Publikationen

From a biomineralization point of view, the protist world is far less investigated than its metazoan counterpart. However, eukaryotic single-celled organisms offer a very unique access to discover biomineralization mechanisms in vivo. With respect to intracellular mechanisms involved in ion enrichment, mineral transport or vesicle formation ciliates represent a good model system. One important group of protists, the ciliates, is very common and numerous studies have been performed on their ecology, cell biology, morphology or genetics. Ciliates are also known for their formation of diverse mineralized intracellular and extracellular structures. However, only limited numbers of detailed studies on the kind of minerals, their properties or their formation mechanisms have been reported so far. This article reviews older and more recent literature on biomineralization in ciliates.

We report the effects of exposure to alkylated silicon nanocrystals ('alkyl-SiNCs' at concentration ~ 7.2 mg/L) and gamma-Fe2O3 nanoparticles coated with ultra-thin silica ('SiO2-coated IONPs' at concentration ~ 150 mg/L) on sea urchins Paracentrotus lividus and Arbacia lixula, respectively, studied with X-ray fluorescence (XRF) and Fourier transform infrared (FTIR) spectroscpoies using excitation from a synchrotron light source. A remarkably low mortality and low incidence of skeletal deformation is observed for exposure to both types of nanoparticles studied, despite the high concentrations employed in this work. XRF mapping demonstrates that both types of nanoparticle are found to agglomerate in the body of the sea urchins. FTIR spectra indicates that alkyl-SiNCs remain intact after ingestion and corresponding XRF maps show increased an oxygen throughout the organisms, possibly related to oxidation products arising from reactive oxygen species generated in the presence of the nanoparticles. Exposure to SiO2-coated IONPs is found to produce sulphur-containing species, which may be the result of a biological response in order to reduce the toxicity of the nanomaterial.

Iron is an essential micronutrient for plants, and iron deficiency requires a variety of physiological adaptations. FIT (FER-LIKE IRON DEFICIENCY-INDUCED TRANSCRIPTION FACTOR) is essential for the regulation of iron uptake in Arabidopsis thaliana roots. FIT is transcriptionally as well as posttranscriptionally regulated in response to iron supply. To investigate to which extent posttranscriptional regulation upon iron deficiency applies to proteins and to determine the dependency on FIT, we performed a parallel proteomic and transcriptomic study with wild-type, a fit knock-out mutant, and a FIT overexpressing Arabidopsis line. Among 92 proteins differentially regulated by iron and/or FIT, we identified 30 proteins, which displayed differential regulation at the transcriptional level. Eleven protein spots were regulated in at least one of the data points even contrary to the respective genes dependent on FIT. We found ten proteins in at least two forms. The analysis of functional classification showed enriched GO terms among the posttranscriptionally regulated genes and of proteins, that were downregulated or absent in the fit knock-out mutant. Taken together, we provide evidence for iron and FIT-dependent posttranscriptional regulation in iron homeostasis in A. thaliana.

In this study, we propose a simple and rapid technique for characterization of free fatty acids and triacylglycerides (TAG) based on palladium nanoparticular (Pd-NP) surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS). The implemented Pd-NP material allowed detection of free fatty acids and TAGs exclusively as [M + K]+ ions in positive ion mode. Under negative ionization conditions, unusual trimetric structures were generated for free fatty acids, while TAGs underwent irreproducible degradation reactions. Importantly, the mass spectra obtained from Pd-NP targets in positive ion mode were very clean without interferences from matrix-derived ions in the low m/z range and readily enabled the detection of intact TAGs in vegetable oils without major fragmentation reactions as compared to conventional MALDI-MS, requiring only a minimal amount of sample preparation.

The sorption of selected hydrophilic pH-sensitive dyes (bromophenol blue, bromothymol blue, bromocresol purple, alizarin red, methyl orange, congo red, rhodamine 6G) on films of anodized aluminium oxide (AAO) was investigated in this study. Depth and pore structure of the AAO channels were adjusted by changing electrolysis time and current density during treatment of aluminium foil in oxalic acid, sulfosalycilic acid and sulfuric acid at concentration levels between 0.2 and 0.6 M. The dyes were immobilized on the AAO surface by direct saturation of the films in dye solutions. It was shown by scanning electron microscopy and X-ray spectral analysis that the dyes penetrated into the AAO channels by more than 1.5 [small mu ]m, even at static saturation conditions. The anionic dyes linked to the porous AAO surface exhibited differential shifts of the UV absorption bands in their acidic/basic forms. By combining several dyes, the films have an application range between pH = 0.5-9 in aqueous media. The dye-modified AAO film was a simple, portable, inexpensive and reusable pH sensor with very fast response time and clear colour transitions.

