Search Results
Gas-Phase Fluorination on PLA Improves Cell Adhesion and Spreading
For the regeneration or creation of functional tissues, biodegradable biomaterials including polylactic acid (PLA) are widely preferred. Modifications of the material surface are quite common to improve cell-material interactions and thereby support the biological outcome. Typical approaches include a wet chemical treatment with mostly hazardous substances or a functionalization with plasma. In the present study, gas-phase fluorination was applied to functionalize the PLA surfaces in a simple and one-step process. The biological response including biocompatibility, cell adhesion, cell spreading, and proliferation was analyzed in cell culture experiments with fibroblasts L929 and correlated with changes in the surface properties. Surface characterization methods including surface energy and isoelectric point measurements, X-ray photoelectron spectroscopy, and atomic force microscopy were applied to identify the effects of fluorination on PLA. Gas-phase fluorination causes the formation of C-F bonds in the PLA backbone, which induce a shift to a more hydrophilic and polar surface. The slightly negatively charged surface dramatically improves cell adhesion and spreading of cells on the PLA even with low fluorine content. The results indicate that this improved biological response is protein-but not integrin-dependent. Gas-phase fluorination is therefore an efficient technique to improve cellular response to biomaterial surfaces without losing cytocompatibility. Copyright © 2020 American Chemical Society.
Superelasticity of Plasma- and Synthetic Membranes Resulting from Coupling of Membrane Asymmetry, Curvature, and Lipid Sorting
Biological cells are contained by a fluid lipid bilayer (plasma membrane, PM) that allows for large deformations, often exceeding 50% of the apparent initial PM area. Isolated lipids self-organize into membranes, but are prone to rupture at small (<2–4%) area strains, which limits progress for synthetic reconstitution of cellular features. Here, it is shown that by preserving PM structure and composition during isolation from cells, vesicles with cell-like elasticity can be obtained. It is found that these plasma membrane vesicles store significant area in the form of nanotubes in their lumen. These act as lipid reservoirs and are recruited by mechanical tension applied to the outer vesicle membrane. Both in experiment and theory, it is shown that a “superelastic” response emerges from the interplay of lipid domains and membrane curvature. This finding allows for bottom-up engineering of synthetic biomaterials that appear one magnitude softer and with threefold larger deformability than conventional lipid vesicles. These results open a path toward designing superelastic synthetic cells possessing the inherent mechanics of biological cells.
EMT-Induced Cell-Mechanical Changes Enhance Mitotic Rounding Strength
To undergo mitosis successfully, most animal cells need to acquire a round shape to provide space for the mitotic spindle. This mitotic rounding relies on mechanical deformation of surrounding tissue and is driven by forces emanating from actomyosin contractility. Cancer cells are able to maintain successful mitosis in mechanically challenging environments such as the increasingly crowded environment of a growing tumor, thus, suggesting an enhanced ability of mitotic rounding in cancer. Here, it is shown that the epithelial–mesenchymal transition (EMT), a hallmark of cancer progression and metastasis, gives rise to cell-mechanical changes in breast epithelial cells. These changes are opposite in interphase and mitosis and correspond to an enhanced mitotic rounding strength. Furthermore, it is shown that cell-mechanical changes correlate with a strong EMT-induced change in the activity of Rho GTPases RhoA and Rac1. Accordingly, it is found that Rac1 inhibition rescues the EMT-induced cortex-mechanical phenotype. The findings hint at a new role of EMT in successful mitotic rounding and division in mechanically confined environments such as a growing tumor.
High-Quality Graphene Using Boudouard Reaction
Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.
Electron Transport across Vertical Silicon/MoS2/Graphene Heterostructures: Towards Efficient Emitter Diodes for Graphene Base Hot Electron Transistors
Heterostructures comprising silicon, molybdenum disulfide (MoS2), and graphene are investigated with respect to the vertical current conduction mechanism. The measured current-voltage (I-V) characteristics exhibit temperature-dependent asymmetric current, indicating thermally activated charge carrier transport. The data are compared and fitted to a current transport model that confirms thermionic emission as the responsible transport mechanism across devices. Theoretical calculations in combination with the experimental data suggest that the heterojunction barrier from Si to MoS2 is linearly temperature-dependent for T = 200-300 K with a positive temperature coefficient. The temperature dependence may be attributed to a change in band gap difference between Si and MoS2, strain at the Si/MoS2 interface, or different electron effective masses in Si and MoS2, leading to a possible entropy change stemming from variation in density of states as electrons move from Si to MoS2. The low barrier formed between Si and MoS2 and the resultant thermionic emission demonstrated here make the present devices potential candidates as the emitter diode of graphene base hot electron transistors for future high-speed electronics. Copyright © 2020 American Chemical Society.
Growth of PdCoO2 films with controlled termination by molecular-beam epitaxy and determination of their electronic structure by angle-resolved photoemission spectroscopy
Utilizing the powerful combination of molecular-beam epitaxy (MBE) and angle-resolved photoemission spectroscopy (ARPES), we produce and study the effect of different terminating layers on the electronic structure of the metallic delafossite PdCoO2. Attempts to introduce unpaired electrons and synthesize new antiferromagnetic metals akin to the isostructural compound PdCrO2 have been made by replacing cobalt with iron in PdCoO2 films grown by MBE. Using ARPES, we observe similar bulk bands in these PdCoO2 films with Pd-, CoO2-, and FeO2-termination. Nevertheless, Pd- and CoO2-terminated films show a reduced intensity of surface states. Additionally, we are able to epitaxially stabilize PdFexCo1-xO2 films that show an anomaly in the derivative of the electrical resistance with respect to temperature at 20 K, but do not display pronounced magnetic order.
