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    Polyethylene glycol-modified poly(styrene-co-ethylene/butylene-co-styrene)/carbon nanotubes composite for humidity sensing
    (Lausanne : Frontiers Media, 2019) Mičušík, Matej; Chatzimanolis, Christos; Tabačiarová, Jana; Kollár, Jozef; Kyritsis, Apostolos; Pissis, Polycarpos; Pionteck, Jürgen; Vegso, Karol; Siffalovic, Peter; Majkova, Eva; Omastová, Mária
    Polymeric composites of the linear triblock copolymer poly(styrene-co-ethylene/butylene-co-styrene) grafted with maleic anhydride units (SEBS-MA) or MA modified by hydrophilic polyethylene glycol (PEG) and containing various amounts of multiwall carbon nanotubes (MWCNTs) as conducting filler—were prepared by solvent casting. The MWCNT surface was modified by a non-covalent approach with a pyrene-based surfactant to achieve a homogeneous dispersion of the conducting filler within the polymeric matrix. The dispersion of the unmodified and surfactant-modified MWCNTs within the elastomeric SEBS-MA and SEBS-MA-PEG matrices was characterized by studying the morphology by TEM and SAXS. Dynamical mechanical analysis was used to evaluate the interaction between the MWCNTs and copolymer matrix. The electrical conductivity of the prepared composites was measured by dielectric relaxation spectroscopy, and the percolation threshold was calculated. The prepared elastomeric composites were characterized and studied as humidity sensor. Our results demonstrated that at MWCNTs concentration slightly above the percolation threshold could result in large signal changes. In our system, good results were obtained for MWCNT loading of 2 wt% and an ~0.1 mm thin composite film. The thickness of the tested elastomeric composites and the source current appear to be very important factors that influence the sensing performance. © 2019 Mičušík, Chatzimanolis, Tabačiarová, Kollár, Kyritsis, Pissis, Pionteck, Vegso, Siffalovic, Majkova and Omastová.
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    Organic Light-Emitting Diodes Based on Conjugation-Induced Thermally Activated Delayed Fluorescence Polymers: Interplay Between Intra- and Intermolecular Charge Transfer States
    (Lausanne : Frontiers Media, 2019) Li, Yungui; Wei, Qiang; Cao, Liang; Fries, Felix; Cucchi, Matteo; Wu, Zhongbin; Scholz, Reinhard; Lenk, Simone; Voit, Brigitte; Ge, Ziyi; Reineke, Sebastian
    In this work, interactions between different host materials and a blue TADF polymer named P1 are systematically investigated. In photoluminescence, the host can have substantial impact on the photoluminescence quantum yield (PLQY) and the intensity of delayed fluorescence (ΦDF), where more than three orders of magnitude difference of ΦDF in various hosts is observed, resulting from a polarity effect of the host material and energy transfer. Additionally, an intermolecular charge-transfer (CT) emission with pronounced TADF characteristics is observed between P1 and 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T), with a singlet-triplet splitting of 7 meV. It is noted that the contribution of harvested triplets in monochrome organic light-emitting diodes (OLEDs) correlates with ΦDF. For devices based on intermolecular CT-emission, the harvested triplets contribute ~90% to the internal quantum efficiency. The results demonstrate the vital importance of host materials on improving the PLQY and sensitizing ΦDF of TADF polymers for efficient devices. Solution-processed polychrome OLEDs with a color close to a white emission are presented, with the emission of intramolecular (P1) and intermolecular TADF (PO-T2T:P1). © Copyright © 2019 Li, Wei, Cao, Fries, Cucchi, Wu, Scholz, Lenk, Voit, Ge and Reineke.
