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Mixed-conducting perovskite-type electrodes which are used as cathodes in solid oxide fuel cells (SOFCs) exhibit pronounced performance improvement after cathodic polarization. The current in situ study addresses the mechanism of this activation process which is still unknown. We chose the new perovskite-type material La(0.75)Sr(0.25)Cr(0.5)Mn(0.5)O(3±δ) which is a potential candidate for use in symmetrical solid oxide fuel cells (SFCs). We prepared La(0.75)Sr(0.25)Cr(0.5)Mn(0.5)O(3±δ) thin film model electrodes on YSZ (111) single crystals by pulsed laser deposition (PLD). Impedance spectroscopy (EIS) measurements show that the kinetics of these electrodes can be drastically improved by applying a cathodic potential. To understand the origin of the enhanced electrocatalytic activity the surfaces of operating LSCrM electrodes were studied in situ (at low pressure) with spatially resolving X-ray photoelectron spectroscopy (μ-ESCA, SPEM) and quasi static secondary ion mass spectrometry (ToF-SIMS) after applying different electrical potentials in the SIMS chamber. We observed that the electrode surfaces which were annealed at 600 °C are enriched significantly in strontium. Subsequent cathodic polarization decreases the strontium surface concentration while anodic polarization increases the strontium accumulation at the electrode surface. We propose a mechanism based on the reversible incorporation of a passivating SrO surface phase into the LSCrM lattice to explain the observed activation/deactivation process.

In ToF-SIMS analysis, the experimental outcome from cell experiments is to a great extent influenced by the sample preparation routine. In order to better judge this critical influence in the case of lipid analysis, a detailed comparison of different sample preparation routines is performed-aiming at an optimized preparation routine for systematic lipid imaging of cell cultures. For this purpose, human mesenchymal stem cells were analyzed: (a) as chemically fixed, (b) freeze-dried, and (c) frozen-hydrated. For chemical fixation, different fixatives, i.e., glutaraldehyde, paraformaldehyde, and a mixture of both, were tested with different postfixative handling procedures like storage in phosphate buffered saline, water or critical point drying. Furthermore, secondary lipid fixation via osmium tetroxide was taken into account and the effect of an ascending alcohol series with and without this secondary lipid fixation was evaluated. Concerning freeze-drying, three different postprocessing possibilities were examined. One can be considered as a pure cryofixation technique while the other two routes were based on chemical fixation. Cryofixation methods known from literature, i.e., freeze-fracturing and simple frozen-hydrated preparation, were also evaluated to complete the comparison of sample preparation techniques. Subsequent data evaluation of SIMS spectra in both, positive and negative, ion mode was performed via principal component analysis by use of peak sets representative for lipids. For freeze-fracturing, these experiments revealed poor reproducibility making this preparation route unsuitable for systematic investigations and statistic data evaluation. Freeze-drying after cryofixation showed improved reproducibility and well preserved lipid contents while the other freeze-drying procedures showed drawbacks in one of these criteria. In comparison, chemical fixation techniques via glutar- and/or paraformaldehyde proved most suitable in terms of reproducibility and preserved lipid contents, while alcohol and osmium treatment led to the extraction of lipids and are therefore not recommended.

The cathodic deposition of silver whiskers as microwires in the electrochemical cell Ag/AgBr/Ag has been investigated. From growth experiments observed with an optical microscope, we conclude that the growth process occurs exclusively at the interface of the silver wires with the solid electrolyte. The basal contacts of the microwires show different morphologies without clear correlation to the substrate. The silver crystals often show a hexagonal morphology, but XRD gives no definite information on the structure of the wires. The measured exchange current density is in the order of 100 mA/cm2. The growth rate and the diameter of the microwires can be controlled by variation of the current.

