Bond-specific fragmentation of oligopeptides via electronic stopping of swift heavy ions in molecular films.

Highly bond-specific fragmentation of oligopeptides induced by swift heavy ion (SHI) irradiation was investigated by means of mass spectrometry. In pronounced contrast to measurements of samples irradiated with keV ions, oligopeptides which were exposed to 946 MeV Au ions show a high abundance of specific fragments. The highly bond-specific nature of SHI-induced fragmentation is attributed to electronic stopping as the most relevant energy loss mechanism for SHI in the oligopeptide samples in combination with the subsequent coupling between the excited electronic and the atomic subsystem. Fragmentation induced by SHI is observed to be further influenced by the structure of the oligopeptides, suggesting that electronic excitation and/or the electronic-vibrational coupling depend on the details of the molecular structure.

Ion irradiation induced strain and structural changes in LiTaO3perovskite.

LiTaO3crystals irradiated with 3 MeV and 1.162 GeV Au ions were studied by single crystal x-ray diffraction and Raman scattering measurements. The maximum lattice strains after 3 MeV Au ion irradiation to a fluence of 1.2 × 1013 cm-2were 1.2% and 0.6% along thec- anda-/b-axes, respectively. Two effects were observed in 1.162 GeV Au ion irradiated samples: (i) the (0006) and (1120) Bragg peaks were split into doublets, which suggested a subtle structural change due to slight modification of chemical composition; and (ii) the pre-damaged 1.2% lattice strain along thec-axis was relaxed to 0.9% after subsequent irradiation with 1.162 GeV Au ions, while relaxation along thea- orb-axis was not obvious. A distinct change in the Raman spectrum of the 〈0001〉 oriented LiTaO3crystals was observed after 1.162 GeV Au ion irradiation, but no obvious change was observed in the 〈1120〉 oriented samples or in 3 MeV Au ion irradiated samples. Strain and structural changes in crystalline LiTaO3, with or without pre-existing defects, upon ion irradiation are delineated in its responding to inelastic ionization and elastic nuclear collisions.

Etched ion tracks in amorphous SiO2 characterized by small angle x-ray scattering: influence of ion energy and etching conditions.

Small angle x-ray scattering was used to study the morphology of conical structures formed in thin films of amorphous SiO2. Samples were irradiated with 1.1 GeV Au ions at the GSI UNILAC in Darmstadt, Germany, and with 185, 89 and 54 MeV Au ions at the Heavy Ion Accelerator Facility at ANU in Canberra, Australia. The irradiated material was subsequently etched in HF using two different etchant concentrations over a series of etch times to reveal conically shaped etched channels of various sizes. Synchrotron based SAXS measurements were used to characterize both the radial and axial ion track etch rates with unprecedented precision. The results show that the ion energy has a significant effect on the morphology of the etched channels, and that at short etch times resulting in very small cones, the increased etching rate of the damaged region in the radial direction with respect to the ion trajectory is significant.

Bond-Breaking Efficiency of High-Energy Ions in Ultrathin Polymer Films.

Thin films of poly(methyl methacrylate) and poly(vinyl chloride) of different thickness are used to investigate the effect of spatial confinement on the efficiency of bond breaking induced by 2 MeV H^{+} and 2.1 GeV Bi ions. Effective cross sections for oxygen and chlorine loss are extracted for films down to a thickness of about 5 nm and are compared to theoretical estimations based on radial energy density profiles simulated with geant-dna. The cross sections are to a large extent thickness independent, indicating that bond breaking is dominated by short-range processes. This is in contrast to the strongly reduced efficiencies found recently for cratering induced by high-energy ions in similar ultrathin polymer films [Phys. Rev. Lett. 114, 118302 (2015)PRLTAO0031-900710.1103/PhysRevLett.114.118302].

Local structure and defects in ion irradiated KTaO3.

The modification of the local structure in cubic perovskite KTaO3 irradiated with 3 MeV and 1.1 GeV Au ions is studied by Raman and x-ray absorption spectroscopy, complemented by density functional theory (DFT) calculations. In the case of irradiation with 3 MeV Au ions where displacement cascade processes are dominant, the Ta L3-edge x-ray absorption measurements suggest that a peak corresponding to the Ta-O bonds in the TaO6 octahedra splits, which is attributed to the formation of TaK antisite defects that are coupled with oxygen vacancies, V O. This finding is consistent with the DFT calculations. Under irradiation with 1.1 GeV ions, the intense ionization and electronic energy deposition lead to a blue shift and an intensity reduction of active Raman bands. In the case of sequential irradiations, extended x-ray absorption fine structure measurements reveal a decrease in concentration of coupled TaK-V O defects under subsequent irradiation with 1.1 GeV Au ions.

