3D Printing of Dual-Cure Networks Based on (Meth)acrylate/Bispropargyl Ether Building Blocks

In recent years, dual-cure chemistry has been exploited to realize interpenetrating networks (IPNs) that provide enhanced thermo-mechanical properties. In this contribution, photoinduced curing of (meth)acrylates is used to build the desired 3D structure, whereas the thermally triggered polymerization reaction of 2H-chromene functionalized building blocks is utilized to create the IPN. This strategy combines the advantages of traditional UV-curable monomers with high-performance thermosets. After the successful synthesis of the bispropargyl ether derivative, i.e., 4,4′-(propane-2,2-diyl)bis((ethynyloxy)benzene), its thermally induced conversion to the corresponding 2H chromene functionalized prepolymer is studied by Fourier-transform infrared spectroscopy and gel permeation chromatography. The network formation as well as the printability of various formulations containing different amounts of the thermo-curable building block is investigated. The obtained IPNs provide enhanced thermo-mechanical properties making these resins suitable for the additive manufacturing of functional 3D parts for high-performance applications.     

Antibacterial Surface Coatings from Zinc Oxide Nanoparticles Embedded in Poly(N‐isopropylacrylamide) Hydrogel Surface Layers

Despite multiple research approaches to prevent bacterial colonization on surfaces, device‐associated infections are currently responsible for about 50% of nosocomial infections in Europe and significantly increase health care costs, which demands development of advanced antibacterial surface coatings. Here, novel antimicrobial composite materials incorporating zinc oxide nanoparticles (ZnO NP) into biocompatible poly(N‐isopropylacrylamide) (PNIPAAm) hydrogel layers are prepared by mixing the PNIPAAm prepolymer with ZnO NP, followed by spin‐coating and photocrosslinking. Scanning electron microscopy (SEM) characterization of the composite film morphology reveals a homogeneous distribution of the ZnO NP throughout the film for every applied NP/polymer ratio. The optical properties of the embedded NP are not affected by the matrix as confirmed by UV‐vis spectroscopy. The nanocomposite films exhibit bactericidal behavior towards Escherichia coli (E. coli) for a ZnO concentration as low as ≈0.74 μg cm^?2 (1.33 mmol cm^?3), which is determined by inductively coupled plasma optical emission spectrometry. In contrast, the coatings are found to be non‐cytotoxic towards a mammalian cell line (NIH/3T3) at bactericidal loadings of ZnO over an extended period of seven days. The differential toxicity of the ZnO/hydrogel nanocomposite thin films between bacterial and cellular species qualifies them as promising candidates for novel biomedical device coatings.     

Design of an Ultrafast G Protein Switch Based on a Mouse Melanopsin Variant

The primary goal of optogenetics is the light-controlled noninvasive and specific manipulation of various cellular processes. Herein, we present a hybrid strategy for targeted protein engineering combining computational techniques with electrophysiological and UV/visible spectroscopic experiments. We validated our concept for channelrhodopsin-2 and applied it to modify the less-well-studied vertebrate opsin melanopsin. Melanopsin is a promising optogenetic tool that functions as a selective molecular light switch for G protein-coupled receptor pathways. Thus, we constructed a model of the melanopsin G_q protein complex and predicted an absorption maximum shift of the Y211F variant. This variant displays a narrow blue-shifted action spectrum and twofold faster deactivation kinetics compared to wild-type melanopsin on G protein-coupled inward rectifying K⁺ (GIRK) channels in HEK293 cells. Furthermore, we verified the in vivo activity and optogenetic potential for the variant in mice. Thus, we propose that our developed concept will be generally applicable to designing optogenetic tools.     

Controlled Individual Skyrmion Nucleation at Artificial Defects Formed by Ion Irradiation

Magnetic skyrmions are particle‐like deformations in a magnetic texture. They have great potential as information carriers in spintronic devices because of their interesting topological properties and favorable motion under spin currents. A new method of nucleating skyrmions at nanoscale defect sites, created in a controlled manner with focused ion beam irradiation, in polycrystalline magnetic multilayer samples with an interfacial Dzyaloshinskii–Moriya interaction, is reported. This new method has three notable advantages: 1) localization of nucleation; 2) stability over a larger range of external field strengths, including stability at zero field; and 3) existence of skyrmions in material systems where, prior to defect fabrication, skyrmions were not previously obtained by field cycling. Additionally, it is observed that the size of defect nucleated skyrmions is uninfluenced by the defect itself—provided that the artificial defects are controlled to be smaller than the inherent skyrmion size. All of these characteristics are expected to be useful toward the goal of realizing a skyrmion‐based spintronic device. This phenomenon is studied with a range of transmission electron microscopy techniques to probe quantitatively the magnetic behavior at the defects with applied field and correlate this with the structural impact of the defects.     

Coking behavior of nickel and a rhodium based catalyst used in steam reforming for power-to-gas applications

This paper proposes partial steam reforming of natural gas as a chemical storage option for excess electricity. Thermodynamic simulations with Aspen Plus^® show that highest process efficiencies are reached at low steam-to-carbon (S/C) ratios in the feed. However, coke deposition due to unwanted side or follow-up reactions and thus catalyst deactivation is likely in this operation range. In an experimental evaluation three catalysts were selected to test their resistance towards coking: two nickel based and one rhodium based noble metal catalyst. They were tested regarding their long-term stability at S/C ratios as low as 0 to 0.1 and reaction temperatures between 450 and 500 °C. A different reaction and deactivation behavior was observed for nickel and the noble metal catalysts. The measured life times of the noble metal catalyst were by a factor of at least 100 higher than for the two selected nickel catalysts at the applied reforming conditions. Furthermore, after each reforming experiment, a temperature-programmed oxidation (TPO) analysis was performed for the spent catalysts. Based on literature data, the measured CO₂ peaks at corresponding temperatures were related to the different forms of solid carbon depositions. Main carbonaceous species found on the nickel catalysts were of filamentous nature, whereas one or two more reactive C species with monoatomic or polymeric structure at much lower amount were detected on the noble metal catalyst. Further SEM analysis confirmed these findings.     

