Search Results
Gas Plasma Technology Augments Ovalbumin Immunogenicity and OT-II T Cell Activation Conferring Tumor Protection in Mice
2021, Clemen, Ramona, Freund, Eric, Mrochen, Daniel, Miebach, Lea, Schmidt, Anke, Rauch, Bernhard H., Lackmann, Jan‐Wilm, Martens, Ulrike, Wende, Kristian, Lalk, Michael, Delcea, Mihaela, Bröker, Barbara M., Bekeschus, Sander
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.
Mixed Ionic-Electronic Conductivity, Redox Behavior and Thermochemical Expansion of Mn-Substituted 5YSZ as an Interlayer Material for Reversible Solid Oxide Cells
2021, Natoli, Alejandro, Arias-Serrano, Blanca I., Rodríguez-Castellón, Enrique, Żurawska, Agnieszka, Frade, Jorge R., Yaremchenko, Aleksey. A.
Manganese-substituted 5 mol.% yttria-stabilized zirconia (5YSZ) was explored as a prospective material for protective interlayers between electrolyte and oxygen electrodes in reversible solid oxide fuel/electrolysis cells. [(ZrO2)0.95(Y2O3)0.05]1−x[MnOy]x (x = 0.05, 0.10 and 0.15) ceramics with cubic fluorite structure were sintered in air at 1600 °C. The characterization included X-ray diffraction (XRD), scanning electron microscopy (SEM)/energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), thermogravimetry and dilatometry in controlled atmospheres, electrical conductivity measurements, and determination of oxygen-ion transference numbers by the electromotive force (EMF) technique. Mn-substituted 5YSZ solid solutions exhibit variable oxygen nonstoichiometry with manganese cations in a mixed 2+/3+ oxidation state under oxidizing conditions. Substitution by manganese gradually increases the extent of oxygen content variation on thermal/redox cycling, chemical contribution to thermal expansion and dimensional changes on reduction. It also deteriorates oxygen-ionic conductivity and improves p-type electronic conductivity under oxidizing conditions, leading to a gradual transformation from predominantly ionic to prevailing electronic transport with increasing x. Mn2+/3+→Mn2+ transformation under reducing atmospheres is accompanied by the suppression of electronic transport and an increase in ionic conductivity. All Mn-substituted 5YSZ ceramics are solid electrolytes under reducing conditions. Prolonged treatments in reducing atmospheres, however, promote microstructural changes at the surface of bulk ceramics and Mn exsolution. Mn-substituted 5YSZ with 0.05 ≤ x < 0.10 is considered the most suitable for the interlayer application, due to the best combination of relevant factors, including oxygen content variations, levels of ionic/electronic conductivity and thermochemical expansion.
Development of Ni-Sr(V,Ti)O3-δ Fuel Electrodes for Solid Oxide Fuel Cells
2021, Serôdio Costa, Bernardo F., Arias-Serrano, Blanca I., Yaremchenko, Aleksey A.
A series of strontium titanates-vanadates (STVN) with nominal cation composition Sr1-xTi1-y-zVyNizO3-δ (x = 0–0.04, y = 0.20–0.40 and z = 0.02–0.12) were prepared by a solid-state reaction route in 10% H2–N2 atmosphere and characterized under reducing conditions as potential fuel electrode materials for solid oxide fuel cells. Detailed phase evolution studies using XRD and SEM/EDS demonstrated that firing at temperatures as high as 1200◦C is required to eliminate undesirable secondary phases. Under such conditions, nickel tends to segregate as a metallic phase and is unlikely to incorporate into the perovskite lattice. Ceramic samples sintered at 1500◦C ex-hibited temperature-activated electrical conductivity that showed a weak p(O2 ) dependence and increased with vanadium content, reaching a maximum of ~17 S/cm at 1000◦C. STVN ceramics showed moderate thermal expansion coefficients (12.5–14.3 ppm/K at 25–1100◦C) compatible with that of yttria-stabilized zirconia (8YSZ). Porous STVN electrodes on 8YSZ solid electrolytes were fabricated at 1100◦C and studied using electrochemical impedance spectroscopy at 700–900◦C in an atmosphere of diluted humidified H2 under zero DC conditions. As-prepared STVN electrodes demonstrated comparatively poor electrochemical performance, which was attributed to insufficient intrinsic electrocatalytic activity and agglomeration of metallic nickel during the high-temperature synthetic procedure. Incorporation of an oxygen-ion-conducting Ce0.9Gd0.1O2-δ phase (20–30 wt.%) and nano-sized Ni as electrocatalyst (≥1 wt.%) into the porous electrode structure via infiltration re-sulted in a substantial improvement in electrochemical activity and reduction of electrode polarization resistance by 6–8 times at 900◦C and ≥ one order of magnitude at 800◦C.
