Marcus Rohnke

Biocompatibility of silver nanoparticles and silver ions in primary human mesenchymal stem cells and osteoblasts

The prevention of implant-related infections is an important issue in medical research. The aim is to exploit the strong antimicrobial effect of silver nanoparticles (AgNP) to develop new antibacterial coatings for implants. However, there is still a serious lack of information on the influence of AgNP on bone metabolism. In the present study we have evaluated the influence of AgNP on cell stress, viability, proliferation and differentiation of primary human mesenchymal stem cells (MSC) and osteoblasts (OB). Finally, cellular uptake of the AgNP was examined. After 21 days impairment of cell viability of MSC and OB occurred at a concentration of 10 μg/g of AgNP. Cytotoxicity and inhibition of proliferation was highly time and dose dependent. No influence on cell differentiation, but an increase in cell stress, was observed. Uptake of AgNP into MSC and OB could be confirmed. In summary, these results demonstrate AgNP-mediated cytotoxicity at higher concentrations. Therefore, a therapeutical window for the application of AgNP in medical products might exist. However, the antibacterial benefits and potential health risks of AgNP need to be weighed in further studies.

A novel and easy-to-prepare strontium(II) modified calcium phosphate bone cement with enhanced mechanical properties

The aim of this study was to evaluate two different approaches to obtaining strontium-modified calcium phosphate bone cements (SrCPCs) without elaborate synthesis of Sr-containing calcium phosphate species as cement precursors that could release biologically effective doses of Sr(2+) and thus could improve the healing of osteoporotic bone defects. Using strontium carbonate as a strontium(II) source, it was introduced into a hydroxyapatite-forming cement either by the addition of SrCO3 to an α-tricalcium phosphate-based cement precursor mixture (A-type) or by substitution of CaCO3 by SrCO3 during precursor composition (S-type). The cements, obtained after setting in a water-saturated atmosphere, contained up to 2.2at.% strontium in different distribution patterns as determined by time-of-flight secondary ion mass spectrometry and energy-dispersive X-ray spectroscopy. The setting time of CPC and A-type cements was in the range of 6.5-7.5min and increased for substitution-type cements (12.5-13.0min). Set cements had an open porosity between 26 and 42%. Compressive strength was found to increase from 29MPa up to 90% in substituted S-type cements (58MPa). SrCPC samples released between 0.45 and 1.53mgg(-1) Sr(2+) within 21days and showed increased radiopacity. Based on these findings, the SrCPC developed in this study could be beneficial for the treatment of defects of systemically impaired (e.g. osteoporotic) bone.

Germanium doping of self-assembled GaN nanowires grown by plasma-assisted molecular beam epitaxy

Germanium doping of GaN nanowires grown by plasma-assisted molecular beam epitaxy on Si(111) substrates is studied. Time of flight secondary ion mass spectrometry measurements reveal a constant Ge-concentration along the growth axis. A linear relationship between the applied Ge-flux and the resulting ensemble Ge-concentration with a maximum content of 3.3×1020 cm−3 is extracted from energy dispersive X-ray spectroscopy measurements and confirmed by a systematic increase of the conductivity with Ge-concentration in single nanowire measurements. Photoluminescence analysis of nanowire ensembles and single nanowires reveals an exciton localization energy of 9.5 meV at the neutral Ge-donor. A Ge-related emission band at energies above 3.475 eV is found that is assigned to a Burstein-Moss shift of the excitonic emission.

Quantitative 3D Fluorescence Imaging of Single Catalytic Turnovers Reveals Spatiotemporal Gradients in Reactivity of Zeolite H-ZSM-5 Crystals upon Steaming

Optimizing the number, distribution, and accessibility of Brønsted acid sites in zeolite-based catalysts is of a paramount importance to further improve their catalytic performance. However, it remains challenging to measure real-time changes in reactivity of single zeolite catalyst particles by ensemble-averaging characterization methods. In this work, a detailed 3D single molecule, single turnover sensitive fluorescence microscopy study is presented to quantify the reactivity of Brønsted acid sites in zeolite H-ZSM-5 crystals upon steaming. This approach, in combination with the oligomerization of furfuryl alcohol as a probe reaction, allowed the stochastic behavior of single catalytic turnovers and temporally resolved turnover frequencies of zeolite domains smaller than the diffraction limited resolution to be investigated with great precision. It was found that the single turnover kinetics of the parent zeolite crystal proceeds with significant spatial differences in turnover frequencies on the nanoscale and noncorrelated temporal fluctuations. Mild steaming of zeolite H-ZSM-5 crystals at 500 °C led to an enhanced surface reactivity, with up to 4 times higher local turnover rates than those of the parent H-ZSM-5 crystals, and revealed remarkable heterogeneities in surface reactivity. In strong contrast, severe steaming at 700 °C significantly dealuminated the zeolite H-ZSM-5 material, leading to a 460 times lower turnover rate. The differences in measured turnover activities are explained by changes in the 3D aluminum distribution due to migration of extraframework Al-species and their subsequent effect on pore accessibility, as corroborated by time-of-flight secondary ion mass spectrometry (TOF-SIMS) sputter depth profiling data.

Intergrowth structure and aluminium zoning of a zeolite ZSM-5 crystal as resolved by synchrotron-based micro-X-ray diffraction imaging

Zeolites represent an important group of heterogeneous catalysts and are heavily used in the petrochemical and refining industries.[1] Since their discovery, zeolites with MFI topology, namely ZSM-5, have been utilized in a number of large-scale industrial applications. The unique combination of acidic properties and pore architecture[2] enabled their use as solid acid catalysts in the alkylation of arenes,[3] the oligomerization of light olefins,[4] and the methanol-to-hydrocarbon reaction.[5] The internal crystallographic architecture, microand mesoporosity, as well as the 3D distribution of Bronsted acid sites play a crucial role in the catalytic performance of zeolites.