Strong influence of polymer architecture on the microstructural evolution of hafnium-alkoxide-modified silazanes upon ceramization

The present study focuses on the synthesis and ceramization of novel hafnium-alkoxide-modified silazanes as well as on their microstructure evolution at high temperatures. The synthesis of hafnia-modified polymer-derived SiCN ceramic nanocomposites is performed via chemical modification of a polysilazane and of a cyclotrisilazane, followed by cross-linking and pyrolysis in argon atmosphere. Spectroscopic investigation (i.e., NMR, FTIR, and Raman) shows that the hafnium alkoxide reacts with the N-H groups of the cyclotrisilazane; in the case of polysilazane, reactions of N-H as well as Si-H groups with the alkoxide are observed. Consequently, scanning and transmission electron microscopy studies reveal that the ceramic nanocomposites obtained from cyclotrisilazane and polysilazane exhibited markedly different microstructures, which is a result of the different reaction pathways of the hafnium alkoxide with cyclotrisilazane and with polysilazane. Furthermore, the two prepared ceramic nanocomposites are unexpectedly found to exhibit extremely different high-temperature behavior with respect to decomposition and crystallization; this essential difference is found to be related to the different distribution of hafnium throughout the ceramic network in the two samples. Thus, the homogeneous distribution of hafnium observed in the polysilazane-derived ceramic leads to an enhanced thermal stability with respect to decomposition, whereas the local enrichment of hafnium within the matrix of the cyclotrisilazane-based sample induces a pronounced decomposition upon annealing at high temperatures. The results indicate that the chemistry and architecture of the precursor has a crucial effect on the microstructure of the resulting ceramic material and consequently on its high-temperature behavior.     

Selective High‐Frequency Mechanical Actuation Driven by the VO2 Electronic Instability

Relaxation oscillators consist of periodic variations of a physical quantity triggered by a static excitation. They are a typical consequence of nonlinear dynamics and can be observed in a variety of systems. VO₂ is a correlated oxide with a solid‐state phase transition above room temperature, where both electrical resistance and lattice parameters undergo a drastic change in a narrow temperature range. This strong nonlinear response allows to realize spontaneous electrical oscillations in the megahertz range under a DC voltage bias. These electrical oscillations are employed to set into mechanical resonance a microstructure without the need of any active electronics, with small power consumption and with the possibility to selectively excite specific flexural modes by tuning the value of the DC electrical bias in a range of few hundreds of millivolts. This actuation method is robust and flexible and can be implemented in a variety of autonomous DC‐powered devices.     

Intercellular Transport of Nanomaterials is Mediated by Membrane Nanotubes In Vivo

So‐called membrane nanotubes are cellular protrusions between cells whose functions include cell communication, environmental sampling, and protein transfer. It has been previously reported that systemically administered carboxyl‐modified quantum dots (cQDs) are rapidly taken up by perivascular macrophages in skeletal muscle of healthy mice. Expanding these studies, it is found, by means of in vivo fluorescence microscopy on the mouse cremaster muscle, rapid uptake of cQDs not only by perivascular macrophages but also by tissue‐resident cells, which are localized more than 100 μm distant from the closest vessel. Confocal microscopy on muscle tissue, immunostained for the membrane dye DiI, reveals the presence of continuous membranous structures between MHC‐II‐positive, F4/80‐positive cells. These structures contain microtubules, components of the cytoskeleton, which clearly colocalize with cQDs. The cQDs are exclusively found inside endosomal vesicles. Most importantly, by using in vivo fluorescence microscopy, this study detected fast (0.8 μm s^?1, mean velocity), bidirectional movement of cQDs in such structures, indicating transport of cQD‐containing vesicles along microtubule tracks by the action of molecular motors. The findings are the first to demonstrate membrane nanotube function in vivo and they suggest a previously unknown route for the distribution of nanomaterials in tissue.     

Optical properties of highly transparent polypropylene cast films: Influence of material structure,additives, and processing conditions

Polypropylene homopolymers and ethylene/propylene‐random‐copolymers formulated with and without anti‐blocking additives were extruded to cast films with an industrial scale extruder equipped with a soft box, a specific air knife that expels a higher volume of air at lower velocity. The films were analyzed as to their optical properties haze and clarity. A comprehensive topographical characterization was performed using atomic force microscopy (AFM) and confocal microscopy. To obtain morphological information on a nanometer scale AFM phase imaging, micro‐thermal analysis and small angle X‐ray scattering (SAXS) were done. A significant effect of additives and processing conditions on the film topography and the optical properties was revealed. The films without anti‐blocking and antacid aids showed the best optical properties and lowest vertical roughness fluctuations. In contrast, the addition of anti‐blocking and antacid aids reduced the optical properties associated with an increase in surface roughness. While for films without anti‐blocking aids an enhanced soft box condition resulted in lower vertical fluctuations of roughness and better optical properties, the behavior was in reverse for films with anti‐blocking aid. By means of SAXS crystalline lamellae with a thickness of about 2.5 nm were detected. High‐resolution phase imaging AFM yielded thicker crystal lamellae on the film surface. POLYM. ENG. SCI., 46:520–531, 2006. © 2006 Society of Plastics Engineers.