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    Nonspherical Nanoparticle Shape Stability Is Affected by Complex Manufacturing Aspects: Its Implications for Drug Delivery and Targeting
    (Weinheim : Wiley-VCH, 2019) Haryadi, Bernard Manuel; Hafner, Daniel; Amin, Ihsan; Schubel, Rene; Jordan, Rainer; Winter, Gerhard; Engert, Julia
    The shape of nanoparticles is known recently as an important design parameter influencing considerably the fate of nanoparticles with and in biological systems. Several manufacturing techniques to generate nonspherical nanoparticles as well as studies on in vitro and in vivo effects thereof have been described. However, nonspherical nanoparticle shape stability in physiological-related conditions and the impact of formulation parameters on nonspherical nanoparticle resistance still need to be investigated. To address these issues, different nanoparticle fabrication methods using biodegradable polymers are explored to produce nonspherical nanoparticles via the prevailing film-stretching method. In addition, systematic comparisons to other nanoparticle systems prepared by different manufacturing techniques and less biodegradable materials (but still commonly utilized for drug delivery and targeting) are conducted. The study evinces that the strong interplay from multiple nanoparticle properties (i.e., internal structure, Young's modulus, surface roughness, liquefaction temperature [glass transition (Tg) or melting (Tm)], porosity, and surface hydrophobicity) is present. It is not possible to predict the nonsphericity longevity by merely one or two factor(s). The most influential features in preserving the nonsphericity of nanoparticles are existence of internal structure and low surface hydrophobicity (i.e., surface-free energy (SFE) > ≈55 mN m−1, material–water interfacial tension <6 mN m−1), especially if the nanoparticles are soft (<1 GPa), rough (Rrms > 10 nm), porous (>1 m2 g−1), and in possession of low bulk liquefaction temperature (<100 °C). Interestingly, low surface hydrophobicity of nanoparticles can be obtained indirectly by the significant presence of residual stabilizers. Therefore, it is strongly suggested that nonsphericity of particle systems is highly dependent on surface chemistry but cannot be appraised separately from other factors. These results and reviews allot valuable guidelines for the design and manufacturing of nonspherical nanoparticles having adequate shape stability, thereby appropriate with their usage purposes. Furthermore, they can assist in understanding and explaining the possible mechanisms of nonspherical nanoparticles effectivity loss and distinctive material behavior at the nanoscale. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Plasma-Assisted Immobilization of a Phosphonium Salt and Its Use as a Catalyst in the Valorization of CO2
    (Weinheim : Wiley-VCH, 2020) Hu, Yuya; Peglow, Sandra; Longwitz, Lars; Frank, Marcus; Epping, Jan Dirk; Breser, Volker; Werner, Thomas
    The first plasma-assisted immobilization of an organocatalyst, namely a bifunctional phosphonium salt in an amorphous hydrogenated carbon coating, is reported. This method makes the requirement for prefunctionalized supports redundant. The immobilized catalyst was characterized by solid-state 13C and 31P NMR spectroscopy, SEM, and energy-dispersive X-ray spectroscopy. The immobilized catalyst (1 mol %) was employed in the synthesis of cyclic carbonates from epoxides and CO2. Notably, the efficiency of the plasma-treated catalyst on SiO2 was higher than those of the SiO2 support impregnated with the catalyst and even the homogeneous counterpart. After optimization of the reaction conditions, 13 terminal and four internal epoxides were converted with CO2 to the respective cyclic carbonates in yields of up to 99 %. Furthermore, the possibility to recycle the immobilized catalyst was evaluated. Even though the catalyst could be reused, the yields gradually decreased from the third run. However, this is the first example of the recycling of a plasma-immobilized catalyst, which opens new possibilities in the recovery and reuse of catalysts. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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    Singlet-Oxygen Generation by Peroxidases and Peroxygenases for Chemoenzymatic Synthesis
    (Weinheim : Wiley-VCH, 2020) Ingenbosch, Kim N.; Quint, Stephan; Dyllick-Brenzinger, Melanie; Wunschik, Dennis S.; Kiebist, Jan; Süss, Philipp; Liebelt, Ute; Zuhse, Ralf; Menyes, Ulf; Scheibner, Katrin; Mayer, Christian; Opwis, Klaus; Gutmann, Jochen S.; Hoffmann-Jacobsen, Kerstin
    Singlet oxygen is a reactive oxygen species undesired in living cells but a rare and valuable reagent in chemical synthesis. We present a fluorescence spectroscopic analysis of the singlet-oxygen formation activity of commercial peroxidases and novel peroxygenases. Singlet-oxygen sensor green (SOSG) is used as fluorogenic singlet oxygen trap. Establishing a kinetic model for the reaction cascade to the fluorescent SOSG endoperoxide permits a kinetic analysis of enzymatic singlet-oxygen formation. All peroxidases and peroxygenases show singlet-oxygen formation. No singlet oxygen activity could be found for any catalase under investigation. Substrate inhibition is observed for all reactive enzymes. The commercial dye-decolorizing peroxidase industrially used for dairy bleaching shows the highest singlet-oxygen activity and the lowest inhibition. This enzyme was immobilized on a textile carrier and successfully applied for a chemical synthesis. Here, ascaridole was synthesized via enzymatically produced singlet oxygen. © 2020 Wiley-VCH GmbH