Influence of oxygen admixture on plasma nitrocarburizing process and monitoring of an active screen plasma treatment
2021, Böcker, Jan, Dalke, Anke, Puth, Alexander, Schimpf, Christian, Röpcke, Jürgen, van Helden, Jean-Pierre H., Biermann, Horst
The effect of a controlled oxygen admixture to a plasma nitrocarburizing process using active screen technology and an active screen made of carbon was investigated to control the carburizing potential within the plasma-assisted process. Laser absorption spectroscopy was used to determine the resulting process gas composition at different levels of oxygen admixture using O2 and CO2, respectively, as well as the long-term trends of the concentration of major reaction products over the duration of a material treatment of ARMCO® iron. The short-term studies of the resulting process gas composition, as a function of oxygen addition to the process feed gases N2 and H2, showed that a stepwise increase in oxygen addition led to the formation of oxygen-containing species, such as CO, CO2, and H2 O, and to a significant decrease in the concentrations of hydrocarbons and HCN. Despite increased oxygen concentration within the process gas, no oxygen enrichment was observed in the compound layer of ARMCO® iron; however, the diffusion depth of nitrogen and carbon increased significantly. Increasing the local nitrogen concentration changed the stoichiometry of the ε-Fe3 (N,C)1+x phase in the compound layer and opens up additional degrees of freedom for improved process control.
Understanding Surface Modifications Induced via Argon Plasma Treatment through Secondary Electron Hyperspectral Imaging
2021, Farr, Nicholas, Thanarak, Jeerawan, Schäfer, Jan, Quade, Antje, Claeyssens, Frederik, Green, Nicola, Rodenburg, Cornelia
Understanding the effects that sterilization methods have on the surface of a biomaterial is a prerequisite for clinical deployment. Sterilization causes alterations in a material's surface chemistry and surface structures that can result in significant changes to its cellular response. Here we compare surfaces resulting from the application of the industry standard autoclave sterilisation to that of surfaces resulting from the use of low-pressure Argon glow discharge within a novel gas permeable packaging method in order to explore a potential new biomaterial sterilisation method. Material surfaces are assessed by applying secondary electron hyperspectral imaging (SEHI). SEHI is a novel low-voltage scanning electron microscopy based characterization technique that, in addition to capturing topographical images, also provides nanoscale resolution chemical maps by utilizing the energy distribution of emitted secondary electrons. Here, SEHI maps are exploited to assess the lateral distributions of diverse functional groups that are effected by the sterilization treatments. This information combined with a range of conventional surface analysis techniques and a cellular metabolic activity assay reveals persuasive reasons as to why low-pressure argon glow discharge should be considered for further optimization as a potential terminal sterilization method for PGS-M, a functionalized form of poly(glycerol sebacate) (PGS).
Tunable Pseudo-Piezoelectric Effect in Doped Calcium Titanate for Bone Tissue Engineering
2021, Riaz, Abdullah, Witte, Kerstin, Bodnar, Wiktor, Seitz, Hermann, Schell, Norbert, Springer, Armin, Burkel, Eberhard
CaTiO3 is a promising candidate as a pseudo-piezoelectric scaffold material for bone implantation. In this study, pure and magnesium/iron doped CaTiO3 are synthesized by sol-gel method and spark plasma sintering. Energy dispersive X-ray mapping confirm the homogenous distribution of doping elements in sintered samples. High-energy X-ray diffraction investigations reveal that doping of nanostructured CaTiO3 increased the strain and defects in the structure of CaTiO3 compared to the pure one. This led to a stronger pseudo-piezoelectric effect in the doped samples. The charge produced in magnesium doped CaTiO3 due to the direct piezoelectric effect is (2.9 ± 0.1) pC which was larger than the one produced in pure CaTiO3 (2.1 ± 0.3) pC, whereas the maximum charge was generated by iron doped CaTiO3 with (3.6 ± 0.2) pC. Therefore, the pseudo-piezoelectric behavior can be tuned by doping. This tuning of pseudo-piezoelectric response provides the possibility to systematically study the bone response using different piezoelectric strengths and possibly adjust for bone tissue engineering.
Bacterial symbiont subpopulations have different roles in a deep-sea symbiosis
2021, Hinzke, Tjorven, Kleiner, Manuel, Meister, Mareike, Schlüter, Rabea, Hentschker, Christian, Pané-Farré, Jan, Hildebrandt, Petra, Felbeck, Horst, Sievert, Stefan M, Bonn, Florian, Völker, Uwe, Becher, Dörte, Schweder, Thomas, Markert, Stephanie
The hydrothermal vent tubeworm Riftia pachyptila hosts a single 16S rRNA phylotype of intracellular sulfur-oxidizing symbionts, which vary considerably in cell morphology and exhibit a remarkable degree of physiological diversity and redundancy, even in the same host. To elucidate whether multiple metabolic routes are employed in the same cells or rather in distinct symbiont subpopulations, we enriched symbionts according to cell size by density gradient centrifugation. Metaproteomic analysis, microscopy, and flow cytometry strongly suggest that Riftia symbiont cells of different sizes represent metabolically dissimilar stages of a physiological differentiation process: While small symbionts actively divide and may establish cellular symbiont-host interaction, large symbionts apparently do not divide, but still replicate DNA, leading to DNA endoreduplication. Moreover, in large symbionts, carbon fixation and biomass production seem to be metabolic priorities. We propose that this division of labor between smaller and larger symbionts benefits the productivity of the symbiosis as a whole.