Combining Hydrophilic and Hydrophobic Materials in 3D Printing for Fabricating Microfluidic Devices with Spatial Wettability
The fabrication of microfluidic flow cells via projection micro-stereolithography (PμSL) has excited researchers in recent years. However, due to the inherent process properties of most commercial PμSL, microfluidic devices are fabricated in a monolithic fashion with uniform material properties across a flow cell. Yet, the large surface-to-volume ratio in microfluidics demands to tailor microchannel surface properties—particularly in planar microchannel arrangements—with spatial control and micron-scale resolution to form a desired flow profile, e.g., emulsion droplets. Here, the fabrication of planar microfluidic devices by PμSLbased 3D printing with spatial control over surface properties is presented. For that, homemade photopolymer formulations being either hydrophilic or hydrophobic are designed. Adding acrylic acid to a resin containing poly(ethylene glycol) diacrylate lowers the contact angle down to 0° against water creating a superhydrophilic surface. By utilizing 1H,1H,2H,2H-perfluorodecyl acrylate, a photopolymer formulation allowing for 3D-printing a hydrophobic microchannel surface with a contact angle >120° against water is obtained. Combining these two materials, microfluidic flow cells with spatially defined wettability are 3D-printed for emulsion formation. Finally, the resin vat of the commercial PμSL printer is switched during the printing process for fabricating multimaterial geometries, as exemplarily applied for realizing a hydrophobic-hydrophilic-hydrophobic device for forming O/W/O double emulsions.
Bio-inspired deposition of electrochemically exfoliated graphene layers for electrical resistance heating applications
Electrochemically exfoliated graphene (eeG) layers possess a variety of potential applications, e.g. as susceptor material for contactless induction heating in dynamic electro-magnetic fields, and as flexible and transparent electrode or resistivity heating elements. Spray coating of eeG dispersions was investigated in detail as a simple and fast method to deposit both, thin conducting layers and ring structures on polycarbonate substrates. The spray coating process was examined by systematic variation of dispersion concentration and volume applied to heated substrates. Properties of the obtained layers were characterized by UV-VIS spectroscopy, SEM and Confocal Scanning Microscopy. Electrical conductivity of eeG ring structures was measured using micro-four-point measurements. Modification of eeG with poly(dopamine) and post-thermal treatment yields in the reduction of the oxidized graphene proportion, an increase in electrical conductivity, and mechanical stabilization of the deposited thin layers. The chemical composition of modified eeG layer was analyzed via x-ray photoelectron spectroscopy pointing to the reductive behavior of poly(dopamine). Application oriented experiments demonstrate the direct electric current heating (Joule-Heating) effect of spray-coated eeG layers.
Gas Plasma Technology Augments Ovalbumin Immunogenicity and OT-II T Cell Activation Conferring Tumor Protection in Mice
Reactive oxygen species (ROS/RNS) are produced during inflammation and elicit protein modifications, but the immunological consequences are largely unknown. Gas plasma technology capable of generating an unmatched variety of ROS/RNS is deployed to mimic inflammation and study the significance of ROS/RNS modifications using the model protein chicken ovalbumin (Ova vs oxOva). Dynamic light scattering and circular dichroism spectroscopy reveal structural modifications in oxOva compared to Ova. T cells from Ova-specific OT-II but not from C57BL/6 or SKH-1 wild type mice presents enhanced activation after Ova addition. OxOva exacerbates this activation when administered ex vivo or in vivo, along with an increased interferon-gamma production, a known anti-melanoma agent. OxOva vaccination of wild type mice followed by inoculation of syngeneic B16F10 Ova-expressing melanoma cells shows enhanced T cell number and activation, decreased tumor burden, and elevated numbers of antigen-presenting cells when compared to their Ova-vaccinated counterparts. Analysis of oxOva using mass spectrometry identifies three hot spots regions rich in oxidative modifications that are associated with the increased T cell activation. Using Ova as a model protein, the findings suggest an immunomodulating role of multi-ROS/RNS modifications that may spur novel research lines in inflammation research and for vaccination strategies in oncology.
In Situ Fabrication of Freestanding Single-Atom-Thick 2D Metal/Metallene and 2D Metal/ Metallene Oxide Membranes: Recent Developments
In recent years, two-dimensional (2D) materials have attracted a lot of research interest as they exhibit several fascinating properties. However, outside of 2D materials derived from van der Waals layered bulk materials only a few other such materials are realized, and it remains difficult to confirm their 2D freestanding structure. Despite that, many metals are predicted to exist as 2D systems. In this review, the authors summarize the recent progress made in the synthesis and characterization of these 2D metals, so called metallenes, and their oxide forms, metallene oxides as free standing 2D structures formed in situ through the use of transmission electron microscopy (TEM) and scanning TEM (STEM) to synthesize these materials. Two primary approaches for forming freestanding monoatomic metallic membranes are identified. In the first, graphene pores as a means to suspend the metallene or metallene oxide and in the second, electron-beam sputtering for the selective etching of metal alloys or thick complex initial materials is employed to obtain freestanding single-atom-thick 2D metal. The data show a growing number of 2D metals/metallenes and 2D metal/ metallene oxides having been confirmed and point to a bright future for further discoveries of these 2D materials.