Isotope Exchange/Depth Profiling (IEDP) using Secondary Ion Mass Spectrometry (SIMS) has been used to determine the oxygen tracer diffusion and surface exchange coefficients of (100) oriented 9.5 mol% yttria stabilised zirconia single crystals. Exchange experiments performed with molecular oxygen are compared with the exchange using an oxygen plasma. The surface exchange coefficient for specimens in a plasma is up to 100 times higher compared to measurements with normal molecular oxygen. For the exchange experiments we used an inductively coupled radio frequency (rf) oxygen plasma with a maximum radio frequency power of 250 W. Double probe measurements and optical emission spectrometry are used for the characterisation of the plasma. The measured electron temperatures are within the range of 5–12 eV.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a well-established technique in material sciences but has not yet been widely explored for implementation in life sciences. Here, we demonstrate the applicability and advantages of ToF-SIMS analysis for the study of minerals and biomolecules in osseous tissue. The locally resolved analysis of fragment ions deriving from the sample surface enables imaging and differentiation of bone tissue and facilitates histology on non-stained cross sections. In a rat model, bilateral ovariectomy combined with either a multi-deficiency diet or steroid treatment was carried out to create osteoporotic conditions. We focused our study on the Ca content of the mineralized tissue and monitored its decline. Calcium mass images of cross sections show the progressive degenerative changes in the bone. We observed a decreased Ca concentration in the edge region of the trabeculae and a decline in the Ca/P ratio. Additionally, we focused on the non-mineralized matrix and identified fragment ions that are characteristic for the collagen matrix. We observed trabeculae with wide ranges of non-mineralized collagen for the diet group owing to an impaired mineralization process. Here, the advantage of coeval monitoring of collagen and minerals indicated an osteomalacic model rather than an osteoporotic one.

ZnO/Zn1−xMgxO single quantum wells (SQWs) were grown by plasma-assisted molecular beam epitaxy on c-plane sapphire substrates. Compositional grading allows the application of optimized growth conditions for the fabrication of Zn1−xMgxO barriers with high crystalline quality and a maximum Mg content of x = 0.23. High resolution x-ray diffraction reveals partial relaxation of the graded barriers. Due to exciton localization, the SQW emission is found to consist of contributions from donor-bound and free excitons. While for narrow SQWs with well width dW≤2.5nm, the observed increase of the exciton binding energy is caused by quantum confinement, the drop of the photoluminescence emission below the ZnO bulk value found for wide SQWs is attributed to the quantum-confined Stark effect. For a Mg content of x = 0.23, a built-in electric field of 630 kV/cm is extracted, giving rise to a decrease of the exciton binding energy and rapid thermal quenching of the SQW emission characterized by an activation energy of (...

ZnO/Zn1 − xMgxO single quantum well (SQW) structures with well widths dW between 1.1 nm and 10.4 nm were grown by plasma-assisted molecular beam epitaxy both heteroepitaxially on c-plane sapphire and homoepitaxially on (0001¯)-oriented bulk ZnO. A significantly reduced Mg incorporation in the top barrier related to the generation of stacking faults is observed for heteroepitaxial samples. Exciton localization is observed for both types of samples, while an enhancement of the exciton binding energy compared to bulk ZnO is only found for homoepitaxial SQWs for 2 nm ≤ dW ≤ 4 nm. Consistently, for homoepitaxial samples, the carrier dynamics are mainly governed by radiative recombination and carrier cooling processes at temperatures below 170 K, whereas thermally activated non-radiative recombination dominates in heteroepitaxial samples. The effects of polarization-induced electric fields are concealed for Mg concentrations x

Based on the increasing number of multi-drug resistant bacteria in periprosthetic infections, improvement of the antibacterial activity of commonly used biomaterials must be achieved. The broad-spectrum, high antimicrobial efficacy has made silver nanoparticles a promising new antibacterial agent. However, there is still a serious lack of knowledge concerning the impact of nanosilver on bone cells. For this reason a study was conducted to evaluate the influence of silver nanoparticles on osteoclastogenesis of human peripheral blood mononuclear cells. Upon incubation with subtoxic concentrations of nanosilver the cells did not exhibit changes in osteoclast differentiation and podosomal structures. However, the osteoclasts were able to uptake the nanoparticles, accumulating them in endo-lysosomal compartments. Furthermore, nanosilver exposure led to an increase in oxidative stress and a decrease in clathrin-dependent endocytosis on the mRNA level. In conclusion, our results indicate nanosilver-induced cell stress at higher concentrations. For this reason antibacterial benefits and possible health risks should be weighed in more detail in further studies.

