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Nanoporous Morphogenesis in Amorphous Carbon Layers: Experiments and Modeling on Energetic Ion Induced Self‐Organization

2021, Hoffmann, Daniel T., Dietrich, Johannes, Mändl, Stephan, Zink, Mareike, Mayr, Stefan G.

Nanoporous amorphous carbon constitutes a highly relevant material for a multitude of applications ranging from energy to environmental and biomedical systems. In the present work, it is demonstrated experimentally how energetic ions can be utilized to tailor porosity of thin sputter deposited amorphous carbon films. The physical mechanisms underlying self-organized nanoporous morphogenesis are unraveled by employing extensive molecular dynamics and phase field models across different length scales. It is demonstrated that pore formation is a defect induced phenomenon, in which vacancies cluster in a spinodal decomposition type of self-organization process, while interstitials are absorbed by the amorphous matrix, leading to additional volume increase and radiation induced viscous flow. The proposed modeling framework is capable to reproduce and predict the experimental observations from first principles and thus opens the venue for computer assisted design of nanoporous frameworks.

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Design of biomimetic collagen matrices by reagent-free electron beam induced crosslinking: Structure-property relationships and cellular response

2019, Riedel, Stefanie, Hietschold, Philine, Krömmelbein, Catharina, Kunschmann, Tom, Konieczny, Robert, Knolle, Wolfgang, Mierke, Claudia T., Zink, Mareike, Mayr, Stefan G.

Novel strategies to mimic mammalian extracellular matrix (ECM) in vitro are desirable to study cell behavior, diseases and new agents in drug delivery. Even though collagen represents the major constituent of mammalian ECM, artificial collagen hydrogels with characteristic tissue properties such as network size and stiffness are difficult to design without application of chemicals which might be even cytotoxic. In our study we investigate how high energy electron induced crosslinking can be utilized to precisely tune collagen properties for ECM model systems. Constituting a minimally invasive approach, collagen residues remain intact in the course of high energy electron treatment. Quantification of the 3D pore size of the collagen network as a function of irradiation dose shows an increase in density leading to decreased pore size. Rheological measurements indicate elevated storage and loss moduli correlating with an increase in crosslinking density. In addition, cell tests show well maintained viability of NIH 3T3 cells for irradiated collagen gels indicating excellent cellular acceptance. With this, our investigations demonstrate that electron beam crosslinked collagen matrices have a high potential as precisely tunable ECM-mimetic systems with excellent cytocompatibility.

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Energetic electron assisted synthesis of highly tunable temperature-responsive collagen/elastin gels for cyclic actuation: macroscopic switching and molecular origins

2019, Wilharm, Nils, Fischer, Tony, Ott, Florian, Konieczny, Robert, Zink, Mareike, Beck-Sickinger, Annette G., Mayr, Stefan G.

Thermoresponsive bio-only gels that yield sufficiently large strokes reversibly and without large hysteresis at a well-defined temperature in the physiological range, promise to be of value in biomedical application. Within the present work we demonstrate that electron beam modification of a blend of natural collagen and elastin gels is a route to achieve this goal, viz. to synthesize a bioresorbable gel with largely reversible volume contractions as large as 90% upon traversing a transition temperature that can be preadjusted between 36 °C and 43 °C by the applied electron dose. Employing circular dichroism and temperature depending confocal laser scanning microscopy measurements, we furthermore unravel the mechanisms underlying this macroscopic behavior on a molecular and network level, respectively and suggest a stringent picture to account for the experimental observations. © 2019, The Author(s).