Publikationen

Summary 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.

Abstract HepaRG is a bipotent stem cell line that can be differentiated towards hepatocyte-like and biliary-like cells. The entire cultivation process requires 1 month and relies on the addition of 2% dimethyl sulfoxide (DMSO) to the culture. Our motivation in this research is to differentiate HepaRG cells (progenitor cells and undifferentiated cells) towards hepatocyte-like cells by minimizing the cultivation time and without using DMSO treatment by instead using a microfluidic device combined with the following strategies: (a) comparison of extracellular matrices (matrigel and collagen I), (b) types of flow (one or both sides), and (c) effects of DMSO. Our results demonstrate that matrigel promotes the differentiation of progenitor cells towards hepatocytes and biliary-like cells. Moreover, the frequent formation of HepaRG cell clusters was observed by a supply of both sides of flow, and the cell viability and liver specific functions were influenced by DMSO. Finally, differentiated HepaRG progenitor cells cultured in a microfluidic device for 14 days without DMSO treatment yielded 70% of hepatocyte-like cells with a highly polarized organization that reacted to stimulation with IL-6 to produce C-reactive protein (CRP). This culture model has high potential for investigating cell differentiation and liver pathophysiology research.

Microbial resistant coatings have raised considerable interest in the biotechnological industry and clinical scenarios to combat the spreading of infections, in particular in implanted medical devices. Polymer brushes covalently attached to surfaces represent a useful platform to identify ideal compositions for preventing bacterial settlement by quantifying bacteria–surface interactions. In this work, a series of polymer brushes with different charges, positively charged poly[2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC), negatively charged poly(3-sulfopropyl methacrylate potassium salt) (PSPMA), and neutral poly(2-hydroxyethyl methacrylate) (PHEMA) were grafted onto glass surfaces by surface-initiated atom transfer radical polymerization in aqueous conditions. The antimicrobial activity of the polymer brushes against Gram-negative Escherichia coli was tested at the nano- and microscopic level on different time scales, that is, from nm to 100 μm, and ms to 24 h, respectively. The interaction between the polymer brushes and E. coli was studied by single-cell force spectroscopy (SCFS) and by quantification of the bacterial density on surfaces incubated with bacterial suspensions. E. coli firmly attached to positive PMETAC brushes with high work required for de-adhesion of 28 ± 9 nN·nm, but did not significantly bind to negatively charged PSPMA and neutral PHEMA brushes. Our studies of bacterial adhesion using polymer brushes with controllable chemistry provide essential insights into bacterial surface interactions and the origins of bacterial adhesion.

Abstract On-demand and long-term delivery of drugs are common requirements in many therapeutic applications, not easy to be solved with available smart polymers for drug encapsulation. This work presents a fundamentally different concept to address such scenarios using a self-replenishing and optogenetically controlled living material. It consists of a hydrogel containing an active endotoxin-free Escherichia coli strain. The bacteria are metabolically and optogenetically engineered to secrete the antimicrobial and antitumoral drug deoxyviolacein in a light-regulated manner. The permeable hydrogel matrix sustains a viable and functional bacterial population and permits diffusion and delivery of the synthesized drug to the surrounding medium at quantities regulated by light dose. Using a focused light beam, the site for synthesis and delivery of the drug can be freely defined. The living material is shown to maintain considerable levels of drug production and release for at least 42 days. These results prove the potential and flexibility that living materials containing engineered bacteria can offer for advanced therapeutic applications.

Abstract Developing materials to encapsulate and deliver functional proteins inside the body is a challenging yet rewarding task for therapeutic purposes. High production costs, mostly associated with the purification process, short-term stability in vivo, and controlled and prolonged release are major hurdles for the clinical application of protein-based biopharmaceuticals. In an attempt to overcome these hurdles, herein, the possibility of incorporating bacteria as protein factories into a material and externally controlling protein release using optogenetics is demonstrated. By engineering bacteria to express and secrete a red fluorescent protein in response to low doses of blue light irradiation and embedding them in agarose hydrogels, living materials are fabricated capable of releasing proteins into the surrounding medium when exposed to light. These bacterial hydrogels allow spatially confined protein expression and dosed protein release over several weeks, regulated by the area and extent of light exposure. The possibility of incorporating such complex functions in a material using relatively simple material and genetic engineering strategies highlights the immense potential and versatility offered by living materials for protein-based biopharmaceutical delivery.

