Publikationen

Monodisperse, crystalline silver nanoparticles are synthesized by sonolytically assisted decomposition of silver oxalate and oleate precursors in dibenzylether. Oleic acid and oleylamine are used as capping agents. The diameters of the obtained particles vary from 6 to 10 nm depending on the sonification time and the precursor material. The particles are stable in non-polar media. A 2D and 3D assembly of the as-prepared nanoparticles is observed. Particle sizes and dispersities are characterized by transmission electron microscopy and image analysis. The decomposition characteristics of the different precursor compounds are investigated using UV–Vis spectroscopy and thermogravimetry.

The metal chelator nicotianamine promotes the bioavailability of Fe and reduces cellular Fe toxicity. For breeding Fe-efficient crops, we need to explore the fundamental impact of nicotianamine on plant development and physiology. The quadruple nas4x-2 mutant of Arabidopsis thaliana cannot synthesize any nicotianamine, shows strong leaf chlorosis, and is sterile. To date, these phenotypes have not been fully explained. Here, we show that sink organs of this mutant were Fe deficient, while aged leaves were Fe sufficient. Upper organs were also Zn deficient. We demonstrate that transport of Fe to aged leaves relied on citrate, which partially complemented the loss of nicotianamine. In the absence of nicotianamine, Fe accumulated in the phloem. Our results show that rather than enabling the long-distance movement of Fe in the phloem (as is the case for Zn), nicotianamine facilitates the transport of Fe from the phloem to sink organs. We delimit nicotianamine function in plant reproductive biology and demonstrate that nicotianamine acts in pollen development in anthers and pollen tube passage in the carpels. Since Fe and Zn both enhance pollen germination, a lack of either metal may contribute to the reproductive defect. Our study sheds light on the physiological functions of nicotianamine.

In biological cells, various transmembrane enzymes function as highly effective chemical reactors confined in space with characteristic length scales of tens of nanometers to micrometer. However, it is still challenging to quantitatively confine membranes in compact reactor platforms without losing their biochemical functions. Here, a simple and straightforward strategy towards the fabrication of a new flow-through reactor by the functional coating of porous silica microparticles with sarcoplasmic reticulum membranes is described. After a short incubation, the membranes achieve the homogeneous, full coverage of the particle surface, spanning across pores with the diameter of about 100 nm. By using the underlying pores as cavity reservoirs, transmembrane enzyme (Ca2+-ATPase) in the membrane retains their capability of ATP hydrolysis. This enables us to confine 1.1 m2 of native membranes containing a large amount of Ca2+-ATPase (approx. 10 nmol) in a column-packaged, flow-through reactor with merely 1.8 mL volume, which cannot be achieved by the reconstitution of proteins in artificial lipid membranes or condensation of membranes in suspensions. The distinct functional levels corresponding to different reaction buffers can be reproduced even after many buffer exchanges over 14 days, confirming the stability and reproducibility of the membrane-particle hybrid reactors.

The synthesis, structural characterization, electrochemistry and luminescence properties of a series of new yttrium and europium(+3) alkoxides bearing thiophene moieties are presented. The yttrium compounds were obtained by the reaction between Y[N(SiMe3)2]3 and the tertiary alcohols HO–C(C16H13S) (2), HO–C(C17H15S) (3), HO–C(C14H11S2) (4) and HO–C(C16H13S) (5) in thf or in a mixture of toluene and pyridine. The X-ray crystal diffraction measurements show a five-coordinated yttrium atom in distorted trigonal-bipyramidal geometry. The metal centres are surrounded by threemethoxido ligands in equatorial positions and two tetrahydrofuran [for {Y[OC(C16H13S)]3(thf)2}·toluene (8), {Y[OC(C17H15S)]3(thf)2}·toluene (10) and {Y[OC(C14H11S2)]3(thf)2}·1/2 toluene (12)] or two pyridine [for {Y[OC(C16H13S)]3(py)2}·toluene (9) and {Y[OC(C17H15S)]3(py)2}·toluene (11)] molecules in axial positions. The compounds Y[OC(C14H11S2)]3(py)2 (13) and Y[OC(C16H13S)]3(py)2 (14) were identified by NMR spectroscopy. In addition, a novel europium(+3) alkoxide {Eu[OC(C4H3S)3]3(thf)3}·thf (15) was synthesized by the reaction between Eu[N(SiMe3)2]3 and the tertiary alcohol HO–C(C4H3S)3 (1) in thf. The molecular structure of this compound reveals an approximately octahedral coordination sphere around the europium(+3) metal centre with three methoxido ligands and three facially arranged tetrahydrofuran molecules. The cyclic voltammograms of the yttrium alkoxides indicate that the electrochemical properties are essentially dominated by the organic ligands. The electrochemical properties of {Eu[OC(C4H3S)3]3(thf)3}·thf (15) are dominated by the oxidation of the thienyl moieties and in addition a reduction wave due to the reduction of Eu3+ to Eu2+ is visible. In comparison to the carbinols, the oxidation peak potentials of the thienyl units for the yttrium and europium(3+) alkoxides are marginally shifted towards higher values. The emission spectra of the carbinols and their derived yttrium compounds display broad bands attributed to the π*→π transitions of the aromatic ligands. Luminescence studies performed on compound 15 reveal the typical f–f transitions of the Eu3+ ions and suggest that an energy transfer from the ligand to the metal atom operates.

