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- ItemBenchmark of Simplified Time-Dependent Density Functional Theory for UV–Vis Spectral Properties of Porphyrinoids(Weinheim : Wiley-VCH Verlag, 2019) Batra, Kamal; Zahn, Stefan; Heine, ThomasTime-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).
- ItemBiocatalytic 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, WolfgangPolyethylene 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.
- ItemDesign 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.
- ItemInfluence of substrate dimensionality on the growth mode of epitaxial 3D-bonded GeTe thin films: From 3D to 2D growth(Amsterdam [u.a.] : Elsevier Science, 2019) Hilmi, Isom; Lotnyk, Andriy; Gerlach, Jürgen W.; Schumacher, Philipp; Rauschenbach, BerndThe pseudo-binary line of Sb2Te3-GeTe contains alloys featuring different crystalline characteristics from two-dimensionally (2D-) bonded Sb2Te3 to three-dimensionally (3D-) bonded GeTe. Here, the growth scenario of 3D-bonded GeTe is investigated by depositing epitaxial GeTe thin films on Si(111) and Sb2Te3-buffered Si(111) substrates using pulsed laser deposition (PLD). GeTe thin films were grown in trigonal structure within a temperature window for epitaxial growth of 210–270 °C on unbuffered Si(111) substrates. An unconventional growth onset was characterized by the formation of a thin amorphous GeTe layer. Nonetheless, the as-grown film is found to be crystalline. Furthermore, by employing a 2D-bonded Sb2Te3 thin film as a seeding layer on Si(111), a 2D growth of GeTe is harnessed. The epitaxial window can substantially be extended especially towards lower temperatures down to 145 °C. Additionally, the surface quality is significantly improved. The inspection of the local structure of the epitaxial films reveals the presence of a superposition of twinned domains, which is assumed to be an intrinsic feature of such thin films. This work might open a way for an improvement of an epitaxy of a 3D-bonded material on a highly-mismatched substrate (e.g. Si (111)) by employing a 2D-bonded seeding layer (e.g. Sb2Te3).
- ItemIon beam figuring machine for ultra-precision silicon spheres correction(Amsterdam [u.a.] : Elsevier Science, 2015) Arnold, Thomas; Pietag, FredIn the framework of the Avogadro project, isotopically enriched 28Si spheres had been manufactured as artifacts for the assessment of various physical quantities including the sphere volume which finally leads to a very accurate determination of the Avogadro constant NA. The Avogadro constant is an important input datum for the redefinition of the unit of mass, the kilogram, on the basis of fundamental physical constants. During the recent measurement campaign, it has turned out that one of the main contributions to the overall uncertainty of NA is the sphericity error and consequently the interferometric volume measurement. Since chemical–mechanical polishing has reached its limits with respect to form accuracy due to the sensitivity of material removal rate to crystal orientation, it has been proposed to use ion beam figuring for further reduction of sphericity error from currently 50 nm PV to values <10 nm PV. In this paper, a new concept and realization of a multi-axis ion beam figuring machine dedicated for deterministic correction of silicon spheres is presented. Aspects of long term tool stability and alignment procedures in order to relate the ion beam footprint to the sphere surface are covered. Furthermore, a process dwell time calculation and tool path generation method dedicated for spheres manufacturing will be presented and discussed.
- ItemEnergetic 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).
- ItemStudying 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, JörgAlthough 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.