Scientific publications

Abstract A substrate mimicking the surface topography and temperature sensitivity of skin goosebumps is fabricated. Close-packed arrays of thermoresponsive microgel particles undergo topographical changes in response to temperature changes between 25 and 37 °C, resembling the goosebump structure that human skin develops in response to temperature changes or other circumstances. Specifically, positively charged poly[2-(methacryloyloxy)ethyltrimethylammonium chloride] (PMETAC) brushes serve as an anchoring substrate for negatively charged poly(NIPAm-co-AA) microgels. The packing density and particle morphology can be tuned by brush layer thickness and pH of the microgel suspension. For brush layer thickness below 50 nm, particle monolayers are observed, with slightly flattened particle morphology at pH 3 and highly collapsed particles at pH above 7. Polymer brush films with thickness above 50 nm lead to the formation of particle multilayers. The temperature responsiveness of the monolayer assemblies allows reversible changes in the film morphology, which in turn affects underwater adhesion and friction at 25 and 37 °C. These results are promising for the design of new functional materials and may also serve as a model for biological structures and processes.

Abstract Transition metal dichalcogenides are attractive two-dimensional electrode materials for electrochemical energy storage devices due to their high reversible charge storage capacity. Hybridization of these materials with carbon promises enhanced performance by facilitating the access to reactive sites and extended mechanical stabilization. Herein, we introduce a NbS2/C hybrid material exhibiting a gyroidal microstructure synthesized through macromolecular co-assembly of a tailored block copolymer and an organometallic niobium precursor and subsequent sulfidation. Our synthesis allows the preparation of mechanically stable monoliths with NbS2 nanocrystals engulfed in a highly porous carbon shell. Due to the curvature of the gyroidal structure, abundant reactive sites are exposed that lead to an attractive performance in a lithium-containing electrolyte with a capacity of up to 400 mAh/g.

Abstract Fibrillar adhesion pads of insects and geckoes have inspired the design of high-performance adhesives enabling a new generation of handling devices. Despite much progress over the last decade, the current understanding of these adhesives is limited to single contact pillars and the behavior of whole arrays is largely unexplored. In the study reported here, a novel approach is taken to gain insight into the detachment mechanisms of whole micropatterned arrays. Individual contacts are imaged by frustrated total internal reflection, allowing in situ observation of contact formation and separation during adhesion tests. The detachment of arrays is found to be governed by the distributed adhesion strength of individual pillars, but no collaborative effect mediated by elastic interactions can be detected. At the maximal force, about 30% of the mushroom structures are already detached. The adhesive forces decrease with reduced air pressure by 20% for the smooth and by 6% for the rough specimen. These contributions are attributed to a suction effect, whose strength depends critically on interfacial defects controlling the sealing quality of the contact. This dominates the detachment process and the resulting adhesion strength.

Two-dimensional photonic structures such as nanostructured pillar gratings are useful for various applications including wave coupling, diffractive optics, and security features. Two-photon lithography facilitates the generation of such nanostructured surfaces with high precision and reproducibility. In this work, we report on nanopillar diffraction gratings fabricated by two-photon lithography with various laser powers close to the polymerization threshold of the photoresist. As a result, defect-free arrays of pillars with diameters down to 184 nm were fabricated. The structure sizes were analyzed by scanning electron microscopy and compared to theoretical predictions obtained from Monte Carlo simulations. The optical reflectivities of the nanopillar gratings were analyzed by optical microscopy and verified by rigorous coupled-wave simulations.

