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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).
- ItemCytocompatible, Injectable, and Electroconductive Soft Adhesives with Hybrid Covalent/Noncovalent Dynamic Network(Weinheim : Wiley-VCH, 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, YixinSynthetic 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.
- 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.
- ItemIn-Gel Direct Laser Writing for 3D-Designed Hydrogel Composites That Undergo Complex Self-Shaping(Weinheim : Wiley-VCH, 2017) Nishiguchi, Akihiro; Mourran, Ahmed; Zhang, Hang; Möller, MartinSelf-shaping and actuating materials inspired by biological system have enormous potential for biosensor, microrobotics, and optics. However, the control of 3D-complex microactuation is still challenging due to the difficulty in design of nonuniform internal stress of micro/nanostructures. Here, we develop in-gel direct laser writing (in-gel DLW) procedure offering a high resolution inscription whereby the two materials, resin and hydrogel, are interpenetrated on a scale smaller than the wavelength of the light. The 3D position and mechanical properties of the inscribed structures could be tailored to a resolution better than 100 nm over a wide density range. These provide an unparalleled means of inscribing a freely suspended microstructures of a second material like a skeleton into the hydrogel body and also to direct isotropic volume changes to bending and distortion motions. In the combination with a thermosensitive hydrogel rather small temperature variations could actuate large amplitude motions. This generates complex modes of motion through the rational engineering of the stresses present in the multicomponent material. More sophisticated folding design would realize a multiple, programmable actuation of soft materials. This method inspired by biological system may offer the possibility for functional soft materials capable of biomimetic actuation and photonic crystal application.
- ItemDNA Nanotechnology Enters Cell Membranes(Weinheim : Wiley-VCH, 2019) Huo, Shuaidong; Li, Hongyan; Boersma, Arnold J.; Herrmann, AndreasDNA is more than a carrier of genetic information: It is a highly versatile structural motif for the assembly of nanostructures, giving rise to a wide range of functionalities. In this regard, the structure programmability is the main advantage of DNA over peptides, proteins, and small molecules. DNA amphiphiles, in which DNA is covalently bound to synthetic hydrophobic moieties, allow interactions of DNA nanostructures with artificial lipid bilayers and cell membranes. These structures have seen rapid growth with great potential for medical applications. In this Review, the current state of the art of the synthesis of DNA amphiphiles and their assembly into nanostructures are first summarized. Next, an overview on the interaction of these DNA amphiphiles with membranes is provided, detailing on the driving forces and the stability of the interaction. Moreover, the interaction with cell surfaces in respect to therapeutics, biological sensing, and cell membrane engineering is highlighted. Finally, the challenges and an outlook on this promising class of DNA hybrid materials are discussed.
- ItemToward Functional Synthetic Cells: In-Depth Study of Nanoparticle and Enzyme Diffusion through a Cross-Linked Polymersome Membrane(Weinheim : Wiley-VCH, 2019) Gumz, Hannes; Boye, Susanne; Iyisan, Banu; Krönert, Vera; Formanek, Petr; Voit, Brigitte; Lederer, Albena; Appelhans, DietmarUnderstanding 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.
- ItemMaking Sense of Complex Carbon and Metal/Carbon Systems by Secondary Electron Hyperspectral Imaging(Weinheim : Wiley-VCH, 2019) Abrams, Kerry J.; Dapor, Maurizio; Stehling, Nicola; Azzolini, Martina; Kyle, Stephan J.; Schäfer, Jan; Quade, Antje; Mika, Filip; Kratky, Stanislav; Pokorna, Zuzana; Konvalina, Ivo; Mehta, Danielle; Black, Kate; Rodenburg, CorneliaCarbon and carbon/metal systems with a multitude of functionalities are ubiquitous in new technologies but understanding on the nanoscale remains elusive due to their affinity for interaction with their environment and limitations in available characterization techniques. This paper introduces a spectroscopic technique and demonstrates its capacity to reveal chemical variations of carbon. The effectiveness of this approach is validated experimentally through spatially averaging spectroscopic techniques and using Monte Carlo modeling. Characteristic spectra shapes and peak positions for varying contributions of sp2-like or sp3-like bond types and amorphous hydrogenated carbon are reported under circumstances which might be observed on highly oriented pyrolytic graphite (HOPG) surfaces as a result of air or electron beam exposure. The spectral features identified above are then used to identify the different forms of carbon present within the metallic films deposited from reactive organometallic inks. While spectra for metals is obtained in dedicated surface science instrumentation, the complex relations between carbon and metal species is only revealed by secondary electron (SE) spectroscopy and SE hyperspectral imaging obtained in a state-of-the-art scanning electron microscope (SEM). This work reveals the inhomogeneous incorporation of carbon on the nanoscale but also uncovers a link between local orientation of metallic components and carbon form.
