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Cytocompatible, Injectable, and Electroconductive Soft Adhesives with Hybrid Covalent/Noncovalent Dynamic Network

2019, Xu, Yong, Patsis, Panagiotis A., Hauser, Sandra, Voigt, Dagmar, Rothe, Rebecca, Günther, Markus, Cui, Meiying, Yang, Xuegeng, Wieduwild, Robert, Eckert, Kerstin, Neinhuis, Christoph, Akbar, Teuku Fawzul, Minev, Ivan R., Pietzsch, Jens, Zhang, Yixin

Synthetic conductive biopolymers have gained increasing interest in tissue engineering, as they can provide a chemically defined electroconductive and biomimetic microenvironment for cells. In addition to low cytotoxicity and high biocompatibility, injectability and adhesiveness are important for many biomedical applications but have proven to be very challenging. Recent results show that fascinating material properties can be realized with a bioinspired hybrid network, especially through the synergy between irreversible covalent crosslinking and reversible noncovalent self-assembly. Herein, a polysaccharide-based conductive hydrogel crosslinked through noncovalent and reversible covalent reactions is reported. The hybrid material exhibits rheological properties associated with dynamic networks such as self-healing and stress relaxation. Moreover, through fine-tuning the network dynamics by varying covalent/noncovalent crosslinking content and incorporating electroconductive polymers, the resulting materials exhibit electroconductivity and reliable adhesive strength, at a similar range to that of clinically used fibrin glue. The conductive soft adhesives exhibit high cytocompatibility in 2D/3D cell cultures and can promote myogenic differentiation of myoblast cells. The heparin-containing electroconductive adhesive shows high biocompatibility in immunocompetent mice, both for topical application and as injectable materials. The materials could have utilities in many biomedical applications, especially in the area of cardiovascular diseases and wound dressing.

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Giant extensional strain of magnetoactive elastomeric cylinders in uniform magnetic fields

2020, Saveliev, Dmitry V., Belyaeva, Inna A., Chashin, Dmitry V., Fetisov, Leonid Y., Romeis, Dirk, Kettl, Wolfgang, Kramarenko, Elena Yu., Saphiannikova, Marina, Stepanov, Gennady V., Shamonin, Mikhail

Elongations of magnetoactive elastomers (MAEs) under ascending-descending uniform magnetic fields were studied experimentally using a laboratory apparatus specifically designed to measure large extensional strains (up to 20%) in compliant MAEs. In the literature, such a phenomenon is usually denoted as giant magnetostriction. The synthesized cylindrical MAE samples were based on polydimethylsiloxane matrices filled with micrometer-sized particles of carbonyl iron. The impact of both the macroscopic shape factor of the samples and their magneto-mechanical characteristics were evaluated. For this purpose, the aspect ratio of the MAE cylindrical samples, the concentration of magnetic particles in MAEs and the effective shear modulus were systematically varied. It was shown that the magnetically induced elongation of MAE cylinders in the maximum magnetic field of about 400 kA/m, applied along the cylinder axis, grew with the increasing aspect ratio. The effect of the sample composition is discussed in terms of magnetic filler rearrangements in magnetic fields and the observed experimental tendencies are rationalized by simple theoretical estimates. The obtained results can be used for the design of new smart materials with magnetic-field-controlled deformation properties, e.g., for soft robotics. © 2020 by the authors.

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Organic vapor sensing behavior of polycarbonate/polystyrene/multi-walled carbon nanotube blend composites with different microstructures

2019, Li, Yilong, Pionteck, Jürgen, Pötschke, Petra, Voit, Brigitte

With the focus on the use as leakage detectors, the vapor sensing behavior of conductive polymer composites (CPCs) based on polycarbonate/polystyrene/multi-walled carbon nanotube (PC/PS/MWCNT) blends with different blend ratios was studied as well as their morphological and electrical properties. In the melt mixed blend composites, the MWCNTs are preferentially localized in PC. At the PC/PS ratio of 70/30 wt%, the composites showed a sea-island structure, while for blends containing 40 wt% or 50 wt% PS co-continuous structures were developed resulting in a reduction in the MWCNT percolation threshold. The saturated vapors of the selected solvents have good interactions to PS but different interactions to PC. At 0.75 wt% MWCNT, sea-island CPCs showed high relative resistance change (Rrel) but poor reversibility towards moderate vapors like ethyl acetate and toluene, while CPCs with co-continuous structure exhibited lower Rrel and better reversibility. All CPCs showed poor reversibility towards vapor of the good solvent dichloromethane due to strong interactions between polymers and vapor. In the vapor of the poor solvent cyclohexane, CPCs with higher PS content showed increased Rrel. After extraction of the PS component by cyclohexane, the sensing response was decreased and the Rrel of the co-continuous blend even reached negative values.

