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- ItemSelf-Adhesive Silicone Microstructures for the Treatment of Tympanic Membrane Perforations(Weinheim : Wiley-VCH, 2021) Lana, Gabriela Moreira; Sorg, Katharina; Wenzel, Gentiana Ioana; Hecker, Dietmar; Hensel, René; Schick, Bernhard; Kruttwig, Klaus; Arzt, EduardInspired by the gecko foot, polymeric microstructures have demonstrated reliable dry adhesion to both stiff objects and sensitive surfaces such as skin. Microstructured silicone patches are proposed, herein, for the treatment of tympanic membrane perforations with the aim of serving as an alternative for current surgical procedures that require anesthesia and ear canal packing. Sylgard 184 PDMS micropillars of 20 μm in diameter and 60 μm in length are topped by a Soft Skin Adhesive (SSA) MG7-1010 terminal layer, of about 25 μm thickness. The adhesion is evaluated by specially designed tack tests against explanted murine eardrums and, for comparison, against a rigid substrate. Functional effects are evaluated using auditory brainstem responses (ABRs) and distortion product otoacoustic emissions (DPOAE). The adhesion strength of the microstructure and unstructured controls to explanted murine tympanic membranes is comparable (typically 12 kPa), but the microstructured patches are easier to handle by the surgeon. For the first time, partial recovery of hearing performance is measured immediately after patch application. The novel patches adhere without the need for further fixation, removing the need for ear canal packing. The proposed material design holds great promise for improving clinical treatments of tympanic membrane perforations.
- ItemTime‐Dependent Cation Selectivity of Titanium Carbide MXene in Aqueous Solution(Weinheim : Wiley-VCH, 2022) Wang, Lei; Torkamanzadeh, Mohammad; Majed, Ahmad; Zhang, Yuan; Wang, Qingsong; Breitung, Ben; Feng, Guang; Naguib, Michael; Presser, VolkerElectrochemical ion separation is a promising technology to recover valuable ionic species from water. Pseudocapacitive materials, especially 2D materials, are up-and-coming electrodes for electrochemical ion separation. For implementation, it is essential to understand the interplay of the intrinsic preference of a specific ion (by charge/size), kinetic ion preference (by mobility), and crystal structure changes. Ti3C2Tz MXene is chosen here to investigate its selective behavior toward alkali and alkaline earth cations. Utilizing an online inductively coupled plasma system, it is found that Ti3C2Tz shows a time-dependent selectivity feature. In the early stage of charging (up to about 50 min), K+ is preferred, while ultimately Ca2+ and Mg2+ uptake dominate; this unique phenomenon is related to dehydration energy barriers and the ion exchange effect between divalent and monovalent cations. Given the wide variety of MXenes, this work opens the door to a new avenue where selective ion-separation with MXene can be further engineered and optimized.
- ItemLight-Driven Proton Transfer for Cyclic and Temporal Switching of Enzymatic Nanoreactors(Weinheim : Wiley-VCH, 2020) Moreno, Silvia; Sharan, Priyanka; Engelke, Johanna; Gumz, Hannes; Boye, Susanne; Oertel, Ulrich; Wang, Peng; Banerjee, Susanta; Klajn, Rafal; Voit, Brigitte; Lederer, Albena; Appelhans, DietmarTemporal activation of biological processes by visible light and subsequent return to an inactive state in the absence of light is an essential characteristic of photoreceptor cells. Inspired by these phenomena, light-responsive materials are very attractive due to the high spatiotemporal control of light irradiation, with light being able to precisely orchestrate processes repeatedly over many cycles. Herein, it is reported that light-driven proton transfer triggered by a merocyanine-based photoacid can be used to modulate the permeability of pH-responsive polymersomes through cyclic, temporally controlled protonation and deprotonation of the polymersome membrane. The membranes can undergo repeated light-driven swelling-contraction cycles without losing functional effectiveness. When applied to enzyme loaded-nanoreactors, this membrane responsiveness is used for the reversible control of enzymatic reactions. This combination of the merocyanine-based photoacid and pH-switchable nanoreactors results in rapidly responding and versatile supramolecular systems successfully used to switch enzymatic reactions ON and OFF on demand.
