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- 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.
- ItemInfluence of Polyvinylpyrrolidone on Thermoelectric Properties of Melt-Mixed Polymer/Carbon Nanotube Composites(Basel : MDPI, 2023) Krause, Beate; Imhoff, Sarah; Voit, Brigitte; Pötschke, PetraFor thermoelectric applications, both p- and n-type semi-conductive materials are combined. In melt-mixed composites based on thermoplastic polymers and carbon nanotubes, usually the p-type with a positive Seebeck coefficient (S) is present. One way to produce composites with a negative Seebeck coefficient is to add further additives. In the present study, for the first time, the combination of single-walled carbon nanotubes (SWCNTs) with polyvinylpyrrolidone (PVP) in melt-mixed composites is investigated. Polycarbonate (PC), poly(butylene terephthalate) (PBT), and poly(ether ether ketone) (PEEK) filled with SWCNTs and PVP were melt-mixed in small scales and thermoelectric properties of compression moulded plates were studied. It could be shown that a switch in the S-value from positive to negative values was only possible for PC composites. The addition of 5 wt% PVP shifted the S-value from 37.8 µV/K to −31.5 µV/K (2 wt% SWCNT). For PBT as a matrix, a decrease in the Seebeck coefficient from 59.4 µV/K to 8.0 µV/K (8 wt% PVP, 2 wt% SWCNT) could be found. In PEEK-based composites, the S-value increased slightly with the PVP content from 48.0 µV/K up to 54.3 µV/K (3 wt% PVP, 1 wt% SWCNT). In addition, the long-term stability of the composites was studied. Unfortunately, the achieved properties were not stable over a storage time of 6 or 18 months. Thus, in summary, PVP is not suitable for producing long-term stable, melt-mixed n-type SWCNT composites.
- ItemHydrogel patterns in microfluidic devices by do-it-yourself UV-photolithography suitable for very large-scale integration(Basel : MDPI, 2020) Beck, Anthony; Obst, Franziska; Busek, Mathias; Grünzner, Stefan; Mehner, Philipp J.; Paschew, Georgi; Appelhans, Dietmar; Voit, Brigitte; Richter, AndreasThe interest in large-scale integrated (LSI) microfluidic systems that perform highthroughput biological and chemical laboratory investigations on a single chip is steadily growing. Such highly integrated Labs-on-a-Chip (LoC) provide fast analysis, high functionality, outstanding reproducibility at low cost per sample, and small demand of reagents. One LoC platform technology capable of LSI relies on specific intrinsically active polymers, the so-called stimuli-responsive hydrogels. Analogous to microelectronics, the active components of the chips can be realized by photolithographic micro-patterning of functional layers. The miniaturization potential and the integration degree of the microfluidic circuits depend on the capability of the photolithographic process to pattern hydrogel layers with high resolution, and they typically require expensive cleanroom equipment. Here, we propose, compare, and discuss a cost-efficient do-it-yourself (DIY) photolithographic set-up suitable to micro-pattern hydrogel-layers with a resolution as needed for very large-scale integrated (VLSI) microfluidics. The achievable structure dimensions are in the lower micrometer scale, down to a feature size of 20 µm with aspect ratios of 1:5 and maximum integration densities of 20,000 hydrogel patterns per cm. Furthermore, we demonstrate the effects of miniaturization on the efficiency of a hydrogel-based microreactor system by increasing the surface area to volume (SA:V) ratio of integrated bioactive hydrogels. We then determine and discuss a correlation between ultraviolet (UV) exposure time, cross-linking density of polymers, and the degree of immobilization of bioactive components. © 2020 by the authors.
- ItemSelf-Replication of Deeply Buried Doped Silicon Structures, which Remotely Control the Etching Process: A New Method for Forming a Silicon Pattern from the Bottom Up(Weinheim : Wiley-VCH, 2021) Schutzeichel, Christopher; Kiriy, Nataliya; Kiriy, Anton; Voit, BrigitteA typical microstructuring process utilizes photolithographic masks to create arbitrary patterns on silicon substrates in a top-down approach. Herein, a new, bottom-up microstructuring method is reported, which enables the patterning of n-doped silicon substrates to be performed without the need for application of etch-masks or stencils during the etching process. Instead, the structuring process developed herein involves a simple alkaline etching performed under illumination and is remotely controlled by the p-doped micro-sized implants, buried beneath a homogeneous n-doped layer at depths of 0.25 to 1 µm. The microstructuring is realized because the buried implants act upon illumination as micro-sized photovoltaic cells, which generate a flux of electrons and increase the negative surface charge in areas above the implants. The locally increased surface charge causes a local protection of the native silicon oxide layer from alkaline etching, which ultimately leads to the microstructuring of the substrate. In this way, substrates having at their top a thick layer of homogeneously n-doped silicon can be structured, reducing the need for costly, time-consuming photolithography steps. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
- ItemSemi-Interpenetrating Polymer Networks Based on N-isopropylacrylamide and 2-acrylamido-2-methylpropane Sulfonic Acid for Intramolecular Force-Compensated Sensors(Bristol : IOP Publishing, 2021) Binder, Simon; Zschoche, Stefan; Voit, Brigitte; Gerlach, GeraldStimulus-responsive hydrogels are swellable polymers that take up a specific volume depending on a measured variable present in solution. Hydrogel-based chemical sensors make use of this ability by converting the resulting swelling pressure, which depends on the measured variable, into an electrical value. Due to the tedious swelling processes, the measuring method of intramolecular force compensation is used to suppress these swelling processes and, thus, significantly increase the sensor's response time. However, intramolecular force compensation requires a bisensitive hydrogel. In addition to the sensitivity of the measured variable the gel has to provide a second sensitivity for intrinsic compensation of the swelling pressure. At the same time, this hydrogel has to meet further requirements, e.g. high compressive strength. Until now, interpenetrating polymer networks (IPN) have been used for such a force-compensatory effective hydrogel, which are complex to manufacture. In order to significantly simplify the sensor design and production, a simpler synthesis of the bisensitive hydrogel is desirable. This paper presents a new bisensitive hydrogel based on semi-interpenetrating polymer networks. It is based on a copolymer network consisting of N-isopropylacrylamide (NiPAAm) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and long PAMPS strands that permeate it. Measurements show, that this hydrogel meets all essential requirements for intramolecular force compensation and is at the same time much easier to synthesize than previously used IPN hydrogels. © 2021 The Author(s).
