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- ItemStrong Wet and Dry Adhesion by Cupped Microstructures(Washington, DC : American Chemical Society, 2019) Wang, Y.; Kang, V.; Arzt, E.; Federle, W.; Hensel, R.Recent advances in bio-inspired microfibrillar adhesives have resulted in technologies that allow reliable attachment to a variety of surfaces. Because capillary and van der Waals forces are considerably weakened underwater, fibrillar adhesives are however far less effective in wet environments. Although various strategies have been proposed to achieve strong reversible underwater adhesion, strong adhesives that work both in air and underwater without additional surface treatments have yet to be developed. In this study, we report a novel design - cupped microstructures (CM) - that generates strong controllable adhesion in air and underwater. We measured the adhesive performance of cupped polyurethane microstructures with three different cup angles (15, 30, and 45°) and the same cup diameter of 100 μm in dry and wet conditions in comparison to standard mushroom-shaped microstructures (MSMs) of the same dimensions. In air, 15°CM performed comparably to the flat MSM of the same size with an adhesion strength (force per real contact area) of up to 1.3 MPa, but underwater, 15°CM achieved 20 times stronger adhesion than MSM (∼1 MPa versus ∼0.05 MPa). Furthermore, the cupped microstructures exhibit self-sealing properties, whereby stronger pulls lead to longer stable attachment and much higher adhesion through the formation of a better seal. © 2019 American Chemical Society.
- ItemModulating Myeloid Immune Cell Migration Using Multivalently Presented Monosaccharide Ligands for Advanced Immunotherapy(Weinheim : Wiley-VCH Verlag, 2019) Taverno, I.; Rodrigo, A.M.; Kandziora, M.; Kuntz, S.; Dernedde, J.; Trautwein, C.; Tacke, F.; Blas-Garcia, A.; Bartneck, M.Due to their importance for the outcome of the inflammatory response, the motile myeloid cells are a focus of novel treatment options. The interplay of selectins and their ligands with leukocytes and endothelial cells, which mediate endothelial attachment and transmigration of immune cells, can be modulated by selectin‐binding structures. Here, a library of selectin‐targeting ligands coupled to either gold, silver, iron oxide nanospheres, or quantum dots of 5–10 nm in size is used to systematically study their impact on immune cell motility. The multivalent presentation of the carbohydrate mimetics results in very low sub‐nanomolar binding to L ‐selectin. Using human primary monocytes, granulocytes, lymphocytes, and macrophages, it is shown that the ligands exhibit only minor effects on uptake, whereas the motility of leukocytes is critically affected as observed in migration assays evaluated by flow cytometry. The carbohydrate mimetic ring structure, sulfation, in particular, and the degree of ligand presentation, are constituents which cohere in this process. Specific carbohydrate ligands can thus selectively regulate leukocyte subsets. These data form the basis for advanced immunotherapy which inhibits the amplification of inflammation by restricting leukocyte influx to injured tissue sites. Furthermore, the targeting ligands may complement existing treatment options for inflammatory diseases.
- ItemPrintability study of metal ion crosslinked PEG-catechol based inks(Cold Spring Harbor : Cold Spring Harbor Laboratory, 2019) Włodarczyk-Biegun, Malgorzata K.; Paez, Julieta I.; Villiou, Maria; Feng, Jun; del Campo, AranzazuInspired by reversible networks present in nature, we have explored the printability of catechol functionalized polyethylene glycol (PEG) based inks with metal-coordination crosslinking. Material formulations containing Al3+, Fe3+ or V3+ as crosslinking ions were tested. The printability and shape fidelity were dependent on the ink composition (metal ion type, pH, PEG molecular weight) and printing parameters (extrusion pressure and printing speed). The relaxation time, recovery rate and viscosity of the inks were analyzed in rheology studies and correlated with thermodynamic and ligand exchange kinetic constants of the dynamic bonds and the printing performance (i.e. shape fidelity of the printed structures). The relevance of the relaxation time and ligand exchange kinetics for printability was demonstrated. Cells seeded on the crosslinked materials were viable, indicating the potential of the formulations to be used as inks for cell encapsulation. The proposed dynamic ink design offers significant flexibility for 3D (bio)printing, and enables straightforward adjustment of the printable formulation to meet application-specific needs.