The curing time of an adhesive material is determined by the polymerization and cross-linking kinetics of the adhesive formulation and needs to be optimized for the particular application. Here, we explore the possibility of tuning the polymerization kinetics and final mechanical properties of tissue-adhesive PEG gels formed by polymerization of end-functionalized star-PEGs with catecholamines with varying substituents. We show strong differences in cross-linking time and cohesiveness of the final gels among the catecholamine-PEG variants. Installation of an electron-withdrawing but π-electron donating chloro substituent on the catechol ring resulted in faster and more efficient cross-linking, while opposite effects were observed with the strongly electron-withdrawing nitro group. Chain substitution slowed down the kinetics and hindered cross-linking due either to chain breakdown (beta-OH group, in norepinephrine) or intramolecular cyclization (α-carboxyl group, in DOPA). Interesting perspectives derive from use of mixtures of catecholamine-PEG precursors offering further opportunities for fine-tuning of the curing parameters. These are interesting properties for the application of catecholamine-PEG gels as tissue glues or biomaterials for cell encapsulation.

Supercapacitors combine efficient electrical energy storage and performance stability based on fast electrosorption of electrolyte ions at charged interfaces. They are a central element of existing and emerging energy concepts. A better understanding of capacitance enhancement options is essential to exploit the full potential of supercapacitors. Here, we report a novel hierarchically structured N-doped carbon material and a significant capacitance enhancement for a specific ionic liquid. Our studies indicate that matching of the electrode material and the ionic liquid specifically leads to a constant normalized resistance of the electrode material (voltage window up to +/-1 V vs. carbon) and a significant enhancement of the specific capacitance. Such effects are not seen for standard organic electrolytes, non-matched ionic liquids, or non-N-doped carbons. A higher N-doping of the electrode material improves the symmetric full cell capacitance of the match and considerably increases its long-term stability at +3 V cell voltage. This novel observance of enhanced specific capacitance for N-doped carbons with matched ionic liquid may enable a new platform for developing supercapacitors with enhanced energy storage capacity.

The structural characterisation of nanoporous carbons is a challenging task as they generally lack long-range order and can exhibit diverse local structures. Such characterisation represents an important step towards understanding and improving the properties and functionality of porous carbons, yet few experimental techniques have been developed for this purpose. Here we demonstrate the application of nuclear magnetic resonance (NMR) spectroscopy and pair distribution function (PDF) analysis as new tools to probe the local structures of porous carbons, alongside more conventional Raman spectroscopy. Together, the PDFs and the Raman spectra allow the local chemical bonding to be probed, with the bonding becoming more ordered for carbide-derived carbons (CDCs) synthesised at higher temperatures. The ring currents induced in the NMR experiment (and thus the observed NMR chemical shifts for adsorbed species) are strongly dependent on the size of the aromatic carbon domains. We exploit this property and use computer simulations to show that the carbon domain size increases with the temperature used in the carbon synthesis. The techniques developed here are applicable to a wide range of porous carbons, and offer new insights into the structures of CDCs (conventional and vacuum-annealed) and coconut shell-derived activated carbons.

Thermal energy is abundantly available, and especially low-grade heat is often wasted in industrial processes as a by-product. Tapping into this vast energy reservoir with cost-attractive technologies may become a key element for the transition to an energy-sustainable economy and society. We propose a novel heat-to-current converter which is based on the temperature dependence of the cell voltage of charged supercapacitors. Using a commercially available supercapacitor, we observed a thermal cell-voltage rise of around 0.6 mV K-1 over a temperature window of 0 [degree]C to 65 [degree]C. Within our theoretical model, this can be used to operate a Stirling-like charge-voltage cycle whose efficiency is competitive to the most-efficient thermoelectric (Seebeck) engines. Our proposed heat-to-current converter is built from cheap materials, contains no moving parts, and could operate with a plethora of electrolytes which can be chosen for optimal performance at specific working temperatures. Therefore, this heat-to-current converter is interesting for small-scale, domestic, and industrial applications.

We present a study on the pseudocapacitive properties of birnessite-type MnO2 grafted on highly graphitized onion-like carbon (OLC/MnO2). In a three-electrode setup, we evaluated two different substrates, namely a platinum disc and nickel foam. The OLC/MnO2 nanohybrid exhibited a large specific capacitance (Csp) of 295 and 323 F g-1 (at 1 A g-1) for the Pt disc and Ni foam, respectively. In addition, the Ni foam substrate exhibited much higher rate capability (power density) than the Pt disc. A symmetrical two-electrode device, fabricated with the Ni foam, showed a large Csp of 254 F g-1, a specific energy density of 5.6 W h kg-1, and a high power density of 74.8 kW kg-1. These values have been the highest for onion-based electrodes so far. The device showed excellent capacity retention when subjected to voltage-holding (floating) experiments for 50 h. In addition, the device showed a very short time constant ([small tau] = 40 ms). This high rate handling ability of the OLC/MnO2 nanohybrid, compared to literature reports, promises new opportunities for the development of aqueous-based pseudocapacitors.