Publikationen

The study of the key parameters impacted surface-assisted laser desorption/ionization-mass spectrometry is of broad interest. In previous studies, it has been shown that surface-assisted laser desorption/ionization-mass spectrometry is a complex process depending on multiple factors. In the presented study, we showed that neither porosity, light absorbance nor surface hydrophobicity alone influence the enhancement phenomena observed from the hybrid metal-semiconductor complexes versus individual targets, but small changes in the analyte attaching to the target significantly affect laser desorption ionization-efficiency. By means of Raman spectroscopy and scanning electron microscopy, it was revealed that the formation of an amorphous analyte layer after drying on a solid substrate was essential for the enhanced laser desorption ionization-signal observed from the hybrid metal-semiconductor targets, and the crystallization properties of the analyte appeared as a function of the substrate. Obtained results were used for the screening of regular and lactose-free milk samples through the hybrid metal-semiconductor target. Copyright © 2016 John Wiley & Sons, Ltd.

The MicroJet reactor technique is an excellent continuous method to produce spherical and homogeneous organically modified silica (ORMOSIL) particles in a large scale (10-15 g min-1). We applied this method to manufacture polyorganosilsesquioxanes with different ratios of phenyl and vinyl functional groups, which were later pyrolyzed to obtain silicon oxycarbides. Such polymer-derived ceramic (PDC) materials are highly suited as precursor for carbide-derived carbon (CDC) synthesis. Chlorine etching of PDC at high temperatures removed silicon and oxygen, yielding the formation of nanoporous carbon. Pure poly(phenyl-silsesquioxane) spheres lost their shape during the thermal process by undergoing further condensation reactions. Yet, the spherical shape was conserved during thermal processing after adding vinyl functionalities. The ratio of vinyl and phenyl functionalities controlled the pore structure and the total CDC yield, enabling an increase from 2 mass% to 22 mass%. The total pore volume varied between 1.3-2.1 cm3 g-1 and the specific surface area between 2014-2114 m2 g-1. The high surface area and large pore volume makes these materials attractive for high power supercapacitor electrodes. The specific capacitance of the best sample at low rates in 1 M tetraethylammonium tetrafluoroborate in acetonitrile was 116 F g-1 (at 5 mA g-1) and still 80 F g-1 at very high rates (at 100 A g-1).

Water-soluble shape-persistent cyclodextrin (CD) polymers with amino-functionalized end groups were prepared starting from diacetylene-modified cyclodextrin monomers by a combined Glaser coupling/click chemistry approach. Structural perfection of the neutral CD polymers and inclusion complex formation with ditopic and monotopic guest molecules were proven by MALDI–TOF and UV–vis measurements. Small-angle neutron and X-ray (SANS/SAXS) scattering experiments confirm the stiffness of the polymer chains with an apparent contour length of about 130 Å. Surface modification of planar silicon wafers as well as AFM tips was realized by covalent bound formation between the terminal amino groups of the CD polymer and a reactive isothiocyanate–silane monolayer. Atomic force measurements of CD polymer decorated surfaces show enhanced supramolecular interaction energies which can be attributed to multiple inclusion complexes based on the rigidity of the polymer backbone and the regular configuration of the CD moieties. Depending on the geometrical configuration of attachment anisotropic adhesion characteristics of the polymer system can be distinguished between a peeling and a shearing mechanism.

The authors develop a protective transparent coating of aluminum oxide through direct oxidation of aluminum-coated glass. Aluminum coatings are deposited on low-iron glass substrates using a physical deposition method and then oxidized at different temperatures. A uniform nano-porous structure with grain sizes of approximately 30–80 nm is observed. X-ray diffraction, TEM images, and EDX analysis indicate the formation of crystalline γ-Al2O3, Si, and stishovite-SiO2 as a result of interdiffusion. The samples treated at different temperatures have hardness values ranging from 5 to 9 H, which is within the desirable range for industrial scratch-resistant coatings. The optical transmission of around 75–85% at visible wavelengths makes the proposed technique useful for the design of protective transparent coatings.

Coating on large surfaces is a critical issue in both academic studies and industrial production. This work proposes a novel method of coating a large flat substrate (50 × 100 cm2) via a wet chemical process using a very small amount (20 ml) of coating solution. The sol material consisted of surface-modified silicon dioxide (SiO2) nanoparticles (10–30 nm), which have the optimal antireflective (AR) function in the visible spectral range for thin films with a thickness ranging from 110 to 120 nm. Ellipsometry results demonstrate a homogeneous thickness of the AR coating on glass (109.4 ± 2.7 nm). A deviation of less than 3% over a large coated surface was observed. Crack-free coatings with homogeneous morphology on the surface of the coatings were observed using scanning electron microscopy. The AR effect was confirmed with UV–vis measurements, with an average transmittance of 91.1% and 94.7%, respectively, in visible wavelengths for the one-sided and double-sided AR coatings (in comparison to 88% for uncoated glass).

