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- ItemSpontaneous fluctuations in a plasma ion assisted deposition – correlation between deposition conditions and vanadium oxide thin film growth(Amsterdam [u.a.] : Elsevier, 2021) Frank, Anna; Dias, Miguel; Hieke, Stefan; Kruth, Angela; Scheu, ChristinaIn this work correlations between thin film crystallinity of plasma ion assisted electron beam evaporated vanadium oxide (VOx) and fluctuations of the deposition parameters during the growth process could be observed by in situ monitoring deposition conditions and electron microscopy studies. In the presented case, unintentional fluctuations in the gas flow at the plasma source caused by inhomogeneous melting of the target material lead to an increase in discharge current and therefore a decrease of the oxygen flow in the plasma source, resulting in the formation of highly crystalline bands due to a temporary increase in energy flux. The major part of the VOx thin film consists of a large number of nanocrystals embedded in an amorphous phase. In-depth structural analysis confirms a mixture of V2O5, in different modifications, VO2, as well as the mixed-valence oxides V4O9 and V6O13, for nanocrystalline parts and crystalline bands. These differ mainly in the degree of crystallinity being influenced by variations in discharge current, and partly in the amount of higher oxidized vanadium oxides. In future, precisely controlled variation of plasma source conditions will open up pathways to control and tailor crystallinity of electron beam evaporated thin films, allowing for production methods for patterned thin films or layers with graduated crystallinity. This may give rise to a new class of coatings of nanohybrids combining amorphous VOx with low electrical conductivity and crystalline domains providing a higher electrical conductivity which is useful for electrochromic displays, smart windows, and solar cells.
- ItemSinglet-Oxygen-Induced Phospholipase A2 Inhibition: A Major Role for Interfacial Tryptophan Dioxidation(Weinheim : Wiley-VCH, 2021) Nasri, Zahra; Memari, Seyedali; Wenske, Sebastian; Clemen, Ramona; Martens, Ulrike; Delcea, Mihaela; Bekeschus, Sander; Weltmann, Klaus-Dieter; von Woedtke, Thomas; Wende, KristianSeveral studies have revealed that various diseases such as cancer have been associated with elevated phospholipase A2 (PLA2) activity. Therefore, the regulation of PLA2 catalytic activity is undoubtedly vital. In this study, effective inactivation of PLA2 due to reactive species produced from cold physical plasma as a source to model oxidative stress is reported. We found singlet oxygen to be the most relevant active agent in PLA2 inhibition. A more detailed analysis of the plasma-treated PLA2 identified tryptophan 128 as a hot spot, rich in double oxidation. The significant dioxidation of this interfacial tryptophan resulted in an N-formylkynurenine product via the oxidative opening of the tryptophan indole ring. Molecular dynamics simulation indicated that the efficient interactions between the tryptophan residue and phospholipids are eliminated following tryptophan dioxidation. As interfacial tryptophan residues are predominantly involved in the attaching of membrane enzymes to the bilayers, tryptophan dioxidation and indole ring opening leads to the loss of essential interactions for enzyme binding and, consequently, enzyme inactivation. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH
- ItemApplication of scanning electrochemical microscopy for topography imaging of supported lipid bilayers(Cambridge : RSC Publ., 2022) Nasri, Zahra; Memari, Seyedali; Striesow, Johanna; Weltmann, Klaus-Dieter; von Woedtke, Thomas; Wende, KristianOxidative stress in cellular environments may cause lipid oxidation and membrane degradation. Therefore, studying the degree of lipid membrane morphological changes by reactive oxygen and nitrogen species will be informative in oxidative stress-based therapies. This study introduces the possibility of using scanning electrochemical microscopy as a powerful imaging technique to follow the topographical changes of a solid-supported lipid bilayer model induced by reactive species produced from gas plasma. The introduced strategy is not limited to investigating the effect of reactive species on the lipid bilayer but could be extended to understand the morphological changes of the lipid bilayer due to the action of membrane proteins or antimicrobial peptides.
