The integration of dynamic covalent bonds into macrocycles has been a tremendously successful strategy for investigating noncovalent interactions and identifying effective host-guest pairs. While numerous studies have focused on the dynamic responses of macrocycles and larger cages to various guests, the corresponding constitutionally dynamic chemistry of cryptands remains unexplored. Reported here is that cryptands based on orthoester bridgeheads offer an elegant entry to experiments in which a metal ion selects its preferred host from a dynamic mixture of competing subcomponents. In such dynamic mixtures, the alkali metal ions Li , Na , K , Rb , and Cs exhibit pronounced preferences for the formation of cryptands of certain sizes and donor numbers, and the selection is rationalized by DFT calculations. Reported is also the first self-assembly of a chiral orthoester cryptate and a preliminary study on the use of stereoisomers as subcomponents.

Phase-change memory technology has become more mature in recent years. But some fundamental problems linked to the electrical transport properties in the amorphous phase of phase-change materials still need to be solved. The increase of resistance over time, called resistance drift, for example, poses a major challenge for the implementation of multilevel storage, which will eventually be necessary to remain competitive in terms of high storage densities. To link structural properties with electrical transport, a broader knowledge of (i) changes in the density of states (DoS) upon structural relaxation and (ii) the influence of defects on electrical transport is required. In this paper, we present temperaturedependent conductivity and photo-conductivity measurements on the archetype phase change material GeTe. It is shown that trap-limited band transport at high temperatures (above 165 K) and variable range hopping at low temperatures are the predominating transport mechanism. Based on measurements of the temperature dependence of the optical band gap, modulated photo-conductivity and photo-thermal deflection spectroscopy, a DoS model for GeTe was proposed. Using this DoS, the temperature dependence of conductivity and photo-conductivity has been simulated. Our work shows how changes in the DoS (band gap and defect distributions) will affect the electrical transport before and after Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution of this work must maintain attribution to the author(s) and the title of the work, journal citation and DOI.temperature-accelerated drift. The decrease in conductivity upon annealing can be explained entirely by an increase of the band gap by about 12%. However, low-temperature photo-conductivity measurements revealed that a change in the defect density may also play a role. New J. Phys. 16 (2014) 043015 D Krebs et al New J. Phys. 16 (2014) 043015 D Krebs et al New J. Phys. 16 (2014) 043015 D Krebs et al 7 New J. Phys. 16 (2014) 043015 D Krebs et al 8

Carbon-based nonvolatile resistive memories are an emerging technology. Switching endurance remains a challenge in carbon memories based on tetrahedral amorphous carbon (ta-C). One way to counter this is by oxygenation to increase the repeatability of reversible switching. Here, we overview the current status of carbon memories. We then present a comparative study of oxygen-free and oxygenated carbon-based memory devices, combining experiments and molecular dynamics (MD) simulations Index Terms-Nonvolatile memory, oxygenated carbon, RRAM, tetrahedral amorphous carbon, diamond-like carbon

Understanding the mechanisms of interstitial cancer migration is of great scientific and medical interest. Creating 3D platforms, conducive to optical microscopy and mimicking the physical parameters (in plane and out of plane) involved in interstitial migration, is a major step forward in this direction. Here, a novel approach is used to directly print free-form, 3D micropores on basal scaffolds containing microgratings optimized for contact guidance. The platforms so formed are validated by monitoring cancer cell migration and micropore penetration with high-resolution optical microscopy. The shapes, sizes and deformability of the micropores are controllable, paving the way to decipher their role in interstitial migration.

Front Cover: http://doi.wiley.com/10.1002/mren.201200416, A. Ferrari, D. Poulikakos, and coworkers present a novel approach to fabricating optically accessible, 3D integrated platforms, simulating the cell microenvironment during interstitial migration. The platforms consist of free‐form, 3D micropores printed on demand on basal scaffolds with microgratings, and are employed to monitor cancer cell migration using highresolution optical microscopy.