transmission electron microscopy and scanning force microscopy.

Characterization of structure and dynamics of submicrometric systems via fluorescence correlation spectroscopy

The presented thesis revolves around the study of thermally-responsive PNIPAAm-based hydrogels in water/based environments, as studied by Fluorescence Correlation Spectroscopy (FCS).rnThe goal of the project was the engineering of PNIPAAm gels into biosensors. Specifically, a gamma of such gels were both investigated concerning their dynamics and structure at the nanometer scale, and their performance in retaining bound bodies upon thermal collapse (which PNIPAAm undergoes upon heating above 32 ºC).rnFCS’s requirements, as a technique, match the limitations imposed by the system. Namely, the need to intimately probe a system in a solvent, which was also fragile and easy to alter. FCS, on the other hand, both requires a fluid environment to work, and is based on the observation of diffusion of fluorescents at nanomolar concentrations. FCS was applied to probe the hydrogels on the nanometer size with minimal invasivity.rnVariables in the gels were addressed in the project including crosslinking degree; structural changes during thermal collapse; behavior in different buffers; the possibility of decreasing the degree of inhomogeneity; behavior of differently sized probes; and the effectiveness of antibody functionalization upon thermal collapse.rnThe evidenced results included the heightening of structural inhomogeneities during thermal collapse and under different buffer conditions; the use of annealing to decrease the inhomogeneity degree; the use of differently sized probes to address different length scale of the gel; and the successful functionalization before and after collapse.rnThe thesis also addresses two side projects, also carried forward via FCS. One, diffusion in inverse opals, produced a predictive simulation model for diffusion of bodies in confined systems as dependent on the bodies’ size versus the characteristic sizes of the system. The other was the observation of interaction of bodies of opposite charge in a water solution, resulting in a phenomenological theory and an evaluation method for both the average residence time of the different bodies together, and their attachment likelihood.

Feasibility studies of the pp pi 0 e + e - electromagnetic channel at PANDA

Among all possible realizations of quark and antiquark assembly, the nucleon (the proton and the neutron) is the most stable of all hadrons and consequently has been the subject of intensive studies. Mass, shape, radius and more complex representations of its internal structure are measured since several decades using different probes. The proton (spin 1/2) is described by the electric GE and magnetic GM form factors which characterise its internal structure. The simplest way to measure the proton form factors consists in measuring the angular distribution of the electron-proton elastic scattering accessing the so-called Space-Like region where q2 < 0. Using the crossed channel antiproton proton <--> e+e-, one accesses another kinematical region, the so-called Time-Like region where q2 > 0. However, due to the antiproton proton <--> e+e- threshold q2th, only the kinematical domain q2 > q2th > 0 is available. To access the unphysical region, one may use the antiproton proton --> pi0 e+ e- reaction where the pi0 takes away a part of the system energy allowing q2 to be varied between q2th and almost 0. This thesis aims to show the feasibility of such measurements with the PANDA detector which will be installed on the new high intensity antiproton ring at the FAIR facility at Darmstadt. To describe the antiproton proton --> pi0 e+ e- reaction, a Lagrangian based approach is developed. The 5-fold differential cross section is determined and related to linear combinations of hadronic tensors. Under the assumption of one nucleon exchange, the hadronic tensors are expressed in terms of the 2 complex proton electromagnetic form factors. An extraction method which provides an access to the proton electromagnetic form factor ratio R = |GE|/|GM| and for the first time in an unpolarized experiment to the cosine of the phase difference is developed. Such measurements have never been performed in the unphysical region up to now. Extended simulations were performed to show how the ratio R and the cosine can be extracted from the positron angular distribution. Furthermore, a model is developed for the antiproton proton --> pi0 pi+ pi- background reaction considered as the most dangerous one. The background to signal cross section ratio was estimated under different cut combinations of the particle identification information from the different detectors and of the kinematic fits. The background contribution can be reduced to the percent level or even less. The corresponding signal efficiency ranges from a few % to 30%. The precision on the determination of the ratio R and of the cosine is determined using the expected counting rates via Monte Carlo method. A part of this thesis is also dedicated to more technical work with the study of the prototype of the electromagnetic calorimeter and the determination of its resolution.