- ItemInfluence of molecular weight of polycation polydimethyldiallylammonium and carbon nanotube content on electric conductivity of layer-by-layer films(Amsterdam [u.a.] : Elsevier, 2022) Neuber, Sven; Sill, Annekatrin; Efthimiopoulos, Ilias; Nestler, Peter; Fricke, Katja; Helm, Christiane A.For biological and engineering applications, nm-thin films with high electrical conductivity and tunable sheet resistance are desirable. Multilayers of polydimethyldiallylammonium chloride (PDADMA) with two different molecular weights (322 and 44.3 kDa) and oxidized carbon nanotubes (CNTs) were constructed using the layer-by-layer technique. The surface coverage of the CNTs was monitored with a selected visible near infrared absorption peak. Both the film thickness and the surface coverage of the CNTs increased linearly with the number of CNT/PDADMA bilayers deposited (film thickness up to 80 nm). Atomic force microscopy images showed a predominantly surface-parallel orientation of CNTs. Ohmic behavior with constant electrical conductivity of each CNT/PDADMA film and conductivity up to 4 · 103 S/m was found. A change in PDADMA molecular weight by almost a factor of ten has no effect on the film thickness and electrical conductivity, only the film/air roughness is reduced. However, increasing CNT concentration in the deposition dispersion from 0.15 up to 0.25 mg/ml results in an increased thickness of a CNT/PDADMA bilayer (by a factor of three). The increased bilayer thickness is accompanied by a decreased electrical conductivity (by a factor of four). The decreased conductivity is attributed to the increased monomer/CNT ratio.
- ItemInfluence of the active screen plasma power during afterglow nitrocarburizing on the surface modification of aisi 316l(Basel : MDPI, 2020) Böcker, Jan; Puth, Alexander; Dalke, Anke; Röpcke, Jürgen; Van Helden, Jean-Pierre H.; Biermann, HorstActive screen plasma nitrocarburizing (ASPNC) increases the surface hardness and lifetime of austenitic stainless steel without deteriorating its corrosion resistance. Using an active screen made of carbon opens up new technological possibilities that have not been exploited to date. In this study, the effect of screen power variation without bias application on resulting concentrations of process gas species and surface modification of AISI 316L steel was studied. The concentrations of gas species (e.g., HCN, NH3, CH4, C2 H2) were measured as functions of the active screen power and the feed gas composition at constant temperature using in situ infrared laser absorption spectroscopy. At constant precursor gas composition, the decrease in active screen power led to a decrease in both the concentrations of the detected molecules and the diffusion depths of nitrogen and carbon. Depending on the gas mixture, a threshold of the active screen power was found above which no changes in the expanded austenite layer thickness were measured. The use of a heating independent of the screen power offers an additional parameter for optimizing the ASPNC process in addition to changes in the feed gas composition and the bias power. In this way, an advanced process control can be established. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
- ItemLiquid assisted plasma enhanced chemical vapour deposition with a non-thermal plasma jet at atmospheric pressure(Amsterdam [u.a.] : Elsevier, 2016) Schäfer, Jan; Fricke, Katja; Mika, Filip; Pokorná, Zuzana; Zajíčková, Lenka; Foest, RüdigerThe present study introduces a process for the synthesis of functional films onto substrates directly from the liquid phase. The reported method is based on the initialization of the synthesis by means of an atmospheric pressure plasma jet operating with argon above a thin liquid film of the starting material. The process is demonstrated by the formation of a thin, solid SiOx film from siloxane-based liquid precursors. Changes in the chemical properties of the precursor were studied in-situ during the polymerization process on the diamond crystal by using Fourier transform infrared spectroscopy The elemental composition of the SiOxCy films was analyzed by X-ray photoelectron spectroscopy (XPS). Furthermore, XPS was applied to study the effect of post-annealing processes on the composition of the films. The obtained deposits exhibit a low concentration of carbon groups. The amount of hydroxyl groups and interstitial water can be reduced significantly by post-process annealing of the films.
- ItemFunctional thin films synthesized from liquid precursors by combining mist chambers and atmospheric-pressure plasma polymerization(Basel : MDPI, 2021) Barillas, Laura; Makhneva, Ekaterina; An, Sehoon; Fricke, KatjaFor the creation of thin films, the use of precursors in liquid phase offers a viable alternative when these chemicals are sensitive to high temperatures and phase changes. However, it requires appropriate liquid handling and deposition technologies capable of dispensing the fluid homogeneously to produce a uniform thin film. We report different tailor-made mist chamber designs integrated in an atmospheric-pressure plasma polymerization process for the synthesis of functional thin polymer films from liquid precursors. A systematic investigation, evaluated by performance indicators, is presented on the characteristics and suitability of metallic 3D-printed mist chambers depending on inner volume, geometry and surface post-treatment, for the deposition of a thin liquid monomer film. To assess the quality of the subsequently obtained plasma-polymerized (pp) films, their properties were characterized in terms of thickness, chemical composition, surface morphology and stability in aqueous environment. It was found that the specification of the mist chambers along with the plasma process parameters influences the pp film’s thickness, surface morphology and degree of monomer conversion. This study is one of the first demonstrations of a controllable process able to tune the cross-linked polymeric chains of plasma-polymers at atmospheric pressure, highlighting the opportunities of using mist chambers and plasma technology to discover tailored organic thin films to materials sciences and life sciences.
