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- ItemTuning the Local Availability of VEGF within Glycosaminoglycan-Based Hydrogels to Modulate Vascular Endothelial Cell Morphogenesis(Weinheim : Wiley-VCH, 2020) Limasale, Yanuar Dwi Putra; Atallah, Passant; Werner, Carsten; Freudenberg, Uwe; Zimmermann, RalfIncorporation of sulfated glycosaminoglycans (GAGs) into cell-instructive polymer networks is shown to be instrumental in controlling the diffusivity and activity of growth factors. However, a subtle balance between local retention and release of the factors is needed to effectively direct cell fate decisions. To quantitatively unravel material characteristics governing these key features, the GAG content and the GAG sulfation pattern of star-shaped poly(ethylene glycol) (starPEG)–GAG hydrogels are herein tuned to control the local availability and bioactivity of GAG-affine vascular endothelial growth factor (VEGF165). Hydrogels containing varying concentrations of heparin or heparin derivatives with different sulfation pattern are prepared and thoroughly characterized for swelling, mechanical properties, and growth factor transport. Mathematical models are developed to predict the local concentration and spatial distribution of free and bound VEGF165 within the gel matrices. The results of simulation and experimental studies concordantly reveal how the GAG concentration and sulfation pattern determine the local availability of VEGF165 within the cell-instructive hydrogels and how the factor—in interplay with cell-instructive gel properties—determines the formation and spatial organization of capillary networks of embedded human vascular endothelial cells. Taken together, this study exemplifies how mathematical modeling and rational hydrogel design can be combined to pave the way for precision tissue engineering. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemPolymers Diffusivity Encoded by Stimuli-Induced Phase Transition: Theory and Application to Poly(N-Isopropylacrylamide) with Hydrophilic and Hydrophobic End Groups(Weinheim : Wiley-VCH, 2018) Schweizerhof, Sjören; Demco, Dan Eugen; Mourran, Ahmed; Fechete, Radu; Möller, MartinThe self-diffusion of various nano-objects investigated by high-resolution nuclear magnetic resonance diffusometry proves to be an efficient method for the characterization of dynamics, aggregation kinetic, and matrix morphology. This study investigates how the two-state model and Boltzmann function approach can be used for the evaluation of the thermodynamic parameters of temperature-induced phase transition encoded in polymer diffusivity. The characteristics of the phase transition given by the transition temperature, change of entropy, and width of transition are obtained for poly(N-isopropylacrylamide) (PNIPAm) linear polymers with hydrophilic and hydrophobic end-group functionalization. The effect of end groups upon the polymer diffusivity is investigated as a function of molecular weight (M n), from which fractal dimensions and hydrodynamic drag coefficients are obtained. The PNIPAm diffusivity is affected strongly by the end groups, and it is reflected in the hydrodynamic radius dependence upon molecular weight that obeys different power-law relations. In this study, the synthesis of α-ω-heterotelechelic PNIPAm of different molecular weights with a thiol end group and a hydrophilic NIPAm-like as well as a hydrophobic benzyl end group are described by reversible addition–fragmentation chain-transfer polymerization.
- ItemStructure formation of ultrathin PEO films at solid interfaces-complex pattern formation by dewetting and crystallization(Basel : MDPI AG, 2013) Braun, H.-G.; Meyer, E.The direct contact of ultrathin polymer films with a solid substrate may result in thin film rupture caused by dewetting. With crystallisable polymers such as polyethyleneoxide (PEO), molecular self-assembly into partial ordered lamella structures is studied as an additional source of pattern formation. Morphological features in ultrathin PEO films (thickness < 10 nm) result from an interplay between dewetting patterns and diffusion limited growth pattern of ordered lamella growing within the dewetting areas. Besides structure formation of hydrophilic PEO molecules, n-alkylterminated (hydrophobic) PEO oligomers are investigated with respect to self-organization in ultrathin films. Morphological features characteristic for pure PEO are not changed by the presence of the n-alkylgroups.
- ItemApplication of Thermal Response Measurements to Investigate Enhanced Water Adsorption Kinetics in Ball-Milled C2N-Type Materials(Weinheim : Wiley-VCH-Verl., 2022) Du, Shengjun; Leistenschneider, Desirée; Xiao, Jing; Dellith, Jan; Troschke, Erik; Oschatz, MartinSorption-based water capture is an attractive solution to provide potable water in arid regions. Heteroatom-decorated microporous carbons with hydrophilic character are promising candidates for water adsorption at low humidity, but the strong affinity between the polar carbon pore walls and water molecules can hinder the water transport within the narrow pore system. To reduce the limitations of mass transfer, C2N-type carbon materials obtained from the thermal condensation of a molecular hexaazatriphenylene-hexacarbonitrile (HAT-CN) precursor were treated mechanochemically via ball milling. Scanning electron microscopy as well as static light scattering reveal that large pristine C2N-type particles were split up to a smaller size after ball milling, thus increasing the pore accessibility which consequently leads to faster occupation of the water vapor adsorption sites. The major aim of this work is to demonstrate the applicability of thermal response measurements to track these enhanced kinetics of water adsorption. The adsorption rate constant of a C2N material condensed at 700 °C remarkably increased from 0.026 s−1 to 0.036 s−1 upon ball milling, while maintaining remarkably high water vapor capacity. This work confirms the advantages of small particle sizes in ultramicroporous materials on their vapor adsorption kinetics. It is demonstrated that thermal response measurements are a valuable and time-saving method to investigate water adsorption kinetics, capacities, and cycling stability.
- ItemAntiphase Boundaries Constitute Fast Cation Diffusion Paths in SrTiO3 Memristive Devices(Weinheim : Wiley-VCH, 2020) Heisig, Thomas; Kler, Joe; Du, Hongchu; Baeumer, Christoph; Hensling, Felix; Glöß, Maria; Moors, Marco; Locatelli, Andrea; Menteş, Tevfik Onur; Genuzio, Francesca; Mayer, Joachim; De Souza, Roger A.; Dittmann, ReginaResistive switching in transition metal oxide-based metal-insulator-metal structures relies on the reversible drift of ions under an applied electric field on the nanoscale. In such structures, the formation of conductive filaments is believed to be induced by the electric-field driven migration of oxygen anions, while the cation sublattice is often considered to be inactive. This simple mechanistic picture of the switching process is incomplete as both oxygen anions and metal cations have been previously identified as mobile species under device operation. Here, spectromicroscopic techniques combined with atomistic simulations to elucidate the diffusion and drift processes that take place in the resistive switching model material SrTiO3 are used. It is demonstrated that the conductive filament in epitaxial SrTiO3 devices is not homogenous but exhibits a complex microstructure. Specifically, the filament consists of a conductive Ti3+-rich region and insulating Sr-rich islands. Transmission electron microscopy shows that the Sr-rich islands emerge above Ruddlesden–Popper type antiphase boundaries. The role of these extended defects is clarified by molecular static and molecular dynamic simulations, which reveal that the Ruddlesden–Popper antiphase boundaries constitute diffusion fast-paths for Sr cations in the perovskites structure. © 2020 The Authors. Published by Wiley-VCH GmbH