Feasibility studies for accessing nucleon structure observables with the PANDA experiment at the future FAIR facility

The availability of a high-intensity antiproton beam with momentum up to 15,GeV/c at the future FAIR will open a unique opportunity to investigate wide areas of nuclear physics with the $overline{P}$ANDA (anti{$overline{P}$}roton ANnihilations at DArmstadt) detector. Part of these investigations concern the Electromagnetic Form Factors of the proton in the time-like region and the study of the Transition Distribution Amplitudes, for which feasibility studies have been performed in this Thesis. rnMoreover, simulations to study the efficiency and the energy resolution of the backward endcap of the electromagnetic calorimeter of $overline{P}$ANDA are presented. This detector is crucial especially for the reconstruction of processes like $bar pprightarrow e^+ e^- pi^0$, investigated in this work. Different arrangements of dead material were studied. The results show that both, the efficiency and the energy resolution of the backward endcap of the electromagnetic calorimeter fullfill the requirements for the detection of backward particles, and that this detector is necessary for the reconstruction of the channels of interest. rnrnThe study of the annihilation channel $bar pprightarrow e^+ e^-$ will improve the knowledge of the Electromagnetic Form Factors in the time-like region, and will help to understand their connection with the Electromagnetic Form Factors in the space-like region. In this Thesis the feasibility of a measurement of the $bar pprightarrow e^+ e^-$ cross section with $overline{P}$ANDA is studied using Monte-Carlo simulations. The major background channel $bar pprightarrow pi^+ pi^-$ is taken into account. The results show a $10^9$ background suppression factor, which assure a sufficiently clean signal with less than 0.1% background contamination. The signal can be measured with an efficiency greater than 30% up to $s=14$,(GeV/c)$^2$. The Electromagnetic Form Factors are extracted from the reconstructed signal and corrected angular distribution. Above this $s$ limit, the low cross section will not allow the direct extraction of the Electromagnetic Form Factors. However, the total cross section can still be measured and an extraction of the Electromagnetic Form Factors is possible considering certain assumptions on the ratio between the electric and magnetic contributions.rnrnThe Transition Distribution Amplitudes are new non-perturbative objects describing the transition between a baryon and a meson. They are accessible in hard exclusive processes like $bar pprightarrow e^+ e^- pi^0$. The study of this process with $overline{P}$ANDA will test the Transition Distribution Amplitudes approach. This work includes a feasibility study for measuring this channel with $overline{P}$ANDA. The main background reaction is here $bar pprightarrow pi^+ pi^- pi^0$. A background suppression factor of $10^8$ has been achieved while keeping a signal efficiency above 20%.rnrnrnPart of this work has been published in the European Physics Journal A 44, 373-384 (2010).rn

Studentischer Umgang mit Studienstrukturen - Bildungsideale und Zeitstrukturen im Bachelorstudium

Die vorliegende Arbeit befasst sich mit den veränderten Studienbedingungen, die durch die europaweite Einführung eines einheitlichen Systems von Bachelor- und Masterstudiengängen entstanden sind. In Deutschland wurde der Bologna-Prozess von umfangreichen Protesten begleitet und in der medialen Öffentlichkeit unter anderem die zeitliche und inhaltliche Überlastung der Studierenden und die verschulten Studiengänge kritisiert, die keinen Raum für die persönliche Entwicklung ließen. rnIm Rahmen des BMBF-geförderten Projekts ZEITLast wurde die zeitliche Belastung von Studierenden untersucht. Der scheinbare Widerspruch zwischen dem objektiv messbaren Zeitaufwand und dem subjektiven Belastungsempfinden der Studierenden stellt den Ausgangspunkt der vorliegenden Arbeit dar. Es wird der Frage nachgegangen, welche Strategien Studierende im Umgang mit den neuen Bachelorstudienstrukturen entwickeln und in welchem Zusammenhang diese mit dem subjektiven Belastungsempfinden stehen. Zur Beantwortung der Fragestellung werden quantitative und qualitative Forschungsmethoden kombiniert. Neben der Auswertung von umfangreichen Zeitbudgetanalysen und Befragungen aus dem Forschungsprojekt ZEITLast werden mit ausgewählten Probanden des Studiengangs Erziehungswissenschaft an der Universität Mainz problemzentrierte Interviews geführt und objektiv hermeneutisch ausgewertet. Eine zeitliche Überlastung der Studierenden lässt sich empirisch nicht nachweisen, dennoch fühlen sich Studierende subjektiv stark belastet Es zeigt sich, dass unterschiedliche subjektive Perspektiven auf die individuelle Studienorganisation und das Belastungsempfinden der Studierenden wirken. Vor allem spielt das individuelle Zeit- und Selbstmanagement bei der erfolgreichen Bewältigung der Anforderungen im Studium eine bedeutende Rolle. Insgesamt wird deutlich, dass Vorgaben im Studium abhängig von individuellen Dispositionen sowohl als Entlastung als auch als Belastung wahrgenommen werden. Die Aufgabe der Hochschule ist es, Studiengänge so zu gestalten, dass sie den unsicheren Studierenden Orientierung und Hilfestellung bieten, während sie den selbstbestimmten Studierenden Freiräume zur individuellen Entwicklung lassen. Aus den Ergebnissen der Arbeit werden abschließend hochschuldidaktische Maßnahmen entwickelt, die zu einer Entlastung der Studierenden beitragen können.