- ItemTrypsin-Free Cultivation of 3D Mini-Tissues in an Adaptive Membrane Bioreactor(Weinheim : Wiley-VCH, 2020) Djeljadini, Suzana; Lohaus, Theresa; Gausmann, Marcel; Rauer, Sebastian; Kather, Michael; Krause, Bernd; Pich, Andrij; Möller, Martin; Wessling, MatthiasThe production of large scaffold-free tissues is a key challenge in regenerative medicine. Nowadays, temperature-responsive polymers allow intact tissue harvesting without needing proteolytic enzymes. This method is limited to tissue culture plastic with limited upscaling capacity and plain process control. Here, a thermoresponsive hollow fiber membrane bioreactor is presented to produce large scaffold-free tissues. Intact tissues, rich in cell-to-cell connections and ECM, are harvested from a poly(N-vinylcaprolactam) microgel functionalized poly(ether sulfone)/poly(vinylpyrrolidone) hollow fiber membrane by a temperature shift. The harvested 3D tissues adhere in successive cultivation and exhibit high vitality for several days. The facile adsorptive coating waives the need for extensive surface treatment. The research is anticipated to be a starting point for upscaling the production of interconnected tissues enabling new opportunities in regenerative medicine, large-scale drug screening on physiological relevant tissues, and potentially opening new chances in cell-based therapies. © 2020 The Authors. Advanced Biosystems published by Wiley-VCH GmbH
- ItemAll-Conjugated Polymer Core-Shell and Core-Shell-Shell Particles with Tunable Emission Profiles and White Light Emission(Weinheim : Wiley-VCH, 2021) Haehnle, Bastian; Schuster, Philipp A.; Chen, Lisa; Kuehne, Alexander J. C.Future applications of conjugated polymer particles (CPP) in medicine, organic photonics, and optoelectronics greatly depend on high performance and precisely adjustable optical properties of the particles. To meet these criteria, current particle systems often combine conjugated polymers with inorganic particles in core-shell geometries, extending the possible optical characteristics of CPP. However, current conjugated polymer particles are restricted to a single polymer phase composed of a distinct polymer or a polymer blend. Here, a synthetic toolbox is presented that enables the synthesis of monodisperse core-shell and core-shell-shell particles, which consist entirely of conjugated polymers but of different types in the core and the shells. Seeded and fed-batch dispersion polymerizations based on Suzuki-Miyaura-type cross-coupling are investigated. The different approaches allow accurate control over the created interface between the conjugated polymer phases and thus also over the energy transfer phenomena between them. This approach opens up completely new synthetic freedom for fine tuning of the optical properties of CPP, enabling, for example, the synthesis of individual white light-emitting particles.
- ItemNanostructured Silicon Matrix for Materials Engineering(Weinheim : Wiley-VCH, 2023) Liu, Poting; Schleusener, Alexander; Zieger, Gabriel; Bochmann, Arne; van Spronsen, Matthijs A.; Sivakov, VladimirTin-containing layers with different degrees of oxidation are uniformly distributed along the length of silicon nanowires formed by a top-down method by applying metalorganic chemical vapor deposition. The electronic and atomic structure of the obtained layers is investigated by applying nondestructive surface-sensitive X-ray absorption near edge spectroscopy using synchrotron radiation. The results demonstrated, for the first time, a distribution effect of the tin-containing phases in the nanostructured silicon matrix compared to the results obtained for planar structures at the same deposition temperatures. The amount and distribution of tin-containing phases can be effectively varied and controlled by adjusting the geometric parameters (pore diameter and length) of the initial matrix of nanostructured silicon. Due to the occurrence of intense interactions between precursor molecules and decomposition by-products in the nanocapillary, as a consequence of random thermal motion of molecules in the nanocapillary, which leads to additional kinetic energy and formation of reducing agents, resulting in effective reduction of tin-based compounds to a metallic tin state for molecules with the highest penetration depth in the nanostructured silicon matrix. This effect will enable clear control of the phase distributions of functional materials in 3D matrices for a wide range of applications.
- ItemMicrogravity Removes Reaction Limits from Nonpolar Nanoparticle Agglomeration(Weinheim : Wiley-VCH, 2022) Pyttlik, Andrea; Kuttich, Björn; Kraus, TobiasGravity can affect the agglomeration of nanoparticles by changing convection and sedimentation. The temperature-induced agglomeration of hexadecanethiol-capped gold nanoparticles in microgravity (µ g) is studied at the ZARM (Center of Applied Space Technology and Microgravity) drop tower and compared to their agglomeration on the ground (1 g). Nonpolar nanoparticles with a hydrodynamic diameter of 13 nm are dispersed in tetradecane, rapidly cooled from 70 to 10 °C to induce agglomeration, and observed by dynamic light scattering at a time resolution of 1 s. The mean hydrodynamic diameters of the agglomerates formed after 8 s in microgravity are 3 times (for low initial concentrations) to 5 times (at high initial concentrations) larger than on the ground. The observations are consistent with an agglomeration process that is closer to the reaction limit on thground and closer to the diffusion limit in microgravity.
