Analytische Chemie
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Computer modelling of non-destructive testing methods has come a long
way from the beginnings in the mid 90s to today. Radiographic modelling for
components with higher wall thicknesses, as they are typical for nuclear
applications, must include precise predictions of scattered radiation and its impact
in terms of contrast reduction. Dedicated or general purpose Monte Carlo methods
with the ability to calculate higher order scattering events are the state of the art for
these applications. Aerospace applications, on the other hand, have stronger
requirements on the modelling code's capabilities to import complex CAD
geometries, and can benefit from faster analytical scatter models, limited to first or
second order scattering events. Similar distinctions can be made for the various
approaches proposed to accurately model geometrical and film unsharpness, film
granularity, film responses, film/foil cartridges and photon noise. This article
presents a state-of-the-art review of radiographic modelling from the perspective of
two important application domains with very different requirements, nuclear and
aerospace.
A set of highly fluorescent, pH-responsive boron dipyrromethene dyes covering the pH range of 5-12 is presented for broad range pH measurements in mixed aqueous-organic median and polymer matrices. Readout in the intensity Domain with low cost and miniaturized Instrumentation utilizes reversible protonation induced switching ON of their initially completely quenched flourescence mediated by photoinduced electron Transfer. All dyes, rationally designed to reveal closely matching Absorption and Emission properties, are accessible via facile two-step reactions in Overall yields of up to 20%. By modifying the Substitution pattern of the meso-Aryl substiuent, the pKa values could be fine-tuned from 6 to 11. Integration of these molecules into polymeric films by a simple mixing procedure yielded reversible and longterm stable pH sensors for naked eye detection.
The photoluminescence quantum yield characterizes the performance of emitters for applications in optical devices, as reporters or probes in material and analytical sciences, and for sensing applications. Quantum yield measurements are challenging for luminescent molecules and nanocrystals immobilized in thin films for many sensor applications, particularly if spatially resolved quantitative luminescence information is desired. We show here that a Drexhage-type experiment, where a silver-coated millimeter-sized sphere is used to modify the local density of states, can provide an elegant approach to counter this challenge. As a representative example of the potential of this method, we measure the pH-dependent photoluminescence quantum yield of fluorescein isothiocyanate bound to a thin mesoporous silica film. The results were compared with those of the studies on the pH dependence of the same dye in solution. We found that our approach can link single fluorophore studies to ensemble measurements and pave the way for the spatially resolved fluorescence measurements of ultralow concentrations of emitters utilized as optically active elements and reporters in thin sensor films or incorporated into membranes.