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    GATA3 promotes the neural progenitor state but not neurogenesis in 3D traumatic injury model of primary human cortical astrocytes
    (Lausanne : Frontiers Media, 2019) Celikkaya, Hilal; Cosacak, Mehmet Ilyas; Papadimitriou, Christos; Popova, Stanislava; Bhattarai, Prabesh; Biswas, Srijeeta Nag; Siddiqui, Tohid; Wistorf, Sabrina; Nevado-Alcalde, Isabel; Naumann, Lisa; Mashkaryan, Violeta; Brandt, Kerstin; Freudenberg, Uwe; Werner, Carsten; Kizil, Caghan
    Astrocytes are abundant cell types in the vertebrate central nervous system and can act as neural stem cells in specialized niches where they constitutively generate new neurons. Outside the stem cell niches, however, these glial cells are not neurogenic. Although injuries in the mammalian central nervous system lead to profound proliferation of astrocytes, which cluster at the lesion site to form a gliotic scar, neurogenesis does not take place. Therefore, a plausible regenerative therapeutic option is to coax the endogenous reactive astrocytes to a pre-neurogenic progenitor state and use them as an endogenous reservoir for repair. However, little is known on the mechanisms that promote the neural progenitor state after injuries in humans. Gata3 was previously found to be a mechanism that zebrafish brain uses to injury-dependent induction of neural progenitors. However, the effects of GATA3 in human astrocytes after injury are not known. Therefore, in this report, we investigated how overexpression of GATA3 in primary human astrocytes would affect the neurogenic potential before and after injury in 2D and 3D cultures. We found that primary human astrocytes are unable to induce GATA3 after injury. Lentivirus-mediated overexpression of GATA3 significantly increased the number of GFAP/SOX2 double positive astrocytes and expression of pro-neural factor ASCL1, but failed to induce neurogenesis, suggesting that GATA3 is required for enhancing the neurogenic potential of primary human astrocytes and is not sufficient to induce neurogenesis alone. © 2019 Celikkaya, Cosacak, Papadimitriou, Popova, Bhattarai, Biswas, Siddiqui, Wistorf, Nevado-Alcalde, Naumann, Mashkaryan, Brandt, Freudenberg, Werner and Kizil.
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    In-situ-investigation of enzyme immobilization on polymer brushes
    (Lausanne : Frontiers Media, 2019) Koenig, Meike; König, Ulla; Eichhorn, Klaus-Jochen; Müller, Martin; Stamm, Manfred; Uhlmann, Petra
    Herein, we report on the use of a combined setup of quartz-crystal microbalance, with dissipation monitoring and spectroscopic ellipsometry, to comprehensively investigate the covalent immobilization of an enzyme to a polymer layer. All steps of the covalent reaction of the model enzyme glucose oxidase with the poly(acrylic acid) brush by carbodiimide chemistry, were monitored in-situ. Data were analyzed using optical and viscoelastic modeling. A nearly complete collapse of the polymer chains was found upon activation of the carboxylic acid groups with N-(3-Dimethylaminopropyl)-N'-ethylcarbodiimide and N-Hydroxysuccinimide. The reaction with the amine groups of the enzyme occurs simultaneously with re-hydration of the polymer layer. Significantly more enzyme was immobilized on the surface compared to physical adsorption at similar conditions, at the same pH. It was found that the pH responsive swelling behavior was almost not affected by the presence of the enzyme. © 2019 Koenig, König, Eichhorn, Müller, Stamm and Uhlmann.
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    Free polyethylenimine enhances substrate-mediated gene delivery on titanium substrates modified with RGD-functionalized poly(acrylic acid) brushes
    (Lausanne : Frontiers Media, 2019) Mantz, Amy; Rosenthal, Alice; Farris, Eric; Kozisek, Tyler; Bittrich, Eva; Nazari, Saghar; Schubert, Eva; Schubert, Mathias; Stamm, Manfred; Uhlmann, Petra; Pannier, Angela K.
