Cargo shuttling by electrochemical switching of core-shell microgels obtained by a facile one-shot polymerization.

Controlling and understanding the electrochemical properties of electroactive polymeric colloids is a highly topical but still a rather unexplored field of research. This is especially true when considering more complex particle architectures like stimuli-responsive microgels, which would entail different kinetic constraints for charge transport within one particle. We synthesize and electrochemically address dual stimuli responsive core-shell microgels, where the temperature-responsiveness modulates not only the internal structure, but also the microgel electroactivity both on an internal and on a global scale. In detail, a facile one-step precipitation polymerization results in architecturally advanced poly(N-isopropylacrylamide-co-vinylferrocene) P(NIPAM-co-VFc) microgels with a ferrocene (Fc)-enriched (collapsed/hard) core and a NIPAM-rich shell. While the remaining Fc units in the shell are electrochemically accessible, the electrochemical activity of Fc in the core is limited due to the restricted mobility of redox active sites and therefore restricted electron transfer in the compact core domain. Still, prolonged electrochemical action and/or chemical oxidation enable a reversible adjustment of the internal microgel structure from core-shell microgels with a dense core to completely oxidized microgels with a highly swollen core and a denser corona. The combination of thermo-sensitive and redox-responsive units being part of the network allows for efficient amplification of the redox response on the overall microgel dimension, which is mainly governed by the shell. Further, it allows for an electrochemical switching of polarity (hydrophilicity/hydrophobicity) of the microgel, enabling an electrochemically triggered uptake and release of active guest molecules. Hence, bactericidal drugs can be released to effectively kill bacteria. In addition, good biocompatibility of the microgels in cell tests suggests suitability of the new microgel system for future biomedical applications.

Near-field imaging and spectroscopy of locally strained GaN using an IR broadband laser.

Scattering-type scanning near-field optical microscopy (SNOM) offers the possibility to analyze material properties like strain in crystals at the nanoscale. In this paper we introduce a SNOM setup employing a newly developed tunable broadband laser source with a covered spectral range from 9 µm to 16 µm. This setup allows for the first time optical analyses of the crystal structure of gallium nitride (GaN) at the nanometer scale by excitation of a near-field phonon resonance around 14.5 µm. On the example of an artificially induced stress field within a GaN wafer, we present a method for a 2D visualization of small deviations in the crystal structure, which allows for fast qualitative characterizations. Subsequently, the stress levels at chosen points were quantified by recording complex near-field spectra and correlating them with theoretical model calculations. Applied to the cross-section of a heteroepitaxially grown GaN wafer, we finally demonstrate the capability of our setup to analyze the relaxation of the crystal structure along the growth axis with a nanometer spatial resolution.

The role of microstructured and interconnected pore channels in a collagen-based nerve guide on axonal regeneration in peripheral nerves.

The use of bioengineered nerve guides as alternatives for autologous nerve transplantation (ANT) is a promising strategy for the repair of peripheral nerve defects. In the present investigation, we present a collagen-based micro-structured nerve guide (Perimaix) for the repair of 2 cm rat sciatic nerve defects. Perimaix is an open-porous biodegradable nerve guide containing continuous, longitudinally orientated channels for orientated nerve growth. The effects of these nerve guides on axon regeneration by six weeks after implantation have been compared with those of ANT. Investigation of the regenerated sciatic nerve indicated that Perimaix strongly supported directed axon regeneration. When seeded with cultivated rat Schwann cells (SC), the Perimaix nerve guide was found to be almost as supportive of axon regeneration as ANT. The use of SC from transgenic green-fluorescent-protein (GFP) rats allowed us to detect the viability of donor SC at 1 week and 6 weeks after transplantation. The GFP-positive SC were aligned in a columnar fashion within the longitudinally orientated micro-channels. This cellular arrangement was not only observed prior to implantation, but also at one week and 6 weeks after implantation. It may be concluded that Perimaix nerve guides hold great promise for the repair of peripheral nerve defects.

Determination of temporal and spatial concentration gradients in hydrogel beads using multiphoton microscopy techniques.

Multiphoton microscopy is a promising technique to detect spatially and temporally resolved concentration gradients of chemical compounds, e.g., reactants in hydrogel-encapsulated biocatalysts. In contrast to current techniques, the improved spatial and temporal resolution of this method in data acquisition and its ability to measure hydrogel beads facilitates the identification of various kinetic phenomena. To our knowledge, multiphoton microscopy is used here for the first time to examine diffusion, mass transfer, and reaction in immobilized hydrogel systems. In a first step, the phenomena of diffusion and diffusion-coupled mass transfer through the phase interface are investigated in the bead center. Finally, the complete system--consisting of diffusion, mass transfer, and enzymatic reaction--is observed by measuring concentration gradients along the bead radius with temporal and spatial resolution. This metrology enables a subsequent mechanistic model identification, which in turn leads to an enhanced knowledge of reaction kinetics and supports the design of biotechnological processes. This task was only possible due to excellent spatial (25 microm) and temporal (5 s) resolution and the accuracy (+/-1%) achieved by using a multiphoton microscopy setup.