2016, Stiller, M., Barzola-Quiquia, J., Esquinazi, P., Spemann, D., Meijer, J., Lorenz, M., Grundmann, M.

The temperature and field dependence of the magnetization of epitaxial, undoped anatase TiO2 thin films on SrTiO3 substrates was investigated. Low-energy ion irradiation was used to modify the surface of the films within a few nanometers, yet with high enough energy to produce oxygen and titanium vacancies. The as-prepared thin film shows ferromagnetism which increases after irradiation with low-energy ions. An optimal and clear magnetic anisotropy was observed after the first irradiation, opposite to the expected form anisotropy. Taking into account the experimental parameters, titanium vacancies as di-Frenkel pairs appear to be responsible for the enhanced ferromagnetism and the strong anisotropy observed in our films. The magnetic impurities concentrations was measured by particle-induced X-ray emission with ppm resolution. They are ruled out as a source of the observed ferromagnetism before and after irradiation.

2013, De Pablos-Martín, A., Muñoz, F., Mather, G.C., Patzig, C., Bhattacharyya, S., Jinschek, J.R., Höche, T., Durán, A., Pascual, M.J.

Nanocrystallisation of the cubic and hexagonal polymorphs of KLaF 4 in a 70SiO2-7Al2O3-16K 2O-7LaF3 (mol%) glass has been achieved by heat treatment above the glass transition temperature. For treatment at 580°C, only the cubic structure crystallises, with a maximum crystallite size of ~9 nm. At higher temperatures, crystallisation of the hexagonal structure also takes place. The crystallisation process has been analysed using several thermal and structural techniques and is revealed to occur from a constant number of nuclei. The formation of a viscous barrier which inhibits further crystal growth and limits the crystal size to the nanometric range is observed. The title materials doped with lanthanide ions may be good candidates for optical applications.

2014, Asenova, I., Manova, D., Mändl, S.

In this paper we investigate the possibility of incorporating nitrogen into amorphous, photocatalytic TiO2 thin films, prepared at room temperature, during the growth process. The aim is to reduce the bandgap of the UV active thin films. Physical vapor deposition experiments employing a titanium vacuum arc with gas backfill ranging from pure oxygen to pure nitrogen, are carried out. The resulting films are characterized for chemical composition, phase composition, optical properties and hydrophilicity in order to determine a correlation between gas composition and thin film properties. The experimental results point that a visible change in the band structure of the deposited layers is achieved.

2012, Lorenz, P., Ehrhardt, M., Zimmer, K.

Laser-induced front side etching (LIFE) is a method for the nanometer-precision structuring of dielectrics, e.g. fused silica, using thin metallic as well as organic absorber layer attached to the laser-irradiated front side of the sample. As laser source an excimer laser with a wavelength of 248 nm and an pulse duration of 25 ns was used. For sub-μm patterning a phase mask illuminated by the top hat laser beam was projected by a Schwarzschild objective. The LIFE process allows the fabrication of well-defined and smooth surface structures with sub-μm lateral etching regions (Δx < 350 nm) and vertical etching depths from 1 nm to sub-mm.

2014, Buchwald, J., Sarmanova, M., Rauschenbach, B., Mayr, S.G.

The mechanical properties of surfaces and nanostructures deviate from their bulk counterparts due to surface stress and reduced dimensionality. Experimental indentation-based techniques present the challenge of measuring these effects, while avoiding artifacts caused by the measurement technique itself. We performed a molecular dynamics study to investigate the mechanical properties of a GaN step of only a few lattice constants step height and scrutinized its applicability to indentation experiments using a finite element approach (FEM). We show that the breakdown of half-space symmetry leads to an "artificial" reduction of the elastic properties of comparable lateral dimensions which overlays the effect of surface stress. Contact resonance atomic force microscopy (CR-AFM) was used to compare the simulation results with experiments.

2010, Manova, D., Gerlach, J.W., Mändl, S.

One important recent trend in deposition technology is the continuous expansion of available processes towards higher ion assistance with the subsequent beneficial effects to film properties. Nowadays, a multitude of processes, including laser ablation and deposition, vacuum arc deposition, ion assisted deposition, high power impulse magnetron sputtering and plasma immersion ion implantation, are available. However, there are obstacles to overcome in all technologies, including line-of-sight processes, particle contaminations and low growth rates, which lead to ongoing process refinements and development of new methods. Concerning the deposited thin films, control of energetic ion bombardment leads to improved adhesion, reduced substrate temperatures, control of intrinsic stress within the films as well as adjustment of surface texture, phase formation and nanotopography. This review illustrates recent trends for both areas; plasma process and solid state surface processes. © 2010 by the authors.

2014, Raz, Y., Adler, J., Vogel, A., Scheidt, H.A., Häupl, T., Abel, B., Huster, D., Miller, Y.