- ItemAdvanced GeSn/SiGeSn Group IV Heterostructure Lasers(Weinheim : Wiley-VCH, 2018) von den Driesch, Nils; Stange, Daniela; Rainko, Denis; Povstugar, Ivan; Zaumseil, Peter; Capellini, Giovanni; Schröder, Thomas; Denneulin, Thibaud; Ikonic, Zoran; Hartmann, Jean-Michel; Sigg, Hans; Mantl, Siegfried; Grützmacher, Detlev; Buca, DanGrowth and characterization of advanced group IV semiconductor materials with CMOS-compatible applications are demonstrated, both in photonics. The investigated GeSn/SiGeSn heterostructures combine direct bandgap GeSn active layers with indirect gap ternary SiGeSn claddings, a design proven its worth already decades ago in the III–V material system. Different types of double heterostructures and multi-quantum wells (MQWs) are epitaxially grown with varying well thicknesses and barriers. The retaining high material quality of those complex structures is probed by advanced characterization methods, such as atom probe tomography and dark-field electron holography to extract composition parameters and strain, used further for band structure calculations. Special emphasis is put on the impact of carrier confinement and quantization effects, evaluated by photoluminescence and validated by theoretical calculations. As shown, particularly MQW heterostructures promise the highest potential for efficient next generation complementary metal-oxide-semiconductor (CMOS)-compatible group IV lasers.
- ItemOn deeper human dimensions in Earth system analysis and modelling(München : European Geopyhsical Union, 2018) Gerten, Dieter; Schönfeld, Martin; Schauberger, BernhardWhile humanity is altering planet Earth at unprecedented magnitude and speed, representation of the cultural driving factors and their dynamics in models of the Earth system is limited. In this review and perspectives paper, we argue that more or less distinct environmental value sets can be assigned to religion – a deeply embedded feature of human cultures, here defined as collectively shared belief in something sacred. This assertion renders religious theories, practices and actors suitable for studying cultural facets of anthropogenic Earth system change, especially regarding deeper, non-materialistic motivations that ask about humans' self-understanding in the Anthropocene epoch. We sketch a modelling landscape and outline some research primers, encompassing the following elements: (i) extensions of existing Earth system models by quantitative relationships between religious practices and biophysical processes, building on databases that allow for (mathematical) formalisation of such knowledge; (ii) design of new model types that specifically represent religious morals, actors and activities as part of co-evolutionary human–environment dynamics; and (iii) identification of research questions of humanitarian relevance that are underrepresented in purely economic–technocratic modelling and scenario paradigms. While this analysis is by necessity heuristic and semi-cohesive, we hope that it will act as a stimulus for further interdisciplinary and systematic research on the immaterial dimension of humanity's imprint on the Earth system, both qualitatively and quantitatively.
- ItemEstimating global cropland production from 1961 to 2010(München : European Geopyhsical Union, 2017) Han, Pengfei; Zeng, Ning; Zhao, Fang; Lin, XiaohuiGlobal cropland net primary production (NPP) has tripled over the last 50 years, contributing 17–45 % to the increase in global atmospheric CO2 seasonal amplitude. Although many regional-scale comparisons have been made between statistical data and modeling results, long-term national comparisons across global croplands are scarce due to the lack of detailed spatiotemporal management data. Here, we conducted a simulation study of global cropland NPP from 1961 to 2010 using a process-based model called Vegetation–Global Atmosphere–Soil (VEGAS) and compared the results with Food and Agriculture Organization of the United Nations (FAO) statistical data on both continental and country scales. According to the FAO data, the global cropland NPP was 1.3, 1.8, 2.2, 2.6, 3.0, and 3.6 PgC yr−1 in the 1960s, 1970s, 1980s, 1990s, 2000s, and 2010s, respectively. The VEGAS model captured these major trends on global and continental scales. The NPP increased most notably in the US Midwest, western Europe, and the North China Plain and increased modestly in Africa and Oceania. However, significant biases remained in some regions such as Africa and Oceania, especially in temporal evolution. This finding is not surprising as VEGAS is the first global carbon cycle model with full parameterization representing the Green Revolution. To improve model performance for different major regions, we modified the default values of management intensity associated with the agricultural Green Revolution differences across various regions to better match the FAO statistical data at the continental level and for selected countries. Across all the selected countries, the updated results reduced the RMSE from 19.0 to 10.5 TgC yr−1 (∼ 45 % decrease). The results suggest that these regional differences in model parameterization are due to differences in socioeconomic development. To better explain the past changes and predict the future trends, it is important to calibrate key parameters on regional scales and develop data sets for land management history.