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249
In der vorliegenden Arbeit wird die Ultraschallausbreitung in akustisch anisotropen, homogenen Werkstoffen mit stengelkristalliner Textur wie austenitischen Plattierungen und Schweißverbindungen, austenitischem Guss oder geschweißten Komponenten aus austenitischem Gus modelliert. Die Ergebnisse dieser Arbeit dienen als Vorgabe für Prüfanweisungen und Regelwerke, die besser als bisher an den Prüfgegenstand angepasst sind.
235
The present work is focused on the study of the spectroscopic and complexometric behavior of different ion-sensitive fl uorescent probes. Three of the four types of probes studied follow a conventional principle of signal generation and their molecular constitution corresponds to either a fl uorescent ligand ( BP(OH)2), so-called intrinsic charge transfer (ICT) fl uorescent probes (donor- acceptor-substituted chalcones), or electron transfer (ET) fl uorescent probes (substituted triaryl-Δ2- pyrazolines). The latter two systems are designed in a modular way and thus, both the signal generating fl uorophore and the complexing receptor can be carefully tuned. Whereas in the case of the ICT probes both units are electronically conjugated, these moieties are more or less electronically decoupled in the ET probes and signal generation is based on the modifi cation of a long range electron transfer process. The fourth type of probe investigated, a boron dipyrromethene derivative (BDP), is also designed in a modular way. But here, due to the highly pretwisted constitution of the molecule, fl uorophore and receptor are only “virtually” decoupled. Besides employing this alternative mechanism of signal generation, control of the selectivity by carefully directed receptor design and improvement of the selectivity and sensitivity of fl uorometric metal ion analysis by recording time resolved emission spectra (TRES) were the main aims of these investigations. Furthermore, with the aid of various model compounds, NMR spectroscopy as well as quantum chemical calculations, a fundamental understanding of the photophysical behavior of the different classes of dyes was obtained. In accordance with its parent compound 2,2‘- bipyridyl, the fl uorescent ligand BP(OH)2 shows complexation induced changes of its absorption and emission behavior in the presence of heavy and transition metal ions. Whereas paramagnetic ions such as CuII or NiII (and also HgII) lead to static fl uorescence quenching, the diamagnetic ions ZnII and CdII form strongly fl uorescent complexes with ion specifi c fl uorescence lifetimes in the ns time range. Both complexes are stable in the excited state which is manifested by a strongly reduced rate constant of non radiative deactivation compared to that of the free ligand. Both the absorption and emission spectra of the complexes largely overlap and a discrimination with steady-state fl uorometry is very limited. Nevertheless, with time resolved fl uorometry a separation of both components is possible and for a series of synthetic ZnII/CdII containing samples this gain in selectivity by global analysis of the time resolved emission spectra (TRES) could be demonstrated. The intrinsic fl uorescent probes of chalcone type contain a cation selective receptor in the donor part of the molecule and show a strong decrease of the intramolecular charge transfer process due to complexation induced weakening of the donor. Depending on molecular probe design and solvent polarity, the fl uorescence of the uncomplexed molecule occurs either from a polar directly exicted (E*) or a highly polar charge transfer state (A*) which is populated via an excited state reaction involving single bond twisting. Here, competing processes include population of a non emissive polar (K*) or weakly polar (P*) transient state. Furthermore, the fl uorescence of these dyes can be quenched by energetically close lying nπ* states (in apolar solvents) or by enhanced internal conversion due to the decreasing energy gap between ground and excited state (in highly polar solvents). As mentioned above, the donor strength is reduced upon cation complexation in polar solvents and a moderate fl uorescence enhancement occurs. Besides increased fl uorescence quantum yields, this effect results in ion specifi c fl uorescence lifetimes of the complexes. Upon exchanging the aza oxa for an aza thia macrocycle in the receptor part of the system, the cation selectivity could be tuned from alkali and alkaline earth metal ions to the thiophilic metal ions AgI and HgII. Here, especially the fl uorescence enhancement in the presence of the well-known quencher HgII is analytically valuable. Upon cation binding the ET probes of the triaryl-Δ2-pyrazoline type show very small spectral shifts but much larger fl uorescence enhancement compared to the ICT probes. Again, by problem specifi c use of different receptors, the selectivities can be controlled. Based on a detailed investigation, for the 5-p-N,N-dialkylanilino-3-benzthiazol-1-phenyl-Δ2-pyrazolines, the intramolecular processes which lead to fl uorescence quencing in the unbound state and “switching on” of the fl uorescence in the complexed state could be identifi ed. For these molecules, the intramolecular charge transfer in the basic chromophore occurs in the sub ps time range and is quenched by an electron transfer process from the largely electronically decoupled receptor to the acceptor part of the basic chromophore on the ps time scale in highly polar solvents. “Virtually” decoupling fl uorophore and receptor in the BDP derivative fi nally makes it possible to yield extremely high complexation induced fl uorescence enhancement signals. For these highly pretwisted donor acceptor biaryls, the directly excited emissive state (LE) forms a highly polar, twisted charge separated charge transfer state (CT) in polar solvents. Emission of the latter is strongly forbidden and, depending on solvent polarity, is largely red shifted compared to the LE fl uorescence. Thus, a largely separated dual fl uorescence is already observed in solvents of medium polarity and in highly polar solvents both fl uorescence bands are nearly completely quenched. Metal ion complexation blocks off the CT process and leads to a “switching on” of the LE emission yielding fl uorescence enhancement factors > 1000. This process is so sensitive that for most of the cation complexes studied, two emissive complex conformers with strongly overlapping absorption and emission spectra occur which could be distinguished by their fl uorescence lifetimes.
277
The use of alternative oils for the lubrication of automobile engines has a potential of ecological and technical advantages. It requires the detailed knowledge of several thermophysical and viscometric properties in a large temperature range (mapping). Therefore, the following properties of up to twenty-eight different oils have been measured in the temperature range from 22 °C to 150 °C: density, heat capacity, thermal conductivity, viscosity at ambient pressure, viscosity under shear rates above 10 6 s-1, and the viscosity at elevated pressures (maximum 100 MPa). The last two have been measured with a substantially improved and a newly developed apparatus, respectively. The pressure- viscosity coefficient has been measured on four hydrocarbon-based, factory-fill oils, a paraffin oil and twenty-three alternative oils. Nine of the alternative oils are based partly or completely on esters, the other fourteen on polyglycols, two of them additionally on water.
245
Die Reduzierung von Schadstoffen im Grundwasser mit reaktiven Wänden ist eine neuartiges passives Sanierungsverfahren. Die am häufigsten angewandten Dekontaminierungsprozesse sind dabei chemische Reduktion, Oxidation, Ausfällung und Sorption, die im Bericht beispielhaft dargestellt sind. Blei, Chrom und insbesondere Uran werden unter den anorganischen Schadstoffen detailliert behandelt, da solche Grundwasserverunreinigung in vielen europäischen Ländern auftreten. Baumethoden für Dichtwände und reaktive Wände weisen gemeinsame Merkmale auf. Neben den gewöhnlichen Methoden werden Bohrverfahren, deep-soil-mixing, Strahltechnologien, Brunnengalerien, Injektionssysteme und Biobarrieren angewendet, um reaktive Wände zu errichten. Die Technik der reaktiven Wände besitzt ein großes Potential für die Sanierungstechnik der Zukunft.