Universität Stuttgart

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    Acid catalyzed cross‐linking of polyvinyl alcohol for humidifier membranes
    (2021) Michele, Andre; Paschkowski, Patrick; Hänel, Christopher; Tovar, Günter E. M.; Schiestel, Thomas; Southan, Alexander
    Polyvinyl alcohol (PVA) is a hydrophilic polymer well known for good film forming properties, high water vapor permeance JW, and low nitrogen permeance. However, depending on molar mass and temperature, PVA swells strongly in water until complete dissolution. This behavior affects the usability of PVA in aqueous environments and makes cross‐linking necessary if higher structural integrity is envisaged. In this work, PVA networks are formed by thermal cross‐linking in the presence of p‐toluenesulfonic acid (TSA) and investigated in a design of experiments approach. Experimental parameters are the cross‐linking period tc, temperature ϑ and the TSA mass fraction wTSA. Cross‐linking is found to proceed via ether bond formation at all reaction conditions. Degradation is promoted especially by a combination of high wTSA, tc and ϑ. Thermal stability of the networks after preparation is strongly improved by neutralizing residual TSA. Humidification membranes with a JW of 6423 ± 63.0 gas permeation units (GPU) are fabricated by coating PVA on polyvinyliden fluoride hollow fibers and cross‐linking with TSA. Summarizing, the present study contributes to a clearer insight into the cross‐linking of PVA in presence of TSA, the thermal stability of the resulting networks and the applicability as selective membrane layers for water vapor transfer.
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    Nano-in-micro-particles consisting of PLGA nanoparticles embedded in chitosan microparticles via spray-drying enhances their uptake in the olfactory mucosa
    (2021) Spindler, Lena Marie; Feuerhake, Andreas; Ladel, Simone; Günday, Cemre; Flamm, Johannes; Günday-Türeli, Nazende; Türeli, Emre; Tovar, Günter E. M.; Schindowski, Katharina; Gruber-Traub, Carmen
    Intranasal delivery has gained prominence since 1990, when the olfactory mucosa was recognized as the window to the brain and the central nervous system (CNS); this has enabled the direct site specific targeting of neurological diseases for the first time. Intranasal delivery is a promising route because general limitations, such as the blood-brain barrier (BBB) are circumvented. In the treatment of multiple sclerosis (MS) or Alzheimer’s disease, for example, future treatment prospects include specialized particles as delivery vehicles. Poly(lactic-co-glycolic acid) (PLGA) nanoparticles are well known as promising delivery systems, especially in the area of nose-to-brain (N2B) delivery. Chitosan is also broadly known as a functional additive due to its ability to open tight junctions. In this study, we produced PLGA nanoparticles of different sizes and revealed for the first time their size-time-dependent uptake mechanism into the lamina propria of porcine olfactory mucosa. The intracellular uptake was observed for 80 and 175 nm within only 5 min after application to the epithelium. After 15 min, even 520 nm particles were detected, associated with nuclei. Especially the presence of only 520 nm particles in neuronal fibers is remarkable, implying transcellular and intracellular transport via the olfactory or the trigeminal nerve to the brain and the CNS. Additionally, we developed successfully specialized Nano-in-Micro particles (NiMPs) for the first time via spray drying, consisting of PLGA nanoparticles embedded into chitosan microparticles, characterized by high encapsulation efficiencies up to 51%, reproducible and uniform size distribution, as well as smooth surface. Application of NiMPs accelerated the uptake compared to purely applied PLGA nanoparticles. NiMPs were spread over the whole transverse section of the olfactory mucosa within 15 min. Faster uptake is attributed to additional paracellular transport, which was examined via tight-junction-opening. Furthermore, a separate chitosan penetration gradient of ∼150 µm caused by dissociation from PLGA nanoparticles was observed within 15 min in the lamina propria, which was demonstrated to be proportional to an immunoreactivity gradient of CD14. Due to the beneficial properties of the utilized chitosan-derivative, regarding molecular weight (150-300 kDa), degree of deacetylation (80%), and particle size (0.1-10 µm) we concluded that M2-macrophages herein initiated an anti-inflammatory reaction, which seems to already take place within 15 min following chitosan particle application. In conclusion, we demonstrated the possibility for PLGA nanoparticles, as well as for chitosan NiMPs, to take all three prominent intranasal delivery pathways to the brain and the CNS; namely transcellular, intracellular via neuronal cells, and paracellular transport.
