Dendritic hPG-amid-C18-mPEG core-multishell nanocarriers (CMS) represent a novel class of unimolecular micelles that hold great potential as drug transporters, e. g., to facilitate topical therapy in skin diseases. Atopic dermatitis is among the most common inflammatory skin disorders with complex barrier alterations which may affect the efficacy of topical treatment. Here, we tested the penetration behavior and identified target structures of unloaded CMS after topical administration in healthy mice and in mice with oxazolone-induced atopic dermatitis. We further examined whole body distribution and possible systemic side effects after simulating high dosage dermal penetration by subcutaneous injection. Following topical administration, CMS accumulated in the stratum corneum without penetration into deeper viable epidermal layers. The same was observed in atopic dermatitis mice, indicating that barrier alterations in atopic dermatitis had no influence on the penetration of CMS. Following subcutaneous injection, CMS were deposited in the regional lymph nodes as well as in liver, spleen, lung, and kidney. However, in vitro toxicity tests, clinical data, and morphometry-assisted histopathological analyses yielded no evidence of any toxic or otherwise adverse local or systemic effects of CMS, nor did they affect the severity or course of atopic dermatitis. Taken together, CMS accumulate in the stratum corneum in both healthy and inflammatory skin and appear to be highly biocompatible in the mouse even under conditions of atopic dermatitis and thus could potentially serve to create a depot for anti-inflammatory drugs in the skin.

This work presents a systematic study on the effects of strain rate and surface cracks on the mechanical properties and behaviour of Balmoral Red granite. The tensile behaviour of the rock was studied at low and high strain rates using Brazilian disc samples. Heat shocks were used to produce samples with different amounts of surface cracks. The surface crack patterns were analysed using optical microscopy, and the complexity of the patterns was quantified by calculating the fractal dimensions of the patterns. The strength of the rock clearly drops as a function of increasing fractal dimensions in the studied strain rate range. However, the dynamic strength of the rock drops significantly faster than the quasi-static strength, and, because of this, also the strain rate sensitivity of the rock decreases with increasing fractal dimensions. This can be explained by the fracture behaviour and fragmentation during the dynamic loading, which is more strongly affected by the heat shock than the fragmentation at low strain rates.

Can the statistical properties of single-electron transfer events be correctly predicted within a common equilibrium ensemble description? This fundamental in nanoworld question of ergodic behavior is scrutinized within a very basic semi-classical curve-crossing problem. It is shown that in the limit of non-adiabatic electron transfer (weak tunneling) well-described by the Marcus-Levich-Dogonadze (MLD) rate the answer is yes. However, in the limit of the so-called solvent-controlled adiabatic electron transfer, a profound breaking of ergodicity occurs. Namely, a common description based on the ensemble reduced density matrix with an initial equilibrium distribution of the reaction coordinate is not able to reproduce the statistics of single-trajectory events in this seemingly classical regime. For sufficiently large activation barriers, the ensemble survival probability in a state remains nearly exponential with the inverse rate given by the sum of the adiabatic curve crossing (Kramers) time and the inverse MLD rate. In contrast, near to the adiabatic regime, the single-electron survival probability is clearly non-exponential, even though it possesses an exponential tail which agrees well with the ensemble description. Initially, it is well described by a Mittag-Leffler distribution with a fractional rate. Paradoxically, the mean transfer time in this classical on the ensemble level regime is well described by the inverse of the nonadiabatic quantum tunneling rate on a single particle level. An analytical theory is developed which perfectly agrees with stochastic simulations and explains our findings.

In many laser based ionization techniques with a subsequent drift time separation, the laser pulse generating the ions is considered as the start time to. Therefore, an accurate temporal definition of this event is crucial for the resolution of the experiments. In this contribution, the laser induced plume dynamics of liquids evaporating into atmospheric pressure are visualized for two distinctively different laser pulse widths, Delta t = 6 nanoseconds and Delta tau = 280 microseconds. For ns-pulses the expansion of the generated vapour against atmospheric pressure is found to lead to turbulences inside the gas phase. This results in spatial and temporal broadening of the nascent clouds. A more equilibrated expansion, without artificial smearing of the temporal resolution can, in contrast, be observed to follow mu s-pulse excitation. This leads to the counterintuitive finding that longer laser pulses results in an increased temporal vapour formation definition. To examine if this fume expansion also eventually results in a better definition of ion formation, the nascent vapour plumes were expanded into a linear drift tube ion mobility spectrometer (IMS). This time resolved detection of ion formation corroborates the temporal broadening caused by collisional impeding of the supersonic expansion at atmospheric pressure and the overall better defined ion formation by evaporation with long laser pulses. A direct comparison of the observed results strongly suggests the coexistence of two individual ion formation mechanisms that can be specifically addressed by the use of appropriate laser sources.