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Dry-jet wet spinning of thermally stable lignin-textile grade polyacrylonitrile fibers regenerated from chloride-based ionic liquids compounds

2020, Al Aiti, Muhannad, Das, Amit, Kanerva, Mikko, Järventausta, Maija, Johansson, Petri, Scheffler, Christina, Göbel, Michael, Jehnichen, Dieter, Brünig, Harald, Wulff, Lucas, Boye, Susanne, Arnhold, Kerstin, Kuusipalo, Jurkka, Heinrich, Gert

In this paper, we report on the use of amorphous lignin, a waste by-product of the paper industry, for the production of high performance carbon fibers (CF) as precursor with improved thermal stability and thermo-mechanical properties. The precursor was prepared by blending of lignin with polyacrylonitrile (PAN), which was previously dissolved in an ionic liquid. The fibers thus produced offered very high thermal stability as compared with the fiber consisting of pure PAN. The molecular compatibility, miscibility, and thermal stability of the system were studied by means of shear rheological measurements. The achieved mechanical properties were found to be related to the temperature-dependent relaxation time (consistence parameter) of the spinning dope and the diffusion kinetics of the ionic liquids from the fibers into the coagulation bath. Furthermore, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical tests (DMA) were utilized to understand in-depth the thermal and the stabilization kinetics of the developed fibers and the impact of lignin on the stabilization process of the fibers. Low molecular weight lignin increased the thermally induced physical shrinkage, suggesting disturbing effects on the semi-crystalline domains of the PAN matrix, and suppressed the chemically induced shrinkage of the fibers. The knowledge gained throughout the present paper allows summarizing a novel avenue to develop lignin-based CF designed with adjusted thermal stability.

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EMT-Induced Cell-Mechanical Changes Enhance Mitotic Rounding Strength

2020, Hosseini, Kamran, Taubenberger, Anna, Werner, Carsten, Fischer-Friedrich, Elisabeth

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.

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Thermal annealing to influence the vapor sensing behavior of co-continuous poly(lactic acid)/polystyrene/multiwalled carbon nanotube composites

2020, Li, Yilong, Pionteck, Jürgen, Pötschke, Petra, Voit, Brigitte

With the main purpose of being used as vapor leakage detector, the volatile organic compound (VOC) vapor sensing properties of conductive polymer blend composites were studied. Poly(lactic acid)/polystyrene/multi-walled carbon nanotube (PLA/PS/MWCNT) based conductive polymer composites (CPCs) in which the polymer components exhibit different interactions with the vapors, were prepared by melt mixing. CPCs with a blend composition of 50/50 wt% resulted in the finest co-continuous structure and selective MWCNT localization in PLA. Therefore, these composites were selected for sensor tests. Thermal annealing was applied aiming to maintain the blend structure but improving the sensing reversibility of CPC sensors towards high vapor concentrations. Different sensing protocols were applied using acetone (good solvent for PS and PLA) and cyclohexane (good solvent for PS but poor solvent for PLA) vapors. Increasing acetone vapor concentration resulted in increased relative resistance change (Rrel) of CPCs. Saturated cyclohexane vapor resulted in lower response than nearly saturated acetone vapor. The thermal annealing at 150 °C did not change the blend morphology but increased the PLA crystallinity, making the CPC sensors more resistant to vapor stimulation, resulting in lower Rrel but better reversibility after vapor exposure.

