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A strategy for the immobilization of the enzyme 2-deoxy-d-ribose-5-phosphate aldolase (DERA) is presented via spray-coating on membrane support material to generate an enzymatically active membrane which can be used in continuously run synthesis modules. A functional, water-soluble copolymer containing addressable units to covalently bind DERA is mixed with the enzyme, followed by spray-coating of the mixture onto polyacrylonitrile/polyethylene imine- (PAN/PEI) membranes and a subsequent post-processing to stabilize the coating. Confirmation of successful immobilization was achieved by atomic force microscopy (AFM) imaging and assessment of retained enzyme activity. Through variation of relevant parameters, improvements in stability and activity were seen, which formed the basis for the following optimization by Design-of-Experiment (DoE). A first fractional factorial design yielded additional performance improvements and important insights into the impacts of experimental parameters and their interaction. A second full factorial design did not result in further improvements, but validated the results of the first design.

Introduction Implant loosening is the most common indication for revision after total hip arthroplasty and is associated with progressive bone destruction. Contained defects can be treated with impaction bone grafting (IBG). Segmental defects are successfully restored with metal augmentation. Considering the increasing number of hip arthroplasty cases in young patients, it would appear sensible to reconstruct the bone stock for future revisions by biological bone defect reduction. The data on the treatment of segmental defects with IBG without additional stabilization are lacking. Materials and methods Paprosky type IIB defects were milled into 15 porcine hemipelves with segmental defect angles of 40°, 80° and 120°. Contained defects without segmental defects (Paprosky type I) and acetabula without defects served as controls. After IBG, a cemented polyethylene cup (PE) was implanted in each case. Cup migration, rotational stiffness and maximum rupture torque were determined under physiological loading conditions after 2500 cycles. Results Compared with the control without defects, IBG cups showed an asymptotic migration of 0.26 mm ± 0.11 mm on average. This seating was not dependent on the size of the defect. The maximum rupture moment was also not dependent on the defect size for cups after IBG. In contrast, the torsional stiffness of cups with an 120° segmental defect angle was significantly lower than in the control group without defects. All other defects did not differ in torsional stiffness from the control without defects. Conclusions IBG did not show inferior biomechanical properties in segmental type IIB defect angles up to 80°, compared to cups without defects.

Programmable oils feature tunable viscosity and therefore possess potential for technical improvements and innovative solutions in many lubricated applications. Herein, we describe the first assessment of the variability of rheological properties of lightprogrammable9-anthracene ester-terminated polydimethylsiloxanes(PDMS-As), including implications that arise with UV-light as an external trigger. We applied a modified rheometer setup that enables the monitoring of dynamic moduli during exposure to UV-light. The reversible dimerization of anthracene esters is used to either link PDMS chains by UV-A radiation (365 nm) or cleave chains by UV-C radiation(254 nm) or at elevated temperatures (>130 °C). Thermal cleavagefully restores the initial material properties, while the photochemical cleavage of dimers occurs only to a limited extent. Prolonged UV radiation causes material damage and in turn reduces the range of programmable rheological properties. The incomplete cleavage contributes to a gradual buildup of viscosity over a course of several switching cycles, which we suggest to result from chain-length-dependent reaction kinetics. Material property gradients induced during radiation due to attenuation of the light beam upon its passing through the oil layer have to be considered, emphasizing the need for proper mixing protocols during the programming step. The material in focus shows integrated photorheology and is suggested to improve the performance of silicone oils in friction systems.

We present a novel protocol for the synthesis of enzymatically active microgels. The protocol is based on the precipitation polymerization of N-isopropylacrylamide (NIPAm) in the presence of an enzyme and a protein binding comonomer. A basic investigation on the influence of different reaction parameters such as monomer concentration and reaction temperature on the microgel size and size distribution is performed and immobilization yields are determined. Microgels exhibiting hydrodynamic diameters between 100 nm and 1 mu m and narrow size distribution could be synthesized while about 31-44% of the enzyme present in the initial reaction mixture can be immobilized. Successful immobilization including a verification of enzymatic activity of the microgels is achieved for glucose oxidase (GOx) and 2-deoxy-d-ribose-5-phosphate aldolase (DERA). The thermoresponsive properties of the microgels are assessed and discussed in the light of activity evolution with temperature. The positive correlation of enzymatic activity with temperature for the GOx containing microgel originates from a direct interaction of the enzyme with the PNIPAm based polymer matrix whose magnitude is highly influenced by temperature.

Die Reaktion 12C(p,γ)13N bestimmt die Rate des Bethe-Weizsäcker-Zyklus in der anfänglichen Entwicklungsphase von Sternen und am äußeren Rand der Sonne. Eine genaue Kenntnis der Reaktionsrate ist somit für die Entwicklung von stellaren Modellen erforderlich. Über das Verhältnis der Raten von den Protoneneinfangreaktionen von 12C und 13C kann außerdem das entsprechende Isotopenverhältnis in Sternen bestimmt werden. Eine Revision der Rate von 12C(p,γ)13N könnte damit einen unerwartet hohen Isotopenanteil von 13C erklären, der in verschiedenen Meteoriteneinschlüssen gemessen wurde und mit den existierenden stellaren Modellen nicht hinreichend in Konsistenz gebracht werden kann. Für den S-Faktor der Reaktion existieren im Energiebereich unterhalb von 190 keV nur Messdaten aus den 1950er Jahren. Bei der Untersuchung von ähnlichen Reaktionen des Wasserstoffbrennens wurden die mit der verwendeten Messtechnik erlangten Messdaten durch moderne Experimente teilweise um einen Faktor zwei oder höher revidiert. Ziel der gegenwärtigen Arbeit war das Messen von S-Faktor-Werten in einem weiten Energiebereich von 130 keV bis 450 keV zur Überprüfung der alten Messdaten und um eine zukünftige präzisere Extrapolation zu astrophysikalisch relevanten Energien hin zu ermöglichen. Dabei wurde eine Messung in inverser Kinematik, eine Methode, für die bisher keine publizierten Daten zu der Reaktion existieren, am HZDR 3 MV Tandetron Beschleuniger durchgeführt mit TiH2-Proben, die mit 12C2+-Ionen bestrahlt wurden. Die Reaktion wurde mittels Gammaspektrometrie ausgewertet und die Proben durch die Methode der Nuklearen Resonanz-Reaktionsanalyse charakterisiert. The reaction 12C(p,γ)13N determines the rate of the Bethe-Weizsäcker cycle in the initial development phase of stars and near the surface of the Sun. An exact knowledge of the reaction rate is thus required for the development of precise stellar models. In addition, the ratio of the rates of the proton capture reactions of 12C and 13C is used to determine the corresponding isotopic ratio in stars. A revision of the rate of 12C(p,γ)13N might help to explain an unexpectedly high isotopic abundance of 13C, which was measured in presolar grains and cannot be sufficiently explained with the existing stellar models. For the S-factor of 12C(p,γ)13N in an energy range below 190 keV, the only existing data were measured in the 1950s. For similar reactions of hydrogen burning, data obtained with these measuring techniques were revised by a factor of two or higher by modern experiments. The aim of the present thesis was to measure S-factor data in a wide energy range from 130 keV to 450 keV in order to verify the old data and to allow a more precise extrapolation towards astrophysically relevant energies in the future. A measurement in inverse kinematics, a method for which no published data on the reaction exist, was performed at the HZDR 3 MV Tandetron accelerator with a 12C2+ ion beam and the use of TiH2 targets. Gamma spectroscopy was used to measure the yield and the targets were characterized with nuclear resonant reaction analysis (NRRA).