- ItemImperceptible Supercapacitors with High Area-Specific Capacitance(Weinheim : Wiley-VCH, 2021) Ge, Jin; Zhu, Minshen; Eisner, Eric; Yin, Yin; Dong, Haiyun; Karnaushenko, Dmitriy D.; Karnaushenko, Daniil; Zhu, Feng; Ma, Libo; Schmidt, Oliver G.Imperceptible electronics will make next-generation healthcare and biomedical systems thinner, lighter, and more flexible. While other components are thoroughly investigated, imperceptible energy storage devices lag behind because the decrease of thickness impairs the area-specific energy density. Imperceptible supercapacitors with high area-specific capacitance based on reduced graphene oxide/polyaniline (RGO/PANI) composite electrodes and polyvinyl alcohol (PVA)/H2SO4 gel electrolyte are reported. Two strategies to realize a supercapacitor with a total device thickness of 5 µm—including substrate, electrode, and electrolyte—and an area-specific capacitance of 36 mF cm−2 simultaneously are implemented. First, the void volume of the RGO/PANI electrodes through mechanical compression is reduced, which decreases the thickness by 83% while retaining 89% of the capacitance. Second, the PVA-to-H2SO4 mass ratio is decreased to 1:4.5, which improves the ion conductivity by 5000% compared to the commonly used PVA/H2SO4 gel. Both advantages enable a 2 µm-thick gel electrolyte for planar interdigital supercapacitors. The impressive electromechanical stability of the imperceptible supercapacitors by wrinkling the substrate to produce folds with radii of 6 µm or less is demonstrated. The supercapacitors will be meaningful energy storage modules for future self-powered imperceptible electronics.
- ItemScreening Arrays of Laminin Peptides on Modified Cellulose for Promotion of Adhesion of Primary Endothelial and Neural Precursor Cells(Weinheim : Wiley-VCH, 2021) Wetzel, Richard; Hauser, Sandra; Lin, Weilin; Berg, Peggy; Werner, Carsten; Pietzsch, Jens; Kempermann, Gerd; Zhang, YixinNeural precursor cells (NPC) are primary cells intensively used in the context of research on adult neurogenesis and modeling of neuronal development in health and diseased states. Substrates that can facilitate NPC adhesion will be very useful for culturing these cells. Due to the presence of laminin in basal lamina as well as their involvement in differentiation, migration, and adhesion of many types of cells, surfaces modified with laminin-derived peptides are focused upon and compared with the widely used fibronectin-derived Arg-Gly-Asp (RGD) peptides. An array of 46 peptides is synthesized on cellulose paper (SPOT) to identify laminin-derived peptides that promote short-term adhesion of murine NPC and human primary endothelial cells. Various previously reported peptide sequences are re-evaluated in this work. Initial adhesion experiments show NPC preferred several laminin-derived peptides by up to 5-time higher cell numbers, compared to the well-known promiscuous integrin binding RGD peptide. Importantly, screening of cell adhesion has revealed a synergetic effect of filamentous matrix, peptide sequence, surface property, ligand density, and the dynamic process of NPC adhesion. © The Authors. Advanced Biology published by Wiley-VCH GmbH
- ItemMultimodal Characterization of Resin Embedded and Sliced Polymer Nanoparticles by Means of Tip-Enhanced Raman Spectroscopy and Force-Distance Curve Based Atomic Force Microscopy(Weinheim : Wiley-VCH, 2020) Höppener, Christiane; Schacher, Felix H.; Deckert, VolkerUnderstanding the property-function relation of nanoparticles in various application fields involves determining their physicochemical properties, which is still a remaining challenge to date. While a multitude of different characterization tools can be applied, these methods by themselves can only provide an incomplete picture. Therefore, novel analytical techniques are required, which can address both chemical functionality and provide structural information at the same time with high spatial resolution. This is possible by using tip-enhanced Raman spectroscopy (TERS), but due to its limited depth information, TERS is usually restricted to investigations of the nanoparticle surface. Here, TERS experiments are established on polystyrene nanoparticles (PS NPs) after resin embedding and microtome slicing. With that, unique access to their internal morphological features is gained, and thus, enables differentiation between information obtained for core- and shell-regions. Complementary information is obtained by means of transmission electron microscopy (TEM) and from force-distance curve based atomic force microscopy (FD-AFM). This multimodal approach achieves a high degree of discrimination between the resin and the polymers used for nanoparticle formulation. The high potential of TERS combined with advanced AFM spectroscopy tools to probe the mechanical properties is applied for quality control of the resin embedding procedure.