- ItemSupercritical fluid extraction-supercritical fluid chromatography of saliva: Single-quadrupole mass spectrometry monitoring of caffeine for gastric emptying studies†(Weinheim : Wiley-VCH, 2021) Hofstetter, Robert K.; Schulig, Lukas; Bethmann, Jonas; Grimm, Michael; Sager, Maximilian; Aude, Philipp; Keßler, Rebecca; Kim, Simon; Weitschies, Werner; Link, AndreasSaliva is an attractive sampling matrix for measuring various endogenous and exogeneous substances but requires sample treatment prior to chromatographic analysis. Exploiting supercritical CO2 for both extraction and chromatography simplifies sample preparation, reduces organic solvent consumption, and minimizes exposure to potentially infectious samples, but has not yet been applied to oral fluid. Here, we demonstrate the feasibility and benefits of online supercritical fluid extraction coupled to supercritical fluid chromatography and single-quadrupole mass spectrometry for monitoring the model salivary tracer caffeine. A comparison of 13C- and 32S-labeled internal standards with external standard calibration confirmed the superiority of stable isotope-labeled caffeine over nonanalogous internal standards. As proof of concept, the validated method was applied to saliva from a magnetic resonance imaging study of gastric emptying. After administration of 35 mg caffeine via ice capsule, salivary levels correlated with magnetic resonance imaging data, corroborating caffeine's usefulness as tracer of gastric emptying (R2 = 0.945). In contrast to off-line methods, online quantification required only minute amounts of organic solvents and a single manual operation prior to online bioanalysis of saliva, thus demonstrating the usefulness of CO2-based extraction and separation techniques for potentially infective biomatrices.
- ItemD-Glucose Oxidation by Cold Atmospheric Plasma-Induced Reactive Species(Washington, DC : ACS Publications, 2022) Ahmadi, Mohsen; Nasri, Zahra; von Woedtke, Thomas; Wende, KristianThe glucose oxidation cascade is fascinating; although oxidation products have high economic value, they can manipulate the biological activity through posttranslational modification such as glycosylation of proteins, lipids, and nucleic acids. The concept of this work is based on the ability of reactive species induced by cold atmospheric plasma (CAP) in aqueous liquids and the corresponding gas-liquid interface to oxidize biomolecules under ambient conditions. Here, we report the oxidation of glucose by an argon-based dielectric barrier discharge plasma jet (kINPen) with a special emphasis on examining the reaction pathway to pinpoint the most prominent reactive species engaged in the observed oxidative transformation. Employing d-glucose and d-glucose-13C6solutions and high-resolution mass spectrometry and ESI-tandem MS/MS spectrometry techniques, the occurrence of glucose oxidation products, for example, aldonic acids and aldaric acids, glucono- and glucaro-lactones, as well as less abundant sugar acids including ribonic acid, arabinuronic acid, oxoadipic acid, 3-deoxy-ribose, glutaconic acid, and glucic acid were surveyed. The findings provide deep insights into CAP chemistry, reflecting a switch of reactive species generation with the feed gas modulation (Ar or Ar/O2with N2curtain gas). Depending on the gas phase composition, a combination of oxygen-derived short-lived hydroxyl (•OH)/atomic oxygen [O(3P)] radicals was found responsible for the glucose oxidation cascade. The results further illustrate that the presence of carbohydrates in cell culture media, gel formulations (agar), or other liquid targets (juices) modulate the availability of CAP-generated species in vitro. In addition, a glycocalyx is attached to many mammalian proteins, which is essential for the respective physiologic role. It might be questioned if its oxidation plays a role in CAP activity.
- ItemRing-Closure Mechanisms Mediated by Laccase to Synthesize Phenothiazines, Phenoxazines, and Phenazines(Washington, DC : ACS Publications, 2020) Hahn, Veronika; Mikolasch, Annett; Weitemeyer, Josephine; Petters, Sebastian; Davids, Timo; Lalk, Michael; Lackmann, Jan-Wilm; Schauer, FriederThe green and environmentally friendly synthesis of highly valuable organic substances is one possibility for the utilization of laccases (EC 1.10.3.2). As reactants for the herein described syntheses, different o-substituted arylamines or arylthiols and 2,5-dihydroxybenzoic acid and its derivatives were used. In this way, the formation of phenothiazines, phenoxazines, and phenazines was achieved in aqueous solution mediated by the laccase of Pycnoporus cinnabarinus in the presence of oxygen. Two types of phenothiazines (3-hydroxy- and 3-oxo-phenothiazines) formed in one reaction assay were described for the first time. The cyclization reactions yielded C–N, C–S, or C–O bonds. The syntheses were investigated with regard to the substitution pattern of the reaction partners. Differences in C–S and C–N bond formations without cyclization are discussed.