    Substrate mediated gene delivery (SMD) is a method of immobilizing DNA complexes to a substrate via covalent attachment or nonspecific adsorption, which allows for increased transgene expression with less DNA compared to traditional bolus delivery. It may also increase cells receptivity to transfection via cell-material interactions. Substrate modifications with poly(acrylic) acid (PAA) brushes may improve SMD by enhancing substrate interactions with DNA complexes via tailored surface chemistry and increasing cellular adhesion via moieties covalently bound to the brushes. Previously, we described a simple method to graft PAA brushes to Ti and further demonstrated conjugation of cell adhesion peptides (i.e., RGD) to the PAA brushes to improve biocompatibility. The objective of this work was to investigate the ability of Ti substrates modified with PAA-RGD brushes (PAA-RGD) to immobilize complexes composed of branched polyethyleneimine and DNA plasmids (bPEI-DNA) and support SMD in NIH/3T3 fibroblasts. Transfection in NIH/3T3 cells cultured on bPEI-DNA complexes immobilized onto PAA-RGD substrates was measured and compared to transfection in cells cultured on control surfaces with immobilized complexes including Flat Ti, PAA brushes modified with a control peptide (RGE), and unmodified PAA. Transfection was two-fold higher in cells cultured on PAA-RGD compared to those cultured on all control substrates. While DNA immobilization measured with radiolabeled DNA indicated that all substrates (PAA-RGD, unmodified PAA, Flat Ti) contained nearly equivalent amounts of loaded DNA, ellipsometric measurements showed that more total mass (i.e., DNA and bPEI, both complexed and free) was immobilized to PAA and PAA-RGD compared to Flat Ti. The increase in adsorbed mass may be attributed to free bPEI, which has been shown to improve transfection. Further transfection investigations showed that removing free bPEI from the immobilized complexes decreased SMD transfection and negated any differences in transfection success between cells cultured on PAA-RGD and on control substrates, suggesting that free bPEI may be beneficial for SMD in cells cultured on bPEI-DNA complexes immobilized on PAA-RGD grafted to Ti. This work demonstrates that substrate modification with PAA-RGD is a feasible method to enhance SMD outcomes on Ti and may be used for future applications such as tissue engineering, gene therapy, and diagnostics. © 2019 Mantz, Rosenthal, Farris, Kozisek, Bittrich, Nazari, Schubert, Schubert, Stamm, Uhlmann and Pannier.
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    Coating of Carbon Nanotube Fibers: Variation of Tensile Properties, Failure Behavior, and Adhesion Strength
    (Lausanne : Frontiers Media, 2015) Mäder, Edith; Liu, Jianwen; Hiller, Janett; Lu, Weibang; Li, Qingwen; Zhandarov, Serge; Chou, Tsu-Wei
    An experimental study of the tensile properties of CNT fibers and their interphasial behavior in epoxy matrices is reported. One of the most promising applications of CNT fibers is their use as reinforcement in multifunctional composites. For this purpose, an increase of the tensile strength of the CNT fibers in unidirectional composites as well as strong interfacial adhesion strength is desirable. However, the mechanical performance of the CNT fiber composites manufactured so far is comparable to that of commercial fiber composites. The interfacial properties of CNT fiber/polymer composites have rarely been investigated and provided CNT fiber/epoxy interfacial shear strength (IFSS) of 14.4 MPa studied by the microbond test. In order to improve the mechanical performance of the CNT fibers, an epoxy compatible coating with nano-dispersed aqueous-based polymeric film formers and low viscous epoxy resin, respectively, was applied. For impregnation of high homogeneity, low molecular weight epoxy film formers and polyurethane film formers were used. The aqueous-based epoxy film formers were not crosslinked and able to interdiffuse with the matrix resin after impregnation. Due to good wetting of the individual CNT fibers by the film formers, the degree of activation of the fibers was improved, leading to increased tensile strength and Young’s modulus. Cyclic tensile loading and simultaneous determination of electric resistance enabled to characterize the fiber’s durability in terms of elastic recovery and hysteresis. The pull-out tests and SEM study reveal different interfacial failure mechanisms in CNT fiber/epoxy systems for untreated and film former treated fibers, on the one hand, and epoxy resin treated ones, on the other hand. The epoxy resin penetrated between the CNT bundles in the reference or film former coated fiber, forming a relatively thick CNT/epoxy composite layer and thus shifting the fracture zone within the fiber. In contrast to this, shear sliding along the interface between the matrix and the outer fiber layer impregnated with the resin was observed for epoxy resin-coated fibers. These fibers have been successfully pulled out of the matrix droplets and shown that the average local interfacial shear stress value was 63 MPa (with apparent IFSS values 33–60 MPa). The interfacial frictional stress between the fiber and the matrix was rather high (9.5 MPa), which can be attributed to the complex structure of the interface and the fiber twisting.