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Friction, abrasion and crack growth behavior of in-situ and ex-situ silica filled rubber composites

2020, Vaikuntam, Sankar Raman, Bhagavatheswaran, Eshwaran Subramani, Xiang, Fei, Wießner, Sven, Heinrich, Gert, Das, Amit, Stöckelhuber, Klaus Werner

The article focuses on comparing the friction, abrasion, and crack growth behavior of two different kinds of silica-filled tire tread compounds loaded with (a) in-situ generated alkoxide silica and (b) commercial precipitated silica-filled compounds. The rubber matrix consists of solution styrene butadiene rubber polymers (SSBR). The in-situ generated particles are entirely different in filler morphology, i.e., in terms of size and physical structure, when compared to the precipitated silica. However, both types of the silicas were identified as amorphous in nature. Influence of filler morphology and surface modification of silica on the end performances of the rubbers like dynamic friction, abrasion index, and fatigue crack propagation were investigated. Compared to precipitated silica composites, in-situ derived silica composites offer better abrasion behavior and improved crack propagation with and without admixture of silane coupling agents. Silane modification, particle morphology, and crosslink density were identified as further vital parameters influencing the investigated rubber properties. © 2020 by the authors.

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Toward Functional Synthetic Cells: In-Depth Study of Nanoparticle and Enzyme Diffusion through a Cross-Linked Polymersome Membrane

2019, Gumz, Hannes, Boye, Susanne, Iyisan, Banu, Krönert, Vera, Formanek, Petr, Voit, Brigitte, Lederer, Albena, Appelhans, Dietmar

Understanding the diffusion of nanoparticles through permeable membranes in cell mimics paves the way for the construction of more sophisticated synthetic protocells with control over the exchange of nanoparticles or biomacromolecules between different compartments. Nanoparticles postloading by swollen pH switchable polymersomes is investigated and nanoparticles locations at or within polymersome membrane and polymersome lumen are precisely determined. Validation of transmembrane diffusion properties is performed based on nanoparticles of different origin—gold, glycopolymer protein mimics, and the enzymes myoglobin and esterase—with dimensions between 5 and 15 nm. This process is compared with the in situ loading of nanoparticles during polymersome formation and analyzed by advanced multiple-detector asymmetrical flow field-flow fractionation (AF4). These experiments are supported by complementary i) release studies of protein mimics from polymersomes, ii) stability and cyclic pH switches test for in polymersome encapsulated myoglobin, and iii) cryogenic transmission electron microscopy studies on nanoparticles loaded polymersomes. Different locations (e.g., membrane and/or lumen) are identified for the uptake of each protein. The protein locations are extracted from the increasing scaling parameters and the decreasing apparent density of enzyme-containing polymersomes as determined by AF4. Postloading demonstrates to be a valuable tool for the implementation of cell-like functions in polymersomes.

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Transparent model concrete with tunable rheology for investigating flow and particle-migration during transport in pipes

2020, Auernhammer, Günter K., Fataei, Shirin, Haustein, Martin A., Patel, Himanshu P., Schwarze, Rüdiger, Secrieru, Egor, Mechtcherine, Viktor

The article describes the adaption and properties of a model concrete for detailed flow studies. To adapt the yield stress and plastic viscosity of the model concrete to the corresponding rheological properties of real concrete, the model concrete is made of a mixture of glass beads and a non-Newtonian fluid. The refractive index of the non-Newtonian fluid is adjusted to the refractive index of the glass beads by the addition of a further constituent. The rheological properties of the model concrete are characterised by measurements in concrete rheometers. Finally, the first exemplary results from experiments with the model concrete are presented, which give incipient impressions of the complex internal dynamics in flowing concrete.

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A Comprehensive Study about the Role of Crosslink Density on the Tribological Behavior of DLC Coated Rubber

2020, Bayrak, Suleyman, Paulkowski, Dominik, Stöckelhuber, Klaus Werner, Staar, Benjamin, Mayer, Bernd

The friction and wear behavior of coated rubber components is strongly dependent on the substrate properties. This work deals with the impact of the crosslink density, i.e., the hardness of the rubber substrate on the tribological performance of uncoated and coated rubber. The hardness of nitrile butadiene rubber (NBR) is varied altering the sulfur content. Both the uncoated and coated rubber samples are characterized in terms of surface and mechanical properties. Tribological tests comprise the examination of the macroscopic contact area and the temperature in the contact zone. It was found that the functional layer enhances the wear resistance significantly. Apparently, the wear and friction behavior of the coated rubber correlates with the hardness and the bulk properties of the substrate material.