Internal Crack Initiation and Growth Starting from Artificially Generated Defects in Additively Manufactured Ti6Al4V Specimen in the VHCF Regime
2021, Wickmann, Carsten, Benz, Christopher, Heyer, Horst, Witte-Bodnar, Kerstin, Schäfer, Jan, Sander, Manuela
The aim of the present work was to investigate the ‘fine granular area’ (FGA) formation based on artificially generated internal defects in additively manufactured Ti6Al4V specimens in the early stage of fatigue crack growth in the ‘very high cycle fatigue’ (VHCF) regime. Fatigue tests were performed with constant amplitude at pure tension-compression loading (R = −1) using an ultrasonic fatigue testing setup. Failed specimens were investigated using optical microscopy, high-resolution ‘scanning electron microscopy’ (SEM), and ‘focused ion beam’ (FIB) techniques. Further, the paper introduces alternative proposals to identify the FGA layer beneath the fracture surfaces in terms of the ‘cross section polishing’ (CSP) technique and metallic grindings with special attention paid to the crack origin, the surrounding microstructure, and the expansion of the nanograin layer beneath the fracture surface. Different existing fracture mechanical approaches were applied to evaluate if an FGA formation is possible. Moreover, the results were discussed in comparison to the experimental findings.
Prenormative verification and validation of a protocol for measuring magnetite–maghemite ratios in magnetic nanoparticles
2021, Bogart, Lara K., Fock, Jeppe, da Costa, Geraldo M., Witte, Kerstin, Greneche, Jean-Marc, Zukrowski, Jan, Sikora, Marcin, Latta, Drew E., Scherer, Michelle M., Hansen, Mikkel Fougt, Frandsen, Cathrine, Pankhurst, Quentin A.
An important step in establishing any new metrological method is a prenormative interlaboratory study, designed to verify and validate the method against its stated aims. Here, the 57Fe Mössbauer spectrometric ‘centre of gravity’ (COG) method was tested as a means of quantifying the magnetite/maghemite (Fe3O4/γ-Fe2O3) composition ratio in biphasic magnetic nanoparticles. The study involved seven laboratories across Europe and North and South America, and six samples—a verification set of three microcrystalline mixtures of known composition, and a validation set of three nanoparticle samples of unknown composition. The spectra were analysed by each participant using in-house fitting packages, and ex post facto by a single operator using an independent package. Repeatability analysis was performed using Mandel’s h statistic and modified Youden plots. It is shown that almost all (83/84) of the Mandel h statistic values fall within the 0.5% significance level, with the one exception being borderline. Youden-based pairwise analysis indicates the dominance of random uncertainties; and in almost all cases the data analysis phase is only a minor contributor to the overall measurement uncertainty. It is concluded that the COG method is a robust and promising candidate for its intended purpose.
Automatic Actin Filament Quantification and Cell Shape Modeling of Osteoblasts on Charged Ti Surfaces
2021, Gruening, Martina, Dawson, Jonathan E., Voelkner, Christian, Neuber, Sven, Fricke, Katja, van Rienen, Ursula, Speller, Sylvia, Helm, Christiane A., Nebe, J. Barbara
Surface charges at the cell–biomaterial interface are known to determine cellular functions. Previous findings on cell signaling indicate that osteoblastic cells favor certain moderately positive surface charges, whereas highly positive charges are not tolerated. In this study, we aimed to gain deeper insights into the influence exerted by surface charges on the actin cytoskeleton and the cell shape. We analyzed surfaces with a negative, moderately positive, and highly positive zeta (ζ) potential: titanium (Ti), Ti with plasma polymerized allylamine (PPAAm), and Ti with a polydiallyldimethylammonium chloride (PDADMA) multilayer, respectively. We used the software FilaQuant for automatic actin filament quantification of osteoblastic MG-63s, analyzed the cell edge height with scanning ion conductance microscopy (SICM), and described the cellular shape via a mathematical vertex model. A significant enhancement of actin filament formation was achieved on moderately positive (+7 mV) compared with negative ζ-potentials (−87 mV). A hampered cell spreading was reflected in a diminished actin filament number and length on highly positively charged surfaces (+50 mV). Mathematical simulations suggested that in these cells, cortical tension forces dominate the cell–substrate adhesion forces. Our findings present new insights into the impact of surface charges on the overall cell shape and even intracellular structures.
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