Il giovane Schopenhauer e Fichte : la duplicità della coscienza

Lo scopo del presente lavoro è gettare la massima luce possibile (in base ai documenti disponibili), sia dal punto di vista teorico che storico, su due questioni che la ricerca schopenhaueriana ha già da tempo considerato come decisive: la frequenza, da parte del giovanissimo Schopenhauer, delle lezioni di Fichte e la genesi, lo sviluppo e infine l’abbandono del filosofema della «coscienza migliore». Il lavoro è perciò diviso in due sezioni: «Analisi degli appunti» e «La coscienza migliore». Schopenhauer frequentò a Berlino, nel semestre invernale 1811-12, quattro lezioni di Fichte «Sullo studio della filosofia», e poi i corsi «Sui fatti della coscienza» e «Sulla dottrina della scienza». Nei suoi appunti concernenti queste lezioni, Schopenhauer ha registrato non soltanto l’esposizione di Fichte, ma anche le sue osservazioni e obbiezioni. L’analisi di questi appunti, condotta nella prima parte, consente perciò di documentare dettagliatamente il primo incontro del giovane Schopenhauer con la filosofia di Fichte e di indicare i punti specifici dell’esposizione di quest’ultimo che possono aver costituito un riferimento teorico significativo per il successivo sviluppo della filosofia schopenhaueriana. La seconda parte del lavoro è dedicata all’analisi dei Manoscritti giovanili di Schopenhauer, redatti dal 1804 al 1814, e soprattutto al filosofema della «coscienza migliore». Il tema della prima parte e il tema della seconda parte del lavoro sono in stretta relazione, in quanto, come è dimostrato nel corso dell’indagine, l’ascolto dei corsi di Fichte mosse Schopenhauer a elaborare i principi fondamentali del filosofema in questione. Quest’ultimo costituisce il primo tentativo di sistema di Schopenhauer. Attraverso l’analisi di tale filosofema si muove perciò un’indagine sistematica sui primissimi esperimenti teorici del giovane Schopenhauer, mettendo in evidenza il percorso e gli influssi attraverso i quali il filosofo tedesco è gradualmente giunto alle sue posizioni definitive concernenti il sistema della volontà di vivere. Nel lavoro si dimostra che la preferenza di Schopenhauer per il sistema della volontà di vivere rispetto al tentativo di sistema della coscienza migliore è necessitato da un’esigenza di coerenza verso quelle che Schopenhauer stesso considera le istanze irrinunciabili del criticismo kantiano. Al tempo stesso, si mostra come il filosofema della «coscienza migliore» abbia costituto, nelle riflessioni del giovane Schopenhauer, un importantissimo “esperimento teorico”, il cui fallimento fornì l’impulso fondamentale per l’elaborazione del sistema della volontà di vivere.

Complex tracer mobilities in polymer networks revealed by fluorescence correlation spectroscopy

Gels are elastic porous polymer networks that are accompanied by pronounced mechanical properties. Due to their biocompatibility, ‘responsive hydrogels’ (HG) have many biomedical applications ranging from biosensors and drug delivery to tissue engineering. They respond to external stimuli such as temperature and salt by changing their dimensions. Of paramount importance is the ability to engineer penetrability and diffusion of interacting molecules in the crowded HG environment, as this would enable one to optimize a specific functionality. Even though the conditions under which biomedical devices operate are rather complex, a bottom-up approach could reduce the complexity of mutually coupled parameters influencing tracer mobility. The present thesis focuses on the interaction-induced tracer diffusion in polymer solutions and their homologous gels, probed by means of Fluorescence Correlation Spectroscopy (FCS). This is a single-molecule-sensitive technique having the advantage of optimal performance under ultralow tracer concentrations, typically employed in biosensors. Two different types of hydrogels have been investigated, a conventional one with broad polydispersity in the distance between crosslink points and a so-called ‘ideal’, with uniform mesh size distribution. The former is based on a thermoresponsive polymer, exhibiting phase separation in water at temperatures close to the human body temperature. The latter represents an optimal platform to study tracer diffusion. Mobilities of different tracers have been investigated in each network, varying in size, geometry and in terms of tracer-polymer attractive strength, as perturbed by different stimuli. The thesis constitutes a systematic effort towards elucidating the role of the strength and nature of different tracer-polymer interactions, on tracer mobilities; it outlines that interactions can still be very important even in the simplified case of dilute polymer solutions; it also demonstrates that the presence of permanent crosslinks exerts distinct tracer slowdown, depending on the tracer type and the nature of the tracer-polymer interactions, expressed differently by each tracer with regard to the selected stimulus. In aqueous polymer solutions, the tracer slowdown is found to be system-dependent and no universal trend seems to hold, in contrast to predictions from scaling theory for non-interacting nanoparticle mobility and empirical relations concerning the mesh size in polymer solutions. Complex tracer dynamics in polymer networks may be distinctly expressed by FCS, depending on the specific synergy among-at least some of - the following parameters: nature of interactions, external stimuli employed, tracer size and type, crosslink density and swelling ratio.