- ItemBioinspired Liposomes for Oral Delivery of Colistin to Combat Intracellular Infections by Salmonella enterica(Weinheim : Wiley-VCH, 2019) Menina, S.; Eisenbeis, J.; Kamal, M.A.M.; Koch, M.; Bischoff, M.; Gordon, S.; Loretz, B.; Lehr, C.-M.Bacterial invasion into eukaryotic cells and the establishment of intracellular infection has proven to be an effective means of resisting antibiotic action, as anti-infective agents commonly exhibit a poor permeability across the host cell membrane. Encapsulation of anti-infectives into nanoscaled delivery systems, such as liposomes, is shown to result in an enhancement of intracellular delivery. The aim of the current work is, therefore, to formulate colistin, a poorly permeable anti-infective, into liposomes suitable for oral delivery, and to functionalize these carriers with a bacteria-derived invasive moiety to enhance their intracellular delivery. Different combinations of phospholipids and cholesterol are explored to optimize liposomal drug encapsulation and stability in biorelevant media. These liposomes are then surface-functionalized with extracellular adherence protein (Eap), derived from Staphylococcus aureus. Treatment of HEp-2 and Caco-2 cells infected with Salmonella enterica using colistin-containing, Eap-functionalized liposomes resulted in a significant reduction of intracellular bacteria, in comparison to treatment with nonfunctionalized liposomes as well as colistin alone. This indicates that such bio-invasive carriers are able to facilitate intracellular delivery of colistin, as necessary for intracellular anti-infective activity. The developed Eap-functionalized liposomes, therefore, present a promising strategy for improving the therapy of intracellular infections. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemTargeted T1 Magnetic Resonance Imaging Contrast Enhancement with Extraordinarily Small CoFe2O4 Nanoparticles(Washington, DC : American Chemical Society, 2019) Piché, Dominique; Tavernaro, Isabella; Fleddermann, Jana; Lozano, Juan G.; Varambhia, Aakash; Maguire, Mahon L.; Koch, Marcus; Ukai, Tomofumi; Hernández Rodríguez, Armando J.; Jones, Lewys; Dillon, Frank; Reyes Molina, Israel; Mitzutani, Mai; González Dalmau, Evelio R.; Maekawa, Toru; Nellist, Peter D.; Kraegeloh, Annette; Grobert, NicoleExtraordinarily small (2.4 nm) cobalt ferrite nanoparticles (ESCIoNs) were synthesized by a one-pot thermal decomposition approach to study their potential as magnetic resonance imaging (MRI) contrast agents. Fine size control was achieved using oleylamine alone, and annular dark-field scanning transmission electron microscopy revealed highly crystalline cubic spinel particles with atomic resolution. Ligand exchange with dimercaptosuccinic acid rendered the particles stable in physiological conditions with a hydrodynamic diameter of 12 nm. The particles displayed superparamagnetic properties and a low r2/r1 ratio suitable for a T1 contrast agent. The particles were functionalized with bile acid, which improved biocompatibility by significant reduction of reactive oxygen species generation and is a first step toward liver-targeted T1 MRI. Our study demonstrates the potential of ESCIoNs as T1 MRI contrast agents.
- ItemReversibly compressible and freestanding monolithic carbon spherogels(Amsterdam : Elsevier, 2019) Salihovic, M.; Zickler, G.A.; Fritz-Popovski, G.; Ulbricht, M.; Paris, O.; Hüsing, N.; Presser, V.; Elsaesser, M.S.We present a versatile strategy to tailor the nanostructure of monolithic carbon aerogels. By use of an aqueous colloidal solution of polystyrene in the sol-gel processing of resorcinol-formaldehyde gels, we can prepare, after supercritical drying and successive carbonization, freestanding monolithic carbon aerogels, solely composed of interconnected and uniformly sized hollow spheres, which we name carbon spherogels. Each sphere is enclosed by a microporous carbon wall whose thickness can be adjusted by the polystyrene concentration, which affects the pore texture as well as the mechanical properties of the aerogel monolith. In this study, we used monodisperse polystyrene spheres of approximately 250 nm diameter, which result in an inner diameter of the final hollow carbon spheres of approximately 200 ± 5 nm due to shrinkage during the carbonization process. The excellent homogeneity of the samples, as well as uniform sphere geometries, are confirmed by small- and angle X-ray scattering. The presence of macropores between the hollow spheres creates a monolithic network with the benefit of being reversibly compressible up to 10% linear strain without destruction. Electrochemical tests demonstrate the applicability of ground and CO2 activated carbon spherogels as electrode materials. © 2019 The Authors