- ItemMWCNT induced negative real permittivity in a copolyester of Bisphenol-A with terephthalic and isophthalic acids(Bristol : IOP Publ., 2020) Özdemir, Zeynep Güven; Daşdan, Dolunay Şakar; Kavak, Pelin; Pionteck, Jürgen; Pötschke, Petra; Voit, Brigitte; SüngüMısırlıoğlu, BanuIn the present study, the negative real permittivity behavior of a copolyester of bisphenol-A with terephthalic acid and isophthalic acid (PAr) containing 1.5 to 7.5 wt% multi-walled carbon nanotubes (MWCNTs) have been investigated in detail. The structural and morphological analysis of the melt-mixed composites was performed by Fourier transform infrared spectroscopy using attenuated total reflection (FTIR-ATR), atomic force microscopy (AFM), X-ray diffraction (XRD), and light microscopy. The influences of the MWCNT filler on the AC impedance, complex permittivity, and AC conductivity of the PAr polymer matrix were investigated at different operating temperatures varied between 296 K and 373 K. The transition from a negative to positive real permittivity was observed at different crossover frequencies depending on the MWCNT content of the composites whereas pure PAr showed positive values at all frequencies. The negative real permittivity characteristic of the composites was discussed in the context of Drude model. © 2020 The Author(s). Published by IOP Publishing Ltd.
- ItemHydrogel microvalves as control elements for parallelized enzymatic cascade reactions in microfluidics(Basel : MDPI, 2020) Obst, Franziska; Beck, Anthony; Bishayee, Chayan; Mehner, Philipp J.; Richter, Andreas; Voit, Brigitte; Appelhans, DietmarCompartmentalized microfluidic devices with immobilized catalysts are a valuable tool for overcoming the incompatibility challenge in (bio) catalytic cascade reactions and high-throughput screening of multiple reaction parameters. To achieve flow control in microfluidics, stimuli-responsive hydrogel microvalves were previously introduced. However, an application of this valve concept for the control of multistep reactions was not yet shown. To fill this gap, we show the integration of thermoresponsive poly(N-isopropylacrylamide) (PNiPAAm) microvalves (diameter: 500 and 600 µm) into PDMS-on-glass microfluidic devices for the control of parallelized enzyme-catalyzed cascade reactions. As a proof-of-principle, the biocatalysts glucose oxidase (GOx), horseradish peroxidase (HRP) and myoglobin (Myo) were immobilized in photopatterned hydrogel dot arrays (diameter of the dots: 350 µm, amount of enzymes: 0.13-2.3 µg) within three compartments of the device. Switching of the microvalves was achieved within 4 to 6 s and thereby the fluid pathway of the enzyme substrate solution (5 mmol/L) in the device was determined. Consequently, either the enzyme cascade reaction GOx-HRP or GOx-Myo was performed and continuously quantified by ultraviolet-visible (UV-Vis) spectroscopy. The functionality of the microvalves was shown in four hourly switching cycles and visualized by the path-dependent substrate conversion. © 2020 by the authors.
- ItemConstruction of Eukaryotic Cell Biomimetics: Hierarchical Polymersomes-in-Proteinosome Multicompartment with Enzymatic Reactions Modulated Protein Transportation(Weinheim : Wiley-VCH, 2021) Wen, Ping; Wang, Xueyi; Moreno, Silvia; Boye, Susanne; Voigt, Dagmar; Voit, Brigitte; Huang, Xin; Appelhans, DietmarThe eukaryotic cell is a smart compartment containing an outer permeable membrane, a cytoskeleton, and functional organelles, presenting part structures for life. The integration of membrane-containing artificial organelles (=polymersomes) into a large microcompartment is a key step towards the establishment of exquisite cellular biomimetics with different membrane properties. Herein, an efficient way to construct a hierarchical multicompartment composed of a hydrogel-filled proteinosome hybrid structure with an outer homogeneous membrane, a smart cytoskeleton-like scaffold, and polymersomes is designed. Specially, this hybrid structure creates a micro-environment for pH-responsive polymersomes to execute a desired substance transport upon response to biological stimuli. Within the dynamic pH-stable skeleton of the protein hydrogels, polymersomes with loaded PEGylated insulin biomacromolecules demonstrate a pH-responsive reversible swelling-deswelling and a desirable, on-demand cargo release which is induced by the enzymatic oxidation of glucose to gluconic acid. This stimulus responsive behavior is realized by tunable on/off states through protonation of the polymersomes membrane under the enzymatic reaction of glucose oxidase, integrated in the skeleton of protein hydrogels. The integration of polymersomes-based hybrid structure into the proteinosome compartment and the stimuli-response on enzyme reactions fulfills the requirements of eukaryotic cell biomimetics in complex architectures and allows mimicking cellular transportation processes.