Tau is a microtubule-associated protein and is involved in microtubule assembly and stabilization. It consists of four repeats that bind to the microtubule. The ΔK280 deletion mutation in the tau R2 repeat region is directly associated with the development of the frontotemporal dementia parkinsonism linked to chromosome 17 (FTDP-17). This deletion mutation is known to accelerate tau R2 repeat aggregation. However, the secondary and the tertiary structures of the self-assembled ΔK280 tau R2 repeat mutant aggregates are still controversial. Moreover, it is unclear whether extensions by one residue in the N- or the C-terminus of this mutant can influence the secondary or the tertiary structure. Herein, we combine solid-state NMR, atomic force microscopy, electron microscopy and all-atom explicit molecular dynamics simulations to investigate the effects of the deletion mutation and the N- and the C-terminal extension of this mutant on the structure. Our main findings show that the deletion mutation induces the formation of small aggregates, such as oligomers, and reduces the formation of fibrils. However, the extensions in the N- or the C-terminus revealed more fibril formation than small aggregates. Further, in the deletion mutation only one structure is preferred, while the N- and the C-terminal extensions strongly lead to polymorphic states. Finally, our broad and combined experimental and computational techniques provide direct structural information regarding ΔK280 tau R2 repeat mutant aggregates and their extensions in the N- and C-terminii by one residue.

2014, Hennes, M., Lotnyk, A., Mayr, S.G.

Magnetically anisotropic as well as magnetic core-shell nanoparticles (CS-NPs) with controllable properties are highly desirable in a broad range of applications. With this background, a setup for the synthesis of heterostructured magnetic core-shell nanoparticles, which relies on (optionally pulsed) DC plasma gas condensation has been developed. We demonstrate the synthesis of elemental nickel nanoparticles with highly tunable sizes and shapes and Ni@Cu CS-NPs with an average shell thickness of 10 nm as determined with scanning electron microscopy, high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy measurements. An analytical model that relies on classical kinetic gas theory is used to describe the deposition of Cu shell atoms on top of existing Ni cores. Its predictive power and possible implications for the growth of heterostructured NP in gas condensation processes are discussed.

2014, Jahangiri, E., Reichelt, S., Thomas, I., Hausmann, K., Schlosser, D., Schulze, A.

The versatile oxidase enzyme laccase was immobilized on porous supports such as polymer membranes and cryogels with a view of using such biocatalysts in bioreactors aiming at the degradation of environmental pollutants in wastewater. Besides a large surface area for supporting the biocatalyst, the aforementioned porous systems also offer the possibility for simultaneous filtration applications in wastewater treatment. Herein a "green" water-based, initiator-free, and straightforward route to highly reactive membrane and cryogel-based bioreactors is presented, where laccase was immobilized onto the porous polymer supports using a water-based electron beam-initiated grafting reaction. In a second approach, the laccase redox mediators 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and syringaldehyde were cross-linked instead of the enzyme via electron irradiation in a frozen aqueous poly(acrylate) mixture in a one pot set-up, yielding a mechanical stable macroporous cryogel with interconnected pores ranging from 10 to 50 μm in size. The membranes as well as the cryogels were characterized regarding their morphology, chemical composition, and catalytic activity. The reactivity towards waste-water pollutants was demonstrated by the degradation of the model compound bisphenol A (BPA). Both membrane- and cryogel-immobilized laccase remained highly active after electron beam irradiation. Apparent specific BPA removal rates were higher for cryogel-than for membrane-immobilized and free laccase, whereas membrane-immobilized laccase was more stable with respect to maintenance of enzymatic activity and prevention of enzyme leakage from the carrier than cryogel-immobilized laccase. Cryogel-immobilized redox mediators remained functional in accelerating the laccase-catalyzed BPA degradation, and especially ABTS was found to act more efficiently in immobilized than in freely dissolved state.

2016, Gladytz, A., John, T., Gladytz, T., Hassert, R., Pagel, M., Risselada, H.J., Naumov, S., Beck-Sickinger, A.G., Abel, B.

Investigating the adsorption of peptides on inorganic surfaces, on the molecular level, is fundamental for medicinal and analytical applications. Peptides can be potent as linkers between surfaces and living cells in biochips or in implantation medicine. Here, we studied the adsorption process of the positively charged pentapeptide RTHRK, a recently identified binding sequence for surface oxidized silicon, and novel analogues thereof to negatively charged mica surfaces. Homogeneous formation of monolayers in the nano- and low micromolar peptide concentration range was observed. We propose an alternative and efficient method to both quantify binding affinity and follow adhesion behavior. This method makes use of the thermodynamic relationship between surface coverage, measured by atomic force microscopy (AFM), and the concomitant free energy of adhesion. A knowledge-based fit to the autocorrelation of the AFM images was used to correct for a biased surface coverage introduced by the finite lateral resolution of the AFM. Binding affinities and mechanisms were further explored by large scale molecular dynamics (MD) simulations. The combination of well validated MD simulations with topological data from AFM revealed a better understanding of peptide adsorption processes on the atomistic scale. We demonstrate that binding affinity is strongly determined by a peptide's ability to form salt bridges and hydrogen bonds with the surface lattice. Consequently, differences in hydrogen bond formation lead to substantial differences in binding affinity despite conservation of the peptide's overall charge. Further, MD simulations give access to relative changes in binding energy of peptide variations in comparison to a lead compound.