Nanoscale density variations induced by high energy heavy ions in amorphous silicon nitride and silicon dioxide.

The cylindrical nanoscale density variations resulting from the interaction of 185 MeV and 2.2 GeV Au ions with 1.0 µm thick amorphous SiN x :H and SiO x :H layers are determined using small angle x-ray scattering measurements. The resulting density profiles resembles an under-dense core surrounded by an over-dense shell with a smooth transition between the two regions, consistent with molecular-dynamics simulations. For amorphous SiN x :H, the density variations show a radius of 4.2 nm with a relative density change three times larger than the value determined for amorphous SiO x :H, with a radius of 5.5 nm. Complementary infrared spectroscopy measurements exhibit a damage cross-section comparable to the core dimensions. The morphology of the density variations results from freezing in the local viscous flow arising from the non-uniform temperature profile in the radial direction of the ion path. The concomitant drop in viscosity mediated by the thermal conductivity appears to be the main driving force rather than the presence of a density anomaly.

Influence of surface states and size effects on the Seebeck coefficient and electrical resistance of Bi1-xSbx nanowire arrays.

The Seebeck coefficient and electrical resistance of Bi1-xSbx nanowire arrays electrodeposited in etched ion-track membranes have been investigated as a function of wire diameter (40-750 nm) and composition (0 ≤ x ≤ 1). The experimental data reveal a non-monotonic dependence between thermopower and wire diameter for three different compositions. Thus, the thermopower values decrease with decreasing wire diameter, exhibiting a minimum around ∼60 nm. This non-monotonic dependence of the Seebeck coefficient is attributed to the interplay of surface and bulk states. On the one hand, the metallic properties of the surface states can contribute to decreasing the thermopower of the nanostructure with increasing surface-to-volume ratio. On the other hand, for wires thinner than ∼60 nm, the relative increase of the thermopower can be tentatively attributed to the presence of quantum-size effects on both surface and bulk states. These measurements contribute to a better understanding of the interplay between bulk and surface states in nanostructures, and indicate that the decrease of Seebeck coefficient with decreasing diameter caused by the presence of surfaces states can possibly be overcome for even thinner nanowires.

Confinement effects of ion tracks in ultrathin polymer films.

We show direct experimental evidence that radiation effects produced by single MeV heavy ions on a polymer surface are weakened when the length of the ion track in the material is confined into layers of a few tens of nanometers. Deviation from the bulk (thick film) behavior of ion-induced craters starts at a critical thickness as large as ∼40 nm, due to suppression of long-range additive effects of excited atoms along the track. Good agreement was found between the experimental results, molecular dynamic simulations, and an analytical model.

Rectification properties of conically shaped nanopores: consequences of miniaturization.

Nanopores attracted a great deal of scientific interest as templates for biological sensors as well as model systems to understand transport phenomena at the nanoscale. The experimental and theoretical analysis of nanopores has been so far focused on understanding the effect of the pore opening diameter on ionic transport. In this article we present systematic studies on the dependence of ion transport properties on the pore length. Particular attention was given to the effect of ion current rectification exhibited in conically shaped nanopores with homogeneous surface charges. We found that reducing the length of conically shaped nanopores significantly lowered their ability to rectify ion current. However, rectification properties of short pores can be enhanced by tailoring the surface charge and the shape of the narrow opening. Furthermore we analyzed the relationship of the rectification behavior and ion selectivity for different pore lengths. All simulations were performed using MsSimPore, a software package for solving the Poisson-Nernst-Planck (PNP) equations. It is based on a novel finite element solver and allows for simulations up to surface charge densities of -2 e per nm(2). MsSimPore is based on 1D reduction of the PNP model, but allows for a direct treatment of the pore with bulk electrolyte reservoirs, a feature which was previously used in higher dimensional models only. MsSimPore includes these reservoirs in the calculations, a property especially important for short pores, where the ionic concentrations and the electric potential vary strongly inside the pore as well as in the regions next to the pore entrance.

SAXS investigations of the morphology of swift heavy ion tracks in α-quartz.

