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    Benchmark of Simplified Time-Dependent Density Functional Theory for UV–Vis Spectral Properties of Porphyrinoids
    (Weinheim : Wiley-VCH Verlag, 2019) Batra, Kamal; Zahn, Stefan; Heine, Thomas
    Time-dependent density functional theory is thoroughly benchmarked for the predictive calculation of UV–vis spectra of porphyrin derivatives. With the aim to provide an approach that is computationally feasible for large-scale applications such as biological systems or molecular framework materials, albeit performing with high accuracy for the Q-bands, the results given by various computational protocols, including basis sets, density-functionals (including gradient corrected local functionals, hybrids, double hybrids and range-separated functionals), and various variants of time-dependent density functional theory, including the simplified Tamm–Dancoff approximation, are compared. An excellent choice for these calculations is the range-separated functional CAM-B3LYP in combination with the simplified Tamm–Dancoff approximation and a basis set of double-ζ quality def2-SVP (mean absolute error [MAE] of ≈0.05 eV). This is not surpassed by more expensive approaches, not even by double hybrid functionals, and solely systematic excitation energy scaling slightly improves the results (MAE ≈0.04 eV).
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    Biocatalytic Degradation Efficiency of Postconsumer Polyethylene Terephthalate Packaging Determined by Their Polymer Microstructures
    (Weinheim : Wiley-VCH, 2019) Wei, Ren; Breite, Daniel; Song, Chen; Gräsing, Daniel; Ploss, Tina; Hille, Patrick; Schwerdtfeger, Ruth; Matysik, Jörg; Schulze, Agnes; Zimmermann, Wolfgang
    Polyethylene terephthalate (PET) is the most important mass-produced thermoplastic polyester used as a packaging material. Recently, thermophilic polyester hydrolases such as TfCut2 from Thermobifida fusca have emerged as promising biocatalysts for an eco-friendly PET recycling process. In this study, postconsumer PET food packaging containers are treated with TfCut2 and show weight losses of more than 50% after 96 h of incubation at 70 °C. Differential scanning calorimetry analysis indicates that the high linear degradation rates observed in the first 72 h of incubation is due to the high hydrolysis susceptibility of the mobile amorphous fraction (MAF) of PET. The physical aging process of PET occurring at 70 °C is shown to gradually convert MAF to polymer microstructures with limited accessibility to enzymatic hydrolysis. Analysis of the chain-length distribution of degraded PET by nuclear magnetic resonance spectroscopy reveals that MAF is rapidly hydrolyzed via a combinatorial exo- and endo-type degradation mechanism whereas the remaining PET microstructures are slowly degraded only by endo-type chain scission causing no detectable weight loss. Hence, efficient thermostable biocatalysts are required to overcome the competitive physical aging process for the complete degradation of postconsumer PET materials close to the glass transition temperature of PET.
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    Fibroblast Response to Nanocolumnar TiO2 Structures Grown by Oblique Angle Sputter Deposition
    (Weinheim : Wiley-VCH, 2021) Kapprell, Uta; Friebe, Sabrina; Grüner, Susann; Grüner, Christoph; Kupferer, Astrid; Rauschenbach, Bernd; Mayr, Stefan G.
    Cells are established to sense and respond to the properties, including nano- and microscale morphology, of the substrate they adhere to, which opens up the possibility to tailor bioactivity. With this background, the potential of tilted TiO2 nanostructures grown by oblique angle sputtering to affect fibroblasts with particular focus on inducing anisotropy in cell behavior is explored. By depositing TiO2 at different oblique angles relative to the substrate normal, morphologies, columnar tilt angle, roughness, and distances between neighbored nanocolumns can be adjusted. To assess bioactivity of the resulting structures, L929-mouse fibroblasts are seeded in vitro on TiO2 nanostructured substrates. Angle-dependent movement and velocity distributions of the cells on differently tilted columns and a smooth reference sample are studied. Cell proliferation rates and cell areas are additional factors which provide information about viability and the well-being of cells. It could be shown that the local topography of the surface has an influence on the directed movement of the cells. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH
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    Nanoporous Morphogenesis in Amorphous Carbon Layers: Experiments and Modeling on Energetic Ion Induced Self‐Organization
    (Weinheim : Wiley-VCH Verlag, 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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    Programing stimuli-responsiveness of gelatin with electron beams: Basic effects and development of a hydration-controlled biocompatible demonstrator
    (London : Nature Publishing Group, 2017) Riedel, Stefanie; Heyart, Benedikt; Apel, Katharina S.; Mayr, Stefan G.