New bone formation was studied in a metaphyseal fracture-defect in ovariectomized rats stimulated by a plain and a strontium-enriched macroporous silica/collagen scaffold (ScB30 and ScB30Sr20) and a compact silica/collagen xerogel (B30). 45 female Sprague-Dawley rats were randomly assigned to three different treatment groups: (1) ScB30 (n=15), (2) ScB30Sr20 (n=15), and (3) B30 (n=15). 12 weeks after bilateral ovariectomy and multi-deficient diet, a 4 mm wedge-shaped fracture-defect was created at the metaphyseal area of the left femur. A 7-hole T-shaped plate at the lateral aspect of the femur stabilized the bone and the defect was filled with ScB30, ScB30Sr20 or B30 subsequently. After six weeks, histomorphometrical analysis revealed a statistically significant higher bone volume/tissue volume ratio in the ScB30Sr20 group compared to ScB30 (p=0.043) and B30 (p=0.0001) indicating an improved formation of new bone by the strontium-enriched macroporous silica/collagen scaffold. Furthermore, immunohistochemical results showed increased expression of BMP2 and OPG and a decreased RANKL expression in the ScB30Sr20 group. This was further confirmed with the gene expression analysis where an increase in prominent bone formation markers (ALP, OCN, Runx2, Col1a1 and Col10a1) was seen. No material remnants were found in the scaffold group indicating an almost complete degradation process of the biomaterials. This is confirmed by ToF-SIMS analysis that did not detect any strontium in the ScB30Sr20 group neither in the defect nor in the surrounding tissue. Taken together, this study shows the stimulating effects of strontium through increased bone formation by up regulation of osteoanabolic markers. This work also indicates the importance of material porosity, geometry and biodegradability in bone healing.

Commonly used implants for therapeutic approaches of non-systemically impaired bone do not sufficiently support the healing process of osteoporotic bone. Since strontium (II) has been proven as an effective anti-osteoporotic drug new types of strontium enriched calcium phosphate bone cements were developed. As osteoporosis is characterized by an imbalance of osteoblast and osteoclast activity the influence of this newly generated strontium enriched biomaterials on the cellular behavior of osteoblast-like cells was investigated by time of flight secondary ion mass spectrometry (ToF-SIMS). ToF-SIMS is used to analyze whether strontium is incorporated in the mineralized extracellular matrix (mECM) and whether there is strontium uptake by osteogenically differentiated human mesenchymal stem cells (hMSCs). Therefore hMSCs were cultured in osteogenic differentiation medium for 21 days on two different strontium enriched bone cements (S100 and A10) and for reference also on the pure calcium phosphate cement (CPC) and on a silicon wafer. The distribution of strontium in the osteoblast-like cells and within their mineralized extracellular matrix was analyzed. A higher intensity of the strontium signal could be detected in the region of the mECM, synthesized by cells cultivated on the Sr- substituted bone cement (S100) in comparison to the reference groups. The osteoblast-like cells used the released strontium from the biomaterial to synthesize their mECM. Apart from that a uniform strontium distribution was measured within all investigated cells. However, different amounts of strontium were found in cells cultured on different biomaterials and substrates. Compared to the negative controls the strontium content in the cells on the strontium enriched biomaterials was much higher. A higher concentration of strontium inside the cells means that more strontium can take part in signaling pathways. As strontium is known for its beneficial effects on osteoblasts by promoting osteoblastic cell replication and differentiation, and reducing apoptosis, the newly developed strontium enriched calcium phosphate cements are promising implant materials for osteoporotic bone. Electronic supplementary material The online version of this article (doi:10.1186/1559-4106-8-17) contains supplementary material, which is available to authorized users.