For the next generation of handling systems, reversible adhesion enabled by micropatterned dry adhesives exhibits high potential. The versatility of polymeric micropatterns in handling objects made from various materials has been demonstrated by several groups. However, specimens reported in most studies have been restricted to the laboratory scale. Upscaling the size and quantity of micropatterned adhesives is the next step to enable successful technology transfer. Towards this aim, we introduce a continuous roll-to-roll replication process for fabrication of high-performance, mushroom-shaped micropatterned dry adhesives. The micropatterns were made from UV-curable polyurethane acrylates. To ensure the integrity of the complex structure during the fabrication process, flexible templates were used. The compression between the template and the wet prepolymer coating was investigated to optimize replication results without structural failures, and hence, to improve adhesion. As a result, we obtained micropatterned adhesive tapes, 10 cm in width and several meters in length, with adhesion strength about 250 kPa to glass, suitable for a wide range of applications

Summary The dragonfish is a voracious predator of the deep sea with an arsenal of tools to hunt prey and remain concealed. In contrast to its dark pigmented skin, the dragonfish is equipped with transparent teeth. Here, we establish the structure, composition, and mechanical properties of the transparent teeth for the first time. We find the enamel-like layer to consist of nanocrystalline hydroxyapatite domains (∼20 nm grain size) embedded in an amorphous matrix, whereas in the dentin layer the nanocrystalline hydroxyapatite coats nanoscale collagen fibrils forming nanorods. This nanoscale structure is responsible for the much-reduced Rayleigh light scattering, which is further ensured by the sufficiently thin walls. Here, we suggest that the nanostructured design of the transparent dragonfish teeth enables predatory success as it makes its wide-open mouth armed with saber-like teeth effectively disappear, showing no contrast to the surrounding blackness of the fish nor the background darkness of the deep sea.

Introduction: Nanoparticles (NPs) are used in numerous products in technical fields and biomedicine; their potential adverse effects have to be considered in order to achieve safe applications. Besides their distribution in tissues, organs, and cellular localization, their impact and penetration during the process of tissue formation occurring in vivo during liver regeneration are critical steps for establishment of safe nanomaterials. Materials and methods: In this study, 3D cell culture of human hepatocarcinoma cells (HepG2) was used to generate cellular spheroids, serving as in vitro liver microtissues. In order to determine their differential distribution and penetration depth in HepG2 spheroids, SiO2 NPs were applied either during or after spheroid formation. The NP penetration was comprehensively studied using confocal laser scanning microscopy and scanning electron microscopy. Results: Spheroids were exposed to 100 µg mL-1 SiO2 NPs either at the beginning of spheroid formation, or during or after formation of spheroids. Microscopy analyses revealed that NP penetration into the spheroid is limited. During and after spheroid formation, SiO2 NPs penetrated about 20 µm into the spheroids, corresponding to about three cell layers. In contrast, because of the addition of SiO2 NPs simultaneously to cell seeding, NP agglomerates were located also in the spheroid center. Application of SiO2 NPs during the process of spheroid formation had no impact on final spheroid size. Conclusion: Understanding the distribution of NPs in tissues is essential for biomedical applications. The obtained results indicate that NPs show only limited penetration into already formed tissue, which is probably caused by the alteration of the tissue structure and cell packing density during the process of spheroid formation.