    Biomimetic materials with programmable stimuli responsiveness constitute a highly attractive material class for building bioactuators, sensors and active control elements in future biomedical applications. With this background, we demonstrate how energetic electron beams can be utilized to construct tailored stimuli responsive actuators for biomedical applications. Composed of collagen-derived gelatin, they reveal a mechanical response to hydration and changes in pH-value and ion concentration, while maintaining their excellent biocompatibility and biodegradability. While this is explicitly demonstrated by systematic characterizing an electron-beam synthesized gelatin-based actuator of cantilever geometry, the underlying materials processes are also discussed, based on the fundamental physical and chemical principles. When applied within classical electron beam lithography systems, these findings pave the way for a novel class of highly versatile integrated bioactuators from micro-to macroscales.
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    Energetic electron assisted synthesis of highly tunable temperature-responsive collagen/elastin gels for cyclic actuation: macroscopic switching and molecular origins
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 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).
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    Studying hydrogen bonding and dynamics of the acetylate groups of the Special Pair of Rhodobacter sphaeroides WT
    ([London] : Macmillan Publishers Limited, part of Springer Nature, 2019) Gräsing, Daniel; Dziubińska-Kühn, Katarzyna M.; Zahn, Stefan; Alia, A.; Matysik, Jörg
    Although the cofactors in the bacterial reaction centre of Rhodobacter sphaeroides wild type (WT) are arranged almost symmetrically in two branches, the light-induced electron transfer occurs selectively in one branch. As origin of this functional symmetry break, a hydrogen bond between the acetyl group of PL in the primary donor and His-L168 has been discussed. In this study, we investigate the existence and rigidity of this hydrogen bond with solid-state photo-CIDNP MAS NMR methods offering information on the local electronic structure due to highly sensitive and selective NMR experiments. On the time scale of the experiment, the hydrogen bond between PL and His-L168 appears to be stable and not to be affected by illumination confirming a structural asymmetry within the Special Pair.
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    Detection of small bunches of ions using image charges
    (London : Nature Publishing Group, 2018) Räcke, Paul; Spemann, Daniel; Gerlach, Jürgen W.; Rauschenbach, Bernd; Meijer, Jan
    A concept for detection of charged particles in a single fly-by, e.g. within an ion optical system for deterministic implantation, is presented. It is based on recording the image charge signal of ions moving through a detector, comprising a set of cylindrical electrodes. This work describes theoretical and practical aspects of image charge detection (ICD) and detector design and its application in the context of real time ion detection. It is shown how false positive detections are excluded reliably, although the signal-to-noise ratio is far too low for time-domain analysis. This is achieved by applying a signal threshold detection scheme in the frequency domain, which - complemented by the development of specialised low-noise preamplifier electronics - will be the key to developing single ion image charge detection for deterministic implantation.
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    Design of biomimetic collagen matrices by reagent-free electron beam induced crosslinking: Structure-property relationships and cellular response
    (Amsterdam [u.a.] : Elsevier Science, 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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    Structural Transitions in Ge2Sb2Te5 Phase Change Memory Thin Films Induced by Nanosecond UV Optical Pulses
    (Basel : MDPI, 2020) Behrens, Mario; Lotnyk, Andriy; Bryja, Hagen; Gerlach, Jürgen W.; Rauschenbach, Bernd
    Ge-Sb-Te-based phase change memory alloys have recently attracted a lot of attention due to their promising applications in the fields of photonics, non-volatile data storage, and neuromorphic computing. Of particular interest is the understanding of the structural changes and underlying mechanisms induced by short optical pulses. This work reports on structural changes induced by single nanosecond UV laser pulses in amorphous and epitaxial Ge2Sb2Te5 (GST) thin films. The phase changes within the thin films are studied by a combined approach using X-ray diffraction and transmission electron microscopy. The results reveal different phase transitions such as crystalline-to-amorphous phase changes, interface assisted crystallization of the cubic GST phase and structural transformations within crystalline phases. In particular, it is found that crystalline interfaces serve as crystallization templates for epitaxial formation of metastable cubic GST phase upon phase transitions. By varying the laser fluence, GST thin films consisting of multiple phases and different amorphous to crystalline volume ratios can be achieved in this approach, offering a possibility of multilevel data storage and realization of memory devices with very low resistance drift. In addition, this work demonstrates amorphization and crystallization of GST thin films by using only one UV laser with one single pulse duration and one wavelength. Overall, the presented results offer new perspectives on switching pathways in Ge-Sb-Te-based materials and show the potential of epitaxial Ge-Sb-Te thin films for applications in advanced phase change memory concepts.