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    Preparation of multifunctional hydrogels with accessible isothiouronium groups via radical cross-linking copolymerization
    (2023) Grübel, Jana; L. Albernaz, Vanessa; Tsianaka, Anastasia; Jauch, Corinna O.; Quirin, Silia; Kerger, Christian; Kohl, Christina G.; Burger-Kentischer, Anke; Tovar, Günter E. M.; Southan, Alexander
    Hydrogels can be equipped with functional groups for specific purposes. Isothiouronium groups can enhance adsorptivity, or allow coupling of other functional groups through mild reactions after transformation to thiol groups. Here we present a method to prepare multifunctional hydrogels by introducing isothiouronium groups into poly(ethylene glycol) diacrylate (PEGDA) hydrogels, and convert them into thiol-functionalized hydrogels by the reduction of the isothiouronium groups. For this purpose, the amphiphilic monomer 2-(11-(acryloyloxy)-undecyl)isothiouronium bromide (AUITB), containing an isothiouronium group, was synthesized and copolymerized with PEGDA. In this convenient way, it was possible to incorporate up to 3 wt% AUITB into the hydrogels without changing their equilibrium swelling degree. The successful functionalization was demonstrated by surface analysis of the hydrogels with water contact angle measurements and increased isoelectric points of the hydrogel surfaces from 4.5 to 9.0 due to the presence of the isothiouronium groups. The hydrogels showed a suitability as an adsorbent, as exemplified by the pronounced adsorption of the anionic drug diclofenac. The potential of the functionalization for (bio)conjugation reactions was demonstrated by the reduction of isothiouronium groups to thiols and subsequent immobilization of the functional enzyme horseradish peroxidase on the hydrogels. The results show that fully accessible isothiouronium groups can be introduced into radically cross-linked hydrogels.
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    Tunable, permanent and instantly available super-wettability states on metal surfaces by laser texturing and plasma coating
    (2025) Holder, Daniel; Reichle, Paul; Umlauf, Georg; Weber, Rudolf; Barz, Jakob; Graf, Thomas
    Wettability, the ability of a liquid to spread on or repel from a surface, holds particular significance for applications requiring extreme control of liquid interaction, including self-cleaning, anti-icing, dropwise condensation, anti-fogging, and enhanced fluid transport. This work investigates the synergistic combination of laser surface texturing and plasma-enhanced chemical vapor deposition (PECVD) to achieve tunable, permanent, and instantly available super-wettability states on metal surfaces. Ultrashort laser pulses were employed to produce various surface textures, ranging from fine nanoscale ripples to rougher microtextures such as microgrooves, spikes, and holes, on stainless steel AISI 304, copper, and the titanium alloy Ti64. PECVD coatings, including thin layers of glass and polymers, were subsequently applied to these textures to modulate surface chemistry and achieve the desired wettability.The results demonstrate that superhydrophilic surfaces with a water contact angle θ  < 10° were achieved by combining rough textures with thin glass coatings, offering long-term stability that could be simply renewed via ultrasonic cleaning. Conversely, superhydrophobic surfaces with a water contact angle θ  > 150° were instantly obtained using polymer coatings on rough textures. These functionalized surfaces also exhibited exceptional liquid repellence for complex liquids, such as milk and beer, making them particularly suitable for special applications using solutions or emulsions. The integration of laser texturing and PECVD coating provides a versatile and simple pathway for fabricating functional surfaces with tunable wettability and long-term performance across multiple metals and fluids.