Atmospheric transport is an understudied mechanism for leaf wax hydrogen isotope applications that contributes to mobilizing and depositing these compounds on the surface of the Earth. While previous efforts have identified the importance of atmospheric leaf wax deposition in remote marine locations, the processes are not well constrained on land in temperate latitudes where lakes are common and sedimentary leaf wax hydrogen isotope values are an attractive tool for understanding past precipitation changes. This work presents results from a field study that was conducted in 2010 and 2011 at Hainich National Park, Germany in order to evaluate the quantity and sources of leaf waxes in the atmosphere. Aerosols were sampled at approximately weekly intervals inside the forest canopy, and n-alkane distributions and hydrogen isotope values were compared with those from major tree species surrounding the sampling site. Despite sampling in what was expected to be a major production center, the distribution and hydrogen isotope values of atmospheric n-alkanes bore little resemblance to those of the local vegetation. Comparison with local meteorological data and to 10-day and 36-h back air mass trajectories indicated shifting effects of winds and temperature, and that mesoscale transport processes were more important than longrange mechanisms. Back trajectories also highlighted source effects, with easterly winds coinciding with relatively lower leaf wax hydrogen isotope values from more continental regions. These results suggest that leaf wax aerosols average over spatial scales that exceed typical surface catchment areas for small lake systems, even in forested areas, yet that the area over which these compounds are derived is still relatively regional. Depositional fluxes were also estimated in order to assess the potential importance of atmospheric transport to sedimentary archives. Although difficult to constrain, these estimates suggest that atmospheric deposition may be non-negligible for lake systems in cases where inputs from rivers or surface runoff are limited. Together, these observations provide new insights on how leaf waxes from different sources are integrated during aeolian transport and the spatial scales over which these processes occur.

We analyze the effects of covalent interactions in Ni 2p3d resonant inelastic X-ray scattering (RIXS) spectra from aqueous Ni2+ ions and find that the relative RIXS intensities of ligand-to-metal charge-transfer final states with respect to the ligand-field final states reflect the covalent mixing between Ni 3d and water orbitals. Specifically, the experimental intensity ratio at the Ni L-3-edge allows to determine that the Ni 3d orbitals have on average 5.5% of water character. We propose that 2p3d RIXS at the Ni L-3-edge can be utilized to quantify covalency in Ni complexes without the use of external references or simulations.

Seit Aufstellung der Bundeswehr 1955 verloren über 3300 Soldaten und Soldatinnen ihr Leben im Dienst. Nur eine kleine Minderheit von ihnen fiel während des Kampfeinsatzes in Afghanistan. Die weitaus meisten Soldaten starben bei Unfällen. Ihnen hat die Bundeswehr lange das öffentliche Gedenken verweigert. Erst mit Beginn des Afghanistan-Einsatzes 2002 setzte letztlich ein Umdenken ein, das in der Einweihung des Berliner Ehrenmales der Bundeswehr 2009 seinen vorläufigen Höhepunkt findet. Seitdem gedenkt die Bundeswehr offiziell und öffentlich ihrer toten Soldaten. Aber warum verweigerte die Bundeswehr ihren Toten so lange ein öffentlich sichtbares und dauerhaftes Gedenken? Julia Katharina Nordmann beleuchtet die komplexen Ursachen für diesen Umgang der Bundeswehr mit ihren Toten. Und sie rekonstruiert den langen und mühsamen Prozess, der zur Ausbildung einer Gedenkkultur geführt hat. Einer Gedenkkultur, die heute in vielfältiger Weise die Toten der Bundeswehr würdigt.

In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D A complexes occur at photon energies below the optical gaps of both the donors and the C-60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C-60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes.

The African Humid Period (AHP) between similar to 15 and 5.5 cal. kyr BP caused major environmental change in East Africa, including filling of the Suguta Valley in the northern Kenya Rift with an extensive (similar to 2150 km(2)), deep (similar to 300 m) lake. Interfingering fluvio-lacustrine deposits of the Baragoi paleo-delta provide insights into the lake-level history and how erosion rates changed during this time, as revealed by delta-volume estimates and the concentration of cosmogenic Be-10 in fluvial sand. Erosion rates derived from delta-volume estimates range from 0.019 to 0.03 mm yr(-1). Be-10-derived paleo-erosion rates at similar to 11.8 cal. kyr BP ranged from 0.035 to 0.086 mm yr(-1), and were 2.7 to 6.6 times faster than at present. In contrast, at similar to 8.7 cal. kyr BP, erosion rates were only 1.8 times faster than at present. Because Be-10-derived erosion rates integrate over several millennia; we modeled the erosion-rate history that best explains the 10Be data using established non-linear equations that describe in situ cosmogenic isotope production and decay. Two models with different temporal constraints (15-6.7 and 12-6.7 kyr) suggest erosion rates that were 25 to 300 times higher than the initial erosion rate (pre-delta formation). That pulse of high erosion rates was short (similar to 4 kyr or less) and must have been followed by a rapid decrease in rates while climate remained humid to reach the modern Be-10-based erosion rate of,similar to 0.013 mm yr(-1). Our simulations also flag the two highest Be-10-derived erosion rates at 11.8 kyr BP related to nonuniform catchment erosion. These changes in erosion rates and processes during the AHP may reflect a strong increase in precipitation, runoff, and erosivity at the arid-to-humid transition either at 15 or similar to 12 cal. kyr BP, before the landscape stabilized again, possibly due to increased soil production and denser vegetation.