The Faradaic processes related to electrochemical water reduction at the nanoporous carbon electrode under negative polarization are reduced when the concentration of aqueous sodium nitrate (NaNO3) is increased or the temperature is decreased. This effect enhances the relative contribution of ion electrosorption to the total charge storage process. Hydrogen chemisorption is reduced in aqueous 8.0 m NaNO3 due to the low degree of hydration of the Na+ cation; consequently, less free water is available for redox contributions, driving the system to exhibit electrical double-layer capacitive characteristics. Hydrogen adsorption/desorption is facilitated in 1.0 m NaNO3 due to the high molar ratio. The excess of water shifts the local pH in carbon nanopores to neutral values, giving rise to a high overpotential for dihydrogen evolution in the latter. The dilution effect on local pH shift in 1.0 m NaNO3 can be reduced by decreasing the temperature. A symmetric activated carbon cell assembled with 8.0 m NaNO3 exhibits a high capacitance and coulombic efficiency, a larger contribution of ion electrosorption to the overall charge storage process, and a stable capacitance performance at 1.6 V.

Abstract We present a facile two-step synthesis of vanadium (III) oxide/carbon core/shell hybrid material for application as lithium-ion battery electrode. The first step is a thermal treatment of a mixture of vanadium carbide (VC) and NiCl2 ⋅ 6H2O at 700 °C in an inert gas atmosphere. Elemental nickel obtained from decomposing NiCl2 ⋅ 6H2O served as a catalyst to trigger the local formation of graphitic carbon. In a second step, residual nickel was removed by washing the material in aqueous HCl. By replacing NiCl2 ⋅ 6H2O with anhydrous NiCl2, we obtained a hybrid material of vanadium carbide-derived carbon and a vanadium carbide core. Material characterization revealed a needle-like morphology of the rhombohedral V2O3 along with two carbon species with a different degree of graphitic ordering. We varied the NiCl2 ⋅ 6H2O-to-VC ratio, and the optimized material yielded a capacity of 110 mAh ⋅ g−1 at 2.5 A ⋅ g−1 which increased to 225 mAh ⋅ g−1 at 0.1 A ⋅ g−1 after 500 cycles in the potential range of 0.01-3.00 V vs. Li/Li+. This enhanced performance is in stark contrast to the loss of lithium uptake capacity when using commercially available V2O3 mixed with carbon black, where 93 % of the initial capacity was lost after 50 cycles.

Negative electrode materials that possess fast lithium insertion kinetics are in high demand for high power lithium-ion batteries and hybrid supercapacitor applications. In this work, hydrogen titanium oxides are synthesized by a proton exchange reaction with sodium titanium oxide, resulting in the H2Ti3O7 phase. We show that a gradual water release in four steps yields intermediate phases of hydrogen titanate with different degrees of interlayer protonation. In addition, a synthesis route using zinc nitrate is explored yielding H2Ti3O7 with a high rutile content. This material dehydrates already at a lower temperature, resulting in a lamellar rutile titania phase. The hydrogen titanate materials with partially protonated interlayers are tested as negative electrodes in a lithium-ion battery and hybrid supercapacitor setup, showing an improved performance compared to the fully protonated phases. The performance in half-cells reaches around 168 mAh/g, with high retention of 42 mAh/g at 10 A/g. This translates to an energy of 88 Wh/kg for a full-cell with a maximum power of 9.2 kW/kg and high cycling stability over 1000 cycles.

Asymmetric hybrid supercapacitors (AHSCs) combine high specific energy and power by merging two electrodes with capacitive and Faradaic charge storage mechanisms. In this study, we introduce AHSC cells that use lithium titanate and activated carbon electrodes in an alkali-ion containing ionic liquid electrolyte. With this cell concept, it is possible to operate the activated carbon electrode in a higher potential window. Consequently, higher cell voltages and a reduced carbon electrode mass can be used, resulting in significantly increased energy compared to aqueous or organic electrolytes. We demonstrate the feasibility of this cell concept for both lithium- and sodium-ion intercalation, underlining the general validity of our approach. Our prototype cells already reach high specific energies of 100 W h/kg, while maintaining a specific power of up to 2 kW/kg and cycling stability of over 1500 cycles. Owing to the IL electrolyte, stable cycling of an AHSC at 80 °C is demonstrated for the first time.

In recent years, a wealth of new desalination technologies based on reversible electrochemical redox reactions has emerged. Among them, the use of redox-active electrolytes is highly attractive due to the high production rate and energy efficiency. Yet, these technologies suffer from the imperfect permselectivity of polymer membranes. Our present work demonstrates the promising desalination performance of a sodium superionic conductor (NASICON) for selective removal of sodium against iodide in a half-cell configuration consisting of an activated carbon electrode in aqueous 600 mM NaI solution. For feedwater with aqueous 600 mM NaCl, the desalination cell exhibited a stable performance over a month with more than 400 operation cycles with the aid of high sodium permselectivity of the NASICON membrane against iodide (99.9–100%). The cell exhibited a maximum sodium removal capacity of 69 ± 4 mg/g (equivalent to the NaCl salt uptake capacity of 87 ± 4 mg/g) with a charge efficiency of 81 ± 3%.