The morphology of swift heavy ion tracks in crystalline α-quartz was investigated using small angle x-ray scattering (SAXS), molecular dynamics (MD) simulations and transmission electron microscopy. Tracks were generated by irradiation with heavy ions with energies between 27 MeV and 2.2 GeV. The analysis of the SAXS data indicates a density change of the tracks of ~2 ± 1% compared to the surrounding quartz matrix for all irradiation conditions. The track radii only show a weak dependence on the electronic energy loss at values above 17 keV nm(-1), in contrast to values previously reported from Rutherford backscattering spectrometry measurements and expectations from the inelastic thermal spike model. The MD simulations are in good agreement at low energy losses, yet predict larger radii than SAXS at high ion energies. The observed discrepancies are discussed with respect to the formation of a defective halo around an amorphous track core, the existence of high stresses and/or the possible presence of a boiling phase in quartz predicted by the inelastic thermal spike model.

Tailoring of keV-ion beams by image charge when transmitting through rhombic and rectangular shaped nanocapillaries.

We report on an unexpected effect of tailoring transmission profiles of Ne(7+) ions through nanocapillaries of rhombic and rectangular cross sections in mica. We find that capillaries of rhombic cross sections produce rectangular shaped ion transmission profiles and, vice versa, that capillaries of rectangular geometry give a rhombic beam shape. This shaping effect only occurs for transmitted ions and is absent for the small fraction of neutralized particles. The experimental findings and simulations of the projectile trajectories give clear evidence that the observed effect is due to the image forces experienced by the transmitting ions. This novel beam shaping mechanism suggests applications for the guiding, focusing, and shaping of ion beams.

Optical spectroscopy study of damage induced in 4H-SiC by swift heavy ion irradiation.

Single crystals of 4H-SiC were irradiated with swift heavy ions (332 MeV Ti, 106 MeV Pb and 2.7 GeV U) in the electronic energy loss regime. The resulting damage was investigated with UV-visible optical absorption spectroscopy and micro-Raman spectroscopy. The evolution of the Raman data with fluence shows an accumulation of isolated point defects without amorphization of the material and a partial recrystallization of the structure, but only at the lowest fluence. Furthermore, the longitudinal optical phonon-plasmon coupling mode disappears upon irradiation, suggesting a strong perturbation of the electronic structure. This evolution is consistent with the optical bandgap decrease and the Urbach edge broadening that was also previously observed for the irradiation with 4 MeV Au ions.

Nanopores in track-etched polymer membranes characterized by small-angle x-ray scattering.

Nanochannels and nanowires with diameters ranging from 30 to 400 nm were produced by etching ion tracks in thin polyarylate and polycarbonate foils. The shape and the size distribution of dry and wet nanochannels, as well as of nanowires grown therein, were examined by small-angle x-ray scattering. The x-ray intensity as a function of the scattering vector exhibits pronounced oscillations showing that both the channels and the wires have a highly cylindrical geometry and a very narrow size distribution. UV exposure before chemical etching significantly improves the monodispersity of the nanopores. For fixed etching conditions, the scattering patterns provide evidence that the diameter of dry and water-filled channels as well as for embedded nanowires are identical, demonstrating that the pores in the polymer are completely filled.

Spatially resolved nuclear spin relaxation, electron spin relaxation and light absorption in swift heavy ion irradiated LiF crystals.

Spatially resolved (19)F and (7)Li spin-lattice relaxation rates are measured for LiF single crystals after irradiation with two kinds of swift heavy ions ((12)C of 133 MeV and (208)Pb of 1.78 GeV incident energy). Like in earlier studies on (130)Xe and (238)U irradiated LiF crystals, we found a strong enhancement of the nuclear spin-lattice relaxation rate within the ion penetration depth and a slight--but still significant--enhancement beyond. By evaluating the nuclear relaxation rate enhancement within the ion range after irradiation with different projectiles, a universal relationship between the spin-lattice relaxation rate and the dose is deduced. The results of accompanying X-band electron paramagnetic resonance relaxation measurements and optical absorption spectroscopy are included in a physical interpretation of this relationship. Also the reason for the enhanced relaxation rate beyond the ion range is further discussed.

[Fencing injuries and stress injuries in modern fencing sport- a questionnaire evaluation]. / Verletzungen und Uberlastungsschäden im modernen Fechtsport - eine Fragebogenerhebung.

Overload injuries and trauma caused by athletic activities in elite and non-elite fencers may be related to a variety of risk factors. The aim of the present study was to investigate the sport specific pattern of injuries in junior and adult elite fencers and potential causative factors for the specific injuries. Questionnaires were distributed in fencing clubs and competitions. A total of 180 athletes participated with 107 being elite fencers (55 male, 52 female) and 73 advanced fencers (77 male, 26 female). Injuries and pain could be ascertained in 167 fencers (92.8 %), and could be related to their activities in competitive fencing.