There is great technological interest in elucidating the effect of particle size on the luminescence efficiency of doped rare earth oxides. This study demonstrates unambiguously that there is a size effect and that it is not dependent on the calcination temperature. The Y2O3:Eu and Gd2O3:Eu particles used in this study were synthesized using wet chemistry to produce particles ranging in size between 7 nm and 326 nm and a commercially available phosphor. These particles were characterized using three excitation methods: UV light at 250 nm wavelength, electron beam at 10 kV, and X-rays generated at 100 kV. Regardless of the excitation source, it was found that with increasing particle diameter there is an increase in emitted light. Furthermore, dense particles emit more light than porous particles. These results can be explained by considering the larger surface area to volume ratio of the smallest particles and increased internal surface area of the pores found in the large particles. For the small particles, the additional surface area hosts adsorbates that lead to non-radiative recombination, and in the porous particles, the pore walls can quench fluorescence. This trend is valid across calcination temperatures and is evident when comparing particles from the same calcination temperature.

Introducing novel shapes to particulate carrier systems adds unique features to modern drug and gene delivery. Depending on the route of administration, particle geometry can influence deposition and fate within biological environments. In this work, a template-assisted engineering technique is applied, providing full control of size and shape in the preparation of aspherical, nanostructured microparticles. Based on the interconnection of nanoparticles, stabilized by a functional layer-by-layer (LbL) coating, the resulting cylindrical micrometer architecture is especially qualified for pulmonary delivery. Designed as gene delivery system, plasmid-DNA (pCMV-luciferase) and branched polyethylenimine are used to reach both structural integrity of the carrier system and delivery of genes into the cells of interest. Due to their size, particles are exclusively taken up by phagocytes, which also adds a targeting effect to the introduced system. The luciferase expression is demonstrated in macrophages showing increasing levels over a time period of at least 7 d. Furthermore, it is shown for the first time that the expression is depending on the LbL design. From in vivo experiments, corresponding luciferase expression is observed in mice alveolar macrophages. Combining site specific transport with the possibility of genetically engineering immunocompetent phagocytes, the presented system offers promising potential to improve applications for cell-based immunotherapy.

Iron is an essential growth determinant for plants, and plants acquire this micronutrient in amounts they need in their environment. Plants can increase iron uptake in response to a regulatory transcription factor cascade. Arabidopsis thaliana serves as model plant to identify and characterize iron regulation genes. Here, we show that overexpression of subgroup Ib bHLH transcription factor bHLH039 (39Ox) caused constitutive iron acquisition responses, which resulted in enhanced iron contents in leaves and seeds. Transcriptome analysis demonstrated that 39Ox plants displayed simultaneously gene expression patterns characteristic of iron deficiency and iron stress signaling. Thereby, we could dissect iron deficiency response regulation. The transcription factor FIT, which is required to regulate iron uptake, was essential for the 39Ox phenotype. We provide evidence that subgroup Ib transcription factors are involved in FIT transcriptional regulation. Our findings pose interesting questions to the feedback control of iron homeostasis.

Summary Engineering of biomaterials with specific biological properties has gained momentum as a means to control stem cell behavior. Here, we address the effect of bifunctionalized hydrogels comprising polylysine (PL) and a 19-mer peptide containing the laminin motif IKVAV (IKVAV) on embryonic and adult neuronal progenitor cells under different stiffness regimes. Neuronal differentiation of embryonic and adult neural progenitors was accelerated by adjusting the gel stiffness to 2 kPa and 20 kPa, respectively. While gels containing IKVAV or PL alone failed to support long-term cell adhesion, in bifunctional gels, IKVAV synergized with PL to promote differentiation and formation of focal adhesions containing β1-integrin in embryonic cortical neurons. Furthermore, in adult neural stem cell culture, bifunctionalized gels promoted neurogenesis via the expansion of neurogenic clones. These data highlight the potential of synthetic matrices to steer stem and progenitor cell behavior via defined mechano-adhesive properties.

Biomaterials for cell culture allowing simple and quantitative presentation of instructive cues enable rationalization of the interplay between cells and their surrounding microenvironment. Poly(acrylamide) (PAAm) hydrogels are popular 2D-model substrates for this purpose. However, quantitative and reproducible biofunctionalization of PAAm hydrogels with multiple ligands in a trustable, controlled, and independent fashion is not trivial. Here, we describe a method for bifunctional modification of PAAm hydrogels with thiol- and amine- containing biomolecules with controlled densities in an independent, orthogonal manner. We developed copolymer networks of AAm with 9% acrylic acid and 2% N-(4-(5-(methylsulfonyl)-1,3,4-oxadiazol-2-yl)phenyl)acrylamide. The covalent binding of thiol- and amine-containing chromophores at tunable concentrations was demonstrated and quantified by UV spectroscopy. The morphology, mechanical properties, and homogeneity of the copolymerized hydrogels were characterized by scanning electron microscopy, dynamic mechanical analysis, and confocal microscopy studies. Our copolymer hydrogels were bifunctionalized with polylysine and a laminin-mimetic peptide using the specific chemistries. We analyzed the effect of binding protocol of the two components in the maturation of cultured postmitotic cortical neurons. Our substrates supported neuronal attachment, proliferation, and neuronal differentiation. We found that neurons cultured on our hydrogels bifunctionalized with ligand-specific chemistries in a sequential fashion exhibited higher maturation at comparable culture times than using a simultaneous bifunctionalization strategy, displaying a higher number of neurites, branches, and dendritic filopodia. These results demonstrate the relevance of quantitative and optimized coupling chemistries for the performance of simple biomaterials and with sensitive cell types.