Glucocorticoids (GCs) are widely prescribed therapeutics for the treatment of inflammatory diseases, and endogenous GCs play a key role in immune regulation. Toll-like receptors (TLRs) enable innate immune cells, such as macrophages, to recognize a wide variety of microbial ligands, thereby promoting inflammation. The interaction of GCs with macrophages in the immunosuppressive resolution phase upon prolonged TLR activation is widely unknown. Treatment of human alveolar macrophages (AMs) with the synthetic GC dexamethasone (Dex) did not alter the expression of TLRs -1, -4, and -6. In contrast, TLR2 was upregulated in a GC receptor-dependent manner, as shown by Western blot and qPCR. Furthermore, long-term lipopolysaccharide (LPS) exposure mimicking immunosuppression in the resolution phase of inflammation synergistically increased Dex-mediated TLR2 upregulation. Analyses of publicly available data sets suggested that TLR2 is induced during the resolution phase of inflammatory diseases, i.e., under conditions associated with high endogenous GC production. TLR2 induction did not enhance TLR2 signaling, as indicated by reduced cytokine production after treatment with TLR2 ligands in Dex- and/or LPS-primed AMs. Thus, we hypothesized that the upregulated membrane-bound TLR2 might serve as a precursor for soluble TLR2 (sTLR2), known to antagonize TLR2-dependent cell actions. Supernatants of LPS/Dex-primed macrophages contained sTLR2, as demonstrated by Western blot analysis. Activation of metalloproteinases resulted in enhanced sTLR2 shedding. Additionally, we detected full-length TLR2 and assumed that this might be due to the production of TLR2-containing extracellular vesicles (EVs). EVs from macrophage supernatants were isolated by sequential centrifugation. Both untreated and LPS/Dex-treated cells produced vesicles of various sizes and shapes, as shown by cryo-transmission electron microscopy. These vesicles were identified as the source of full-length TLR2 in macrophage supernatants by Western blot and mass spectrometry. Flow cytometric analysis indicated that TLR2-containing EVs were able to bind the TLR2 ligand Pam3CSK4. In addition, the presence of EVs reduced inflammatory responses in Pam3CSK4-treated endothelial cells and HEK Dual reporter cells, demonstrating that TLR2-EVs can act as decoy receptors. In summary, our data show that sTLR2 and full-length TLR2 are released by macrophages under anti-inflammatory conditions, which may contribute to GC-induced immunosuppression.

Continuous roll-to-roll fabrication is essential for transferring the idea of bio-inspired, fibrillar dry adhesives into large-scale, synthetic, high-performance adhesive tapes. Toward this aim, we investigated process parameters that allow us to control the morphology and the resulting adhesion of mushroom-shaped micropatterned surfaces. Flexible silicone templates enabled the replication process of the polyurethane acrylate pre-polymer involving UV-light-induced cross-linking. For this paper, we particularly tailored the polyurethane acrylate pre-polymer by adding chemical components to tune UV curing kinetics and to reduce oxygen inhibition of radicals. We found that higher intensities of the UV light and faster reaction kinetics improved the quality of the microstructures, i.e., a larger cap diameter of the mushroom tips was achieved. The polymer blend U6E4 exhibited the fastest curing kinetics, which resulted in a micromorphology similar to that of the Ni-shim master structures. Best adhesion results were obtained for adhesive tapes made from U6E4 with 116 kPa pull-off stress, 1.4 N cm−1 peel strength and 71 kPa shear strength. In addition, repeated attachment–detachment tests over 100,000 cycles demonstrated strong robustness and reusability.

Nanotechnologies are characterized by a growing legacy of already marketed and novel manufactured nanomaterials (MNMs) and nano-enabled products with a lack of a coherent risk governance system to address their safety effectively. In response to this situation, a proactive system is needed to minimize the gap between the pace of innovation and the pace of developing nano-specific risk governance. With the Safe Innovation Approach (SIA), we seek to enhance the ability of all stakeholders to address the safety assessment of innovations in a robust yet agile manner. The SIA is an approach that combines a) the Safe-by-Design (SbD) concept, which recommends industry to integrate safety considerations as early as possible into the innovation process, and b) the Regulatory Preparedness (RP) concept which aims to improve anticipation of regulators in order that they can facilitate the development of adaptable (safety) regulation that can keep up with the pace of knowledge generation and innovation of MNMs and MNM-enabled products. SIA promotes a safe and responsible approach for industry when developing innovative products and materials, and stimulates a proactive attitude amongst policymakers and regulators to minimize the time gap between appearance and approval of innovation and appropriate legislation. Here we introduce a SIA framework consisting of creating SIA awareness, developing a SIA methodology (SbD scenarios, SbD methodology including information needs, functionality, and grouping, SIA Toolbox and a nano-specific database), bringing the Trusted Environment and RP concept into an operational level, and the development of novel business for industry and novel governance models for regulators. The SIA framework once implemented will result in a system for MNMs and nano-enabled products that is agile and robust. Current international efforts such as in the OECD are now trying to bring this concept to practice.