Fine structure in swift heavy ion tracks in amorphous SiO2.

We report on the observation of a fine structure in ion tracks in amorphous SiO2 using small angle x-ray scattering measurements. Tracks were generated by high energy ion irradiation with Au and Xe between 27 MeV and 1.43 GeV. In agreement with molecular dynamics simulations, the tracks consist of a core characterized by a significant density deficit compared to unirradiated material, surrounded by a high density shell. The structure is consistent with a frozen-in pressure wave originating from the center of the ion track as a result of a thermal spike.

Flexible fluidic microchips based on thermoformed and locally modified thin polymer films.

This paper presents a fundamentally new approach for the manufacturing and the possible applications of lab on a chip devices, mainly in the form of disposable fluidic microchips for life sciences applications. The new technology approach is based on a novel microscale thermoforming of thin polymer films as core process. The flexibility not only of the semi-finished but partly also of the finished products in the form of film chips could enable future reel to reel processes in production but also in application. The central so-called 'microthermoforming' process can be surrounded by pairs of associated pre- and postprocesses for micro- and nanopatterned surface and bulk modification or functionalisation of the formed films. This new approach of microscale thermoforming of thin polymer film substrates overlaid with a split local modification of the films is called 'SMART', which stands for 'substrate modification and replication by thermoforming'. In the process, still on the unformed, plane film, the material modifications of the preprocess define the locations where later, then on the spatially formed film, the postprocess generates the final local modifications. So, one can obtain highly resolved modification patterns also on hardly accessible side walls and even behind undercuts. As a first application of the new technology, we present a flexible chip-sized scaffold for three dimensional cell cultivation in the form of a microcontainer array. The spatially warped container walls have been provided with micropores, cell adhesion micropatterns and thin film microelectrodes.

Spatially resolved characterization of Xe ion irradiated LiF crystals using static field gradient NMR.

Spatially resolved (19)F and (7)Li nuclear magnetic resonance (NMR) spin-lattice relaxation rates have been measured in LiF crystals irradiated with 1.44 GeV Xe ions at fluences from 10(10) to 10(12) ions cm(-2). In addition, the F-centre concentration has been measured by optical absorption spectroscopy and the concentration of paramagnetic centres by electron paramagnetic resonance (EPR). Within the ion range, the relaxation rate turns out to increase linearly with the concentration of paramagnetic centres but super-linearly with the F-centre concentration. Beyond the ion range, the relaxation rate is still significantly enhanced compared to non-irradiated LiF.

3D tissue culture substrates produced by microthermoforming of pre-processed polymer films.

We describe a new technology based on thermoforming as a microfabrication process. It significantly enhances the tailoring of polymers for three dimensional tissue engineering purposes since for the first time highly resolved surface and bulk modifications prior to a microstructuring process can be realised. In contrast to typical micro moulding techniques, the melting phase is avoided and thus allows the forming of pre-processed polymer films. The polymer is formed in a thermoelastic state without loss of material coherence. Therefore, previously generated modifications can be preserved. To prove the feasibility of our newly developed technique, so called SMART = Substrate Modification And Replication by Thermoforming, polymer films treated by various polymer modification methods, like UV-based patterned films, and films modified by the bombardment with energetic heavy ions, were post-processed by microthermoforming. The preservation of locally applied specific surface and bulk features was demonstrated e.g. by the selective adhesion of cells to patterned microcavity walls.

[Molds in air-sampling and detection. Validation of sampling methods to verify molds in air]. / Schimmelpilze in Luft-Probenahme und Bestimmung. Validierung von Probenahmeverfahren zur Bestimmung von Schimmelpilzen in Luft.

The assessment of mold concentrations in air samples requires generally accepted evaluation criteria. It is not possible to derive guideline values based on risk assessment. Background concentrations are therefore used as the basis for the assessment of measured concentrations. The assessment criteria established by the Federal Environmental Agency in Berlin and by the State Health Agency of Baden-Wurttemberg are founded on the experience of some laboratories. The general application of these criteria is only meaningful if validated and generally applied methods of analysis are used. Until now, laboratories have been using many different methods for sampling and detection of culturable molds and total spore counts in air. In this study, different steps for sampling by impaction or filtration are validated. The results presented will contribute to standardization of sampling and detection of molds in air.