Insolubility is one of the possible functions of proteins involved in biomineralization, which often limits their native purification. This becomes a major problem especially when recombinant expression systems are required to obtain larger amounts. For example, the mollusc shell provides a rich source of unconventional proteins, which can interfere in manifold ways with different mineral phases and interfaces. Therefore, the relevance of such proteins for biotechnological processes is still in its infancy. Here we report a simple and reproducible purification procedure for a GFP-tagged lectin involved in biomineralization, originally isolated from mother-of-pearl in abalone shells. An optimization of E. coli host cell culture conditions was the key to obtain reasonable yields and high degrees of purity by using simple one-step affinity chromatography. We identified a dual functional role for the GFP domain when it became part of a mineralizing system in vitro. First, the GFP domain improved the solubility of an otherwise insoluble protein, in this case recombinant perlucin derivatives. Second, GFP inhibited calcium carbonate precipitation in a concentration dependent manner. This was demonstrated here using a simple bulk assay over a time period of 400 seconds. At concentrations of 2 mg/ml and higher, the inhibitory effect was observed predominantly for HCO3−as the first ionic interaction partner, but not necessarily for
Ca2+. The interference of GFP-tagged perlucin derivatives with the precipitation of calcium carbonate generated different types of GFP-fluorescent composite calcite crystals. GFP-tagging offers therefore a genetically tunable tool to gently modify mechanical and optical properties of synthetic biocomposite minerals.

The size, morphology and species-specific texture of mollusc shell biominerals is one of the unresolved questions in nature. In search of molecular control principles, chitin has been identified by Weiner and Traub (FEBS Lett. 1980, 111 : 311-316) as one of the organic compounds with a defined co-organization with mineral phases. Chitin fibers can be aligned with certain mineralogical axes of crystalline calcium carbonate in a speciesspecific manner. These original observations motivated the functional characterization of chitin forming enzymes in molluscs. The full-length cDNA cloning of mollusc chitin synthases identified unique myosin domains as part of the biological control system. The potential impact of molecular motors and other conserved domains of these complex transmembrane enzymes on the evolution of shell biomineralization is investigated and discussed in this article.

High power electrochemical double layer capacitors (also called supercapacitors) rely on highly conductive electrode materials with a large specific surface area, which is easily accessible for ions. Exohedral materials with a large ion-accessible outer surface and little or no porosity within the particles are particularly attractive for supercapacitor electrodes because they decrease mass transport limitations and enable very high charge/discharge rates. This study focuses on the investigation of charge induced expansion effects of spherical exohedral carbons, that is, onion-like carbons (OLC, diameter: 5–7 nm) and carbon black (diameter: ≈40 nm). Employing electrochemical in-situ dilatometry we studied the expansion behavior within ±1 V potential window versus carbon in an organic electrolyte (tetraethylammonium-tetrafluoroborate in acetonitrile). The expansion had a very small amplitude (<0.2% at ±0.08 C·m-2 accumulated charge; i.e., approximately ±1 V versus carbon) and was fully reversible. This was explained by ion adsorption on the exohedral carbons. Molecular dynamics (MD) simulations were employed to calculate the solvation shell of the respective cation and anion and the results were used to further evaluate the measured expansion. In summary, the experiments and simulations revealed that ion intercalation or ion sieving, which are commonly found in microporous (endohedral) carbons, were absent. Finally, low sweep rates resulted in a slight electrode compaction on a cycle-by-cycle basis, which can be explained by charge-induced restructuring of the nanoparticle network.

Sierpinski carbon: Macroporous carbide-derived carbon monoliths (DUT-38) were synthesized starting from SiC-PolyHIPEs, resulting in a hierarchical micro-, meso-, and macroporous structure. The high specific surface area and high macropore volume renders PolyHIPE-CDC an excellent adsorbent combining high storage capacity with excellent adsorption rates in gas storage and air filtration.