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    Plasma electron acceleration in a non-resonant microwave heating scheme below the electron cyclotron frequency
    (2022) Köhn-Seemann, Alf; Birkenmeier, Gregor; Diez, Peter; Holzhauer, Eberhard; Merli, Stefan; Ramisch, Mirko; Sichardt, Garbriel; Stroth, Ulrich
    Microwave heating of over-dense plasmas is routinely achieved in the stellarator TJ-K. In contrast to usually applied heating scenarios in tokamaks or stellarators, an operational regime is described where the heating occurs well below the electron cyclotron frequency but still well above the lower hybrid frequency. Microwave energy is deposited at the so-called O-resonance, accompanied by a small population of high-energy electrons with an energy up to 100 keV. These electrons are responsible for a significant toroidal net current and the occurrence of hard x-rays. Requirements for achieving this heating regime are described together with a novel scheme for plasma-electron acceleration.
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    Oral bioavailability of omega-3 fatty acids and carotenoids from the microalgae Phaeodactylum tricornutum in healthy young adults
    (2021) Stiefvatter, Lena; Lehnert, Katja; Frick, Konstantin; Montoya-Arroyo, Alexander; Frank, Jan; Vetter, Walter; Schmid-Staiger, Ulrike; Bischoff, Stephan C.
    The microalgae Phaeodactylum tricornutum (PT) contains valuable nutrients such as proteins, polyunsaturated omega-3 fatty acids (n-3 PUFA), particularly eicosapentaenoic acid (EPA) and some docosahexaenoic acid (DHA), carotenoids such as fucoxanthin (FX), and beta-glucans, which may confer health benefits. In a randomized intervention trial involving 22 healthy individuals, we administered for two weeks in a crossover manner the whole biomass of PT (5.3 g/day), or fish oil (FO) containing equal amounts of EPA and DHA (together 300 mg/day). In an additional experiment, sea fish at 185 g/week resulting in a similar EPA and DHA intake was administered in nine individuals. We determined the bioavailability of fatty acids and carotenoids and assessed safety parameters. The intake of PT resulted in a similar increase in the n-3 PUFA and EPA content and a decrease in the PUFA n-6:n-3 ratio in plasma. PT intake caused an uptake of FX that is metabolized to fucoxanthinol (FXOH) and amarouciaxanthin A (AxA). No relevant adverse effects occurred following PT consumption. The study shows that PT is a safe and effective source of EPA and FX—and likely other nutrients—and therefore should be considered as a future sustainable food item.
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    Hydrogele aus Polyethylenglykol und methacryloylierter Gelatine für biosensorische Oberflächen
    (2024) Grübel, Jana; Tovar, Günter E. M. (Prof. Dr.)
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    Unravelling parameter interactions in calcium alginate/polyacrylamide double network hydrogels using a design of experiments approach for the optimization of mechanical properties
    (2024) Gorke, Oliver; Stuhlmüller, Marc; Tovar, Günter E. M.; Southan, Alexander
    Calcium alginate/polyacrylamide double network hydrogels were reported to be exceptionally tough. However, literature reports so far varied the sample compositions mainly by one parameter at a time approaches, thus only drawing an incomplete picture of achievable material properties. In this contribution, sample compositions are varied according to a face-centered central composite experimental design taking into account the four parameters of alginate concentration cAlg, high/low molar mass alginate mixing ratio RP, acrylamide concentration cAAm, and N,N′-methylenebisacrylamide concentration cMBA. Each sample composition is investigated in triplicate. Thus, 75 samples were investigated by tensile testing, and a detailed analysis of the significant parameters and parameter interactions influencing the mechanical properties is conducted. The data shows that two parameter interactions, involving all four tested parameters, have a large effect on the Young's modulus, the strength, the toughness and the strain at material failure. As a consequence, it becomes evident that the experimental procedure from previous studies did not always result in optimum sample compositions. The results allow optimization of the mechanical properties within the studied parameter space, and a new maximum value of the strength of 710 kPa is reported. The data also give rise to the assumption that other parameters and parameter interactions ignored also in this study may allow further tailoring of mechanical properties.
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    Microwave absorption of layer materials
    (2026) Hentrich, Andreas; Tovar, Günter E. M. (Prof. Dr.)
    The influence of the production process of atmospheric plasma sprayed ceramic coatings on the resonant absorption of millimeter waves was investigated. The main focus of the work was the application of these coatings as microwave absorbers in nuclear fusion related experiments. The production and optimization process for these absorbers was described in detail and most practically relevant parameter dependencies were investigated both in experiment and model.