Publikationen

The C-H activation and subsequent carbonylation mediated by metal complexes, i. e., Rh(I) complexes, has drawn considerable attention in the past. To extend the mechanistic insight from Rh complexes featuring monodentate ligands like P(Me)3 towards more active bisphosphines (PLP), a computationally derived fully conclusive mechanistic picture of the Rh(I)-catalyzed C-H activation and carbonylation is presented here. Depending on the nature of the bisphosphine ligand, the highest lying transition state (TS) is associated either to the initial C-H activation in [Rh(PLP)(CO)(Cl)] or to the rearrangement of the chloride in [Rh(PLP)(H)(R)(Cl)]. The chloride rearrangement was found to play a key role in the subsequent carbonylation. A set of 20 complexes of different architectures was studied, in order to fine tune the C-H activation in a knowledge-driven approach. The computational analysis suggests that a flexible ligand architecture with aromatic rings can potentially increase the performance of Rh-based catalysts for the C-H activation.

The principle of droplet-based microfluidics was used for the characterization of dose/response functions of the soil bacteria Rhodococcus sp. and Chromobacterium vaccinii using a combination of optical and electrical sensors for the detection of bacterial growth and metabolic activity. For electrical characterization, a micro flow-through impedance module was developed which assessed the response of bacterial populations inside 500 nL fluid segments without direct galvanic contact between the electrodes and the electrolyte. It was found that the impedance sensor can detect an increase in cell density and is particularly suited for monitoring the metabolic response due to changes in the cultivation medium inside the separated fluid segments. Due to this sensitivity, the sensor is useful for investigating growing bacteria or cell cultures in small fluid compartments and obtaining highly resolved dose-response functions by microfluid segment sequences. The impedimetric data agree well with the optical data concerning the characteristic response of bacteria populations in the different concentration regions of heavy metal ions. However, the sensor supplies valuable complementary data on metabolic activity in case of low or negligible cell division rates.

A multistage optimization method is developed yielding Tesla valves that are efficient even at low flow rates, characteristic, e.g., for almost all microfluidic systems, where passive valves have intrinsic advantages over active ones. We report on optimized structures that show a diodicity of up to 1.8 already at flow rates of 20 μl s^-1 corresponding to a Reynolds number of 36. Centerpiece of the design is a topological optimization based on the finite element method. It is set-up to yield easy-to-fabricate valve structures with a small footprint that can be directly used in microfluidic systems. Our numerical two-dimensional optimization takes into account the finite height of the channel approximately by means of a so-called shallow-channel approximation. Based on the three-dimensionally extruded optimized designs, various test structures were fabricated using standard, widely available microsystem manufacturing techniques. The manufacturing process is described in detail since it can be used for the production of similar cost-effective microfluidic systems. For the experimentally fabricated chips, the efficiency of the different valve designs, i.e., the diodicity defined as the ratio of the measured pressure drops in backward and forward flow directions, respectively, is measured and compared to theoretical predictions obtained from full 3D calculations of the Tesla valves. Good agreement is found. In addition to the direct measurement of the diodicities, the flow profiles in the fabricated test structures are determined using a two-dimensional microscopic particle image velocimetry (μPIV) method. Again, a reasonable good agreement of the measured flow profiles with simulated predictions is observed.

Polyethersulfone (PES) is a widely used polymer in consumer and technical products. An important application is PES membranes used in the biopharmaceutical industry for sterilizing-grade filtration and for filtration of food and beverages. For both uses, detailed information about migrating compounds that can be extracted from the polymeric material into a liquid must be gathered. In the pharmaceutical industry, comprehensive extractables studies are required for contact materials, and the data is used in the qualification of the process equipment. PES is generated via polycondensation, which forms cyclic oligomers as a by-product of the reaction. However, no structural information is available for these cyclic oligomers so far. In this publication, we present the analytical determination of PES cyclic oligomers. Their presence in extracts of PES membrane filters is confirmed. The structure of the PES cyclic trimer is elucidated by X-ray and NMR investigation, obtained as crystals from the sublimation of the PES raw material. A strategy is shown to assess the toxicity of such cyclic oligomers and to derive a permitted daily exposure (PDE). The data will reduce the levels of unknowns in extractables and leachables screenings and supports the risk assessment of PES sterile filters.

Light-induced degradation (LID) in boron-doped Czochralski grown (CZ) silicon is a severe problem for silicon devices such as solar cells or radiation detectors. Herein, boron-doped CZ silicon is investigated by low-temperature photoluminescence (LTPL) spectroscopy. An LID-related photoluminescence peak is already found while analyzing indium-doped p-type silicon samples and is associated with the ASi-Sii defect model. Herein, it is investigated whether a similar peak is present in the spectra of boron-doped p-type CZ silicon samples. The presence of change in the photoluminescence signal intensity due to activation of the boron defect is investigated as well. Numerous measurements on boron-doped samples are made. For this purpose, samples with four different boron doping concentrations are analyzed. The treatments for activation of the boron defect are based on the LID cycle. During an LID cycle, an additional peak or shoulder neither in the areas of the boron-bound exciton transverse acoustic and nonphonon-assisted peaks (BTA, BNP) nor in the area of the boron-bound exciton transverse optical phonon-assisted peak (BTO) is found. The defect formation also does not lead to a lower photoluminescence (PL) intensity ratio BTO(BE)/ITO(FE).