Strontium substitution in apatitic CaP cements effectively attenuates osteoclastic resorption but does not inhibit osteoclastogenesis.

UNLABELLED Strontium ions were discovered to exert a dual effect on bone turnover, namely an inhibition of cell-driven bone resorption and a simultaneous stimulation of new bone tissue formation. A variety of strontium containing calcium phosphate bone cements (SrCPC) have been developed to benefit from both effects to locally support the healing of osteoporotic bone defects. While the stimulating effect of strontium modification on bone forming cells has been demonstrated in a number of studies, this study focuses on the inhibition and/or reduction of osteoclastogenesis and osteoclastic resorption by a strontium substituted calcium phosphate bone cement (SrCPC). Human peripheral blood mononuclear cells (PBMC) were differentiated into osteoclasts in the presence of different Sr(2+)-concentrations as well as on the surface of SrCPC disks. Osteoclastogenesis of PBMC was shown to be merely unaffected by medium Sr(2+)-concentrations comparable to those released from SrCPC in vitro (0.05-0.15mM). However, an altering effect of 0.1mM strontium on the cytoskeleton of osteoclast-like cells was shown. In direct contact to SrCPC disks, these cells exhibited typical morphological features and osteoclast markers on both RNA and protein level were formed. However, calcium phosphate resorption was significantly decreased on strontium-containing cements in comparison to a strontium-free control. This was accompanied by an intracellular accumulation of strontium that increased with substrate strontium content as demonstrated by Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). This study illustrates that SrCPC do not inhibit osteoclastogenesis but significantly attenuate osteoclastic substrate resorption in vitro. STATEMENT OF SIGNIFICANCE Strontium ions have been shown to promote bone formation and inhibit bone resorption. Therefore strontium is successfully used in the treatment of osteoporosis and also inspired the development of strontium-containing strontium/calcium phosphate bone cements (SrCPC). Studies have shown the positive effects of SrCPC on bone formation, however, the inhibiting effect of strontium on bone resorption in the context of such cements has not been shown so far. We found that the formation of bone-resorbing osteoclasts is not inhibited, but that their resorption activity is decreased in contact to SrCPC. The former is important since those cells play an important role in the bone cell signaling. The latter is a key requirement in osteoporosis therapy, which addresses excess bone resorption.

Applicability of ToF-SIMS for monitoring compositional changes in bone in a long-term animal model

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.

Large zeolite H-ZSM-5 crystals as models for the methanol-to-hydrocarbons process : bridging the gap between single-particle examination and bulk catalyst analysis

The catalytic, deactivation, and regeneration characteristics of large coffin-shaped H-ZSM-5 crystals were investigated during the methanol-to-hydrocarbons (MTH) reaction at 350 and 500 °C. Online gas-phase effluent analysis and examination of retained material thereof were used to explore the bulk properties of large coffin-shaped zeolite H-ZSM-5 crystals in a fixed-bed reactor to introduce them as model catalysts for the MTH reaction. These findings were related to observations made at the individual particle level by using polarization-dependent UV-visible microspectroscopy and mass spectrometric techniques after reaction in an in situ microspectroscopy reaction cell. Excellent agreement between the spectroscopic measurements and the analysis of hydrocarbon deposits by means of retained hydrocarbon analysis and time-of-flight secondary-ion mass spectrometry of spent catalyst materials was observed. The obtained data reveal a shift towards more condensed coke deposits on the outer zeolite surface at higher reaction temperatures. Zeolites in the fixed-bed reactor setup underwent more coke deposition than those reacted in the in situ microspectroscopy reaction cell. Regeneration studies of the large zeolite crystals were performed by oxidation in O2 /inert gas mixtures at 550 °C. UV-visible microspectroscopic measurements using the oligomerization of styrene derivatives as probe reaction indicated that the fraction of strong acid sites decreased during regeneration. This change was accompanied by a slight decrease in the initial conversion obtained after regeneration. H-ZSM-5 deactivated more rapidly at higher reaction temperature.

A biomimetic principle for the chemical modification of metal surfaces: synthesis of tripodal catecholates as analogues of siderophores and mussel adhesion proteins.

By following a biomimetic design principle, tetravalent scaffolds based on an adamantyl and trisalkylmethyl core structure have been synthesized. These scaffolds have been coupled to three catecholamines, thus resembling the characteristic tripodal recognition motif of many natural metal binders, such as mussel adhesion proteins and siderophores, for example, enterobactin. Besides this tripodal recognition element, our scaffolds provide a fourth position for the conjugation of effector molecules. These effectors can be conjugated through biocompatible conjugation techniques to the scaffold and can be used to tailor the properties of different metal surfaces for a range of applications, for example, in implant engineering. Herein, we describe the synthesis of several tripodal metal binders and their immobilization on TiO(2) surfaces by using a simple dip-coating procedure. Furthermore, we demonstrate the conjugation of our surface binders to the dye eosin Y as an effector molecule by peptide coupling. The resulting surfaces have been analyzed by using ellipsometry, time-of-flight secondary ion mass spectrometry, IR spectroscopy, and contact-angle measurements to confirm the specific loading on TiO(2) films and nanoparticles with our trivalent surface binders. As a proof of concept, we have demonstrated the functionalization of TiO(2) nanoparticles with the eosin Y dye.

Exciton confinement in homo- and heteroepitaxial ZnO/Zn1 − xMgxO quantum wells with x < 0.1

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 < 0.1 due to the reduction of the exciton binding energy, the screening by residual c...