- ItemMembrane Tension Orchestrates Rear Retraction in Matrix-Directed Cell Migration(Amsterdam : Elsevier, 2019) Hetmanski, J.H.R.; de, Belly, H.; Busnelli, I.; Waring, T.; Nair, R.V.; Sokleva, V.; Dobre, O.; Cameron, A.; Gauthier, N.; Lamaze, C.; Swift, J.; del, Campo, A.; Starborg, T.; Zech, T.; Goetz, J.G.; Paluch, E.K.; Schwartz, J.-M.; Caswell, P.T.In development, wound healing, and cancer metastasis, vertebrate cells move through 3D interstitial matrix, responding to chemical and physical guidance cues. Protrusion at the cell front has been extensively studied, but the retraction phase of the migration cycle is not well understood. Here, we show that fast-moving cells guided by matrix cues establish positive feedback control of rear retraction by sensing membrane tension. We reveal a mechanism of rear retraction in 3D matrix and durotaxis controlled by caveolae, which form in response to low membrane tension at the cell rear. Caveolae activate RhoA-ROCK1/PKN2 signaling via the RhoA guanidine nucleotide exchange factor (GEF) Ect2 to control local F-actin organization and contractility in this subcellular region and promote translocation of the cell rear. A positive feedback loop between cytoskeletal signaling and membrane tension leads to rapid retraction to complete the migration cycle in fast-moving cells, providing directional memory to drive persistent cell migration in complex matrices. © 2019 The AuthorsCell migration through 3D matrix is critical to developmental and disease processes, but the mechanisms that control rear retraction are poorly understood. Hetmanski et al. show that differential membrane tension allows caveolae to form at the rear of migrating cells and activate the contractile actin cytoskeleton to promote rapid retraction. © 2019 The Authors
- ItemModeling the contact mechanics of hydrogels(Basel : MDPI, 2019) Mueser, M.H.; Li, H.; Bennewitz, R.A computationally lean model for the coarse-grained description of contact mechanics of hydrogels is proposed and characterized. It consists of a simple bead-spring model for the interaction within a chain, potentials describing the interaction between monomers and mold or confining walls, and a coarse-grained potential reflecting the solvent-mediated effective repulsion between non-bonded monomers. Moreover, crosslinking only takes place after the polymers have equilibrated in their mold. As such, the model is able to reflect the density, solvent quality, and the mold hydrophobicity that existed during the crosslinking of the polymers. Finally, such produced hydrogels are exposed to sinusoidal indenters. The simulations reveal a wavevector-dependent effective modulus E*(q) with the following properties: (i) stiffening under mechanical pressure, and a sensitivity of E*(q) on (ii) the degree of crosslinking at large wavelengths, (iii) the solvent quality, and (iv) the hydrophobicity of the mold in which the polymers were crosslinked. Finally, the simulations provide evidence that the elastic heterogeneity inherent to hydrogels can suffice to pin a compressed hydrogel to a microscopically frictionless wall that is undulated at a mesoscopic length scale. Although the model and simulations of this feasibility study are only two-dimensional, its generalization to three dimensions can be achieved in a straightforward fashion. © 2019 by the authors.
- ItemCombining soft polysilazanes with melt-shear organization of core–shell particles: On the road to polymer-templated porous ceramics(Basel : MDPI, 2019) Boehm, A.K.; Ionescu, E.; Koch, M.; Gallei, M.The preparation of ordered macroporous SiCN ceramics has attracted significant interest and is an attractive area for various applications, e.g., in the fields of catalysis, gas adsorption, or membranes. Non-oxidic ceramics, such as SiCN, own a great stability based on the covalent bonds between the containing elements, which leads to interesting properties concerning resistance and stability at high temperature. Their peculiar properties have become more and more important for a manifold of applications, like catalysis or separation processes, at high temperatures. Within this work, a feasible approach for the preparation of ordered porous materials by taking advantage of polymer-derived ceramics is presented. To gain access to free-standing films consisting of porous ceramic materials, the combination of monodisperse organic polymer-based colloids with diameters of 130 nm and 180 nm featuring a processable preceramic polymer is essential. For this purpose, the tailored design of hybrid organic/inorganic particles featuring anchoring sites for a preceramic polymer in the soft shell material is developed. Moreover, polymer-based core particles are used as sacrificial template for the generation of pores, while the preceramic shell polymer can be converted to the ceramic matrix after thermal treatment. Two different routes for the polymer particles, which can be obtained by emulsion polymerization, are followed for covalently linking the preceramic polysilazane Durazane1800 (Merck, Germany): (i) Free radical polymerization and (ii) atom transfer radical polymerization (ATRP) conditions. These hybrid hard core/soft shell particles can be processed via the so-called melt-shear organization for the one-step preparation of free-standing particle films. A major advantage of this technique is the absence of any solvent or dispersion medium, enabling the core particles to merge into ordered particle stacks based on the soft preceramic shell. Subsequent ceramization of the colloidal crystal films leads to core particle degradation and transformation into porous ceramics with ceramic yields of 18–54%. © 2019 by the authors.
- ItemNanopillar diffraction gratings by two-photon lithography(Basel : MDPI, 2019) Purtov, J.; Rogin, P.; Verch, A.; Johansen, V.E.; Hensel, R.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. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.