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    Time-resolved luminescence detection of peroxynitrite using a reactivity-based lanthanide probe
    (Cambridge : RSC, 2020) Breen, Colum; Pal, Robert; Elsegood, Mark R.J.; Teat, Simon J.; Iza, Felipe; Wende, Kristian; Buckley, Benjamin R.; Butler, Stephen
    Peroxynitrite (ONOO-) is a powerful and short-lived oxidant formed in vivo, which can react with most biomolecules directly. To fully understand the roles of ONOO- in cell biology, improved methods for the selective detection and real-time analysis of ONOO- are needed. We present a water-soluble, luminescent europium(iii) probe for the rapid and sensitive detection of peroxynitrite in human serum, living cells and biological matrices. We have utilised the long luminescence lifetime of the probe to measure ONOO- in a time-resolved manner, effectively avoiding the influence of autofluorescence in biological samples. To demonstrate the utility of the Eu(iii) probe, we monitored the production of ONOO- in different cell lines, following treatment with a cold atmospheric plasma device commonly used in the clinic for skin wound treatment. This journal is © The Royal Society of Chemistry.
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    Self-assembled mono- and bilayers on gold electrodes to assess antioxidants—a comparative study
    (Berlin ; Heidelberg ; New York : Springer, 2020) Ravandeh, Mehdi; Thal, Dana; Kahlert, Heike; Wende, Kristian; Lalk, Michael
    Oxidative stress is considered as an imbalance of reactive species over antioxidants, leading to diseases and cell death. Various methods have been developed to determine the antioxidant potential of natural or synthetic compounds based on the ability to scavenge free radicals. However, most of them lack biological relevance. Here, a gold-based self-assembled monolayer (SAM) was compared with a gold-supported lipid bilayer as models for the mammalian cell membrane to evaluate the free radical scavenging activity of different antioxidants. The oxidative damage induced by reactive species was verified by cyclic and differential pulse voltammetry and measured by the increase of electrochemical peak current of a redox probe. Trolox, caffeic acid (CA), epigallocatechin gallate (EGCG), ascorbic acid (AA), and ferulic acid (FA) were used as model antioxidants. The change in the decrease of the electrochemical signal reflecting oxidative membrane damage confirms the expected protective role. Both model systems showed similar efficacies of each antioxidant, the achieved order of radical scavenging potential is as follows: Trolox > CA > EGCG > AA > FA. The results showed that the electrochemical assay with SAM-modified electrodes is a stable and powerful tool to estimate qualitatively the antioxidative activity of a compound with respect to cell membrane protection against biologically relevant reactive species. © 2020, The Author(s).
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    Does the energy transfer from Ar(1s) atoms to N2 lead to dissociation?
    (Hoboken, NJ : Wiley Interscience, 2020) Klages, Claus‐Peter; Martinovs, Andris; Bröcker, Lars; Loffhagen, Detlef
    Dielectric-barrier discharges (DBDs) in Ar–N2 mixtures, with N2 fractions in 0.1–1% range, would be attractive alternatives to DBDs in pure N2 if energy-transfer reactions between Ar(1s) atoms and N2 molecules were an efficient source of N atoms. Attempts to functionalize polyolefins in flowing postdischarges fed by such DBDs, as well as the search for the First Positive System in the emission spectrum, however, failed. Evidently, the energy-transfer reactions do not produce N atoms. For Ar(1s3) and Ar(1s5) metastable states, this fact has already been reported in the literature. For Ar(1s2) and Ar(1s4) resonant states, a quantitative argument is derived in this paper: energy transfer from Ar(1s) atoms to N2 molecules is not an efficient source of N atoms.
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    Plasma medical oncology: Immunological interpretation of head and neck squamous cell carcinoma
    (Hoboken, NJ : Wiley Interscience, 2020) Witzke, Katharina; Seebauer, Christian; Jesse, Katja; Kwiatek, Elisa; Berner, Julia; Semmler, Marie‐Luise; Boeckmann, Lars; Emmert, Steffen; Weltmann, Klaus‐Dieter; Metelmann, Hans‐Robert; Bekeschus, Sander
    The prognosis of patients suffering from advanced-stage head and neck squamous cell carcinoma (HNSCC) remains poor. Medical gas plasma therapy receives growing attention as a novel anticancer modality. Our recent prospective observational study on HNSCC patients suffering from contaminated tumor ulcerations without lasting remission after first-line anticancer therapy showed remarkable efficacy of gas plasma treatment, with the ulcerated tumor surface decreasing by up to 80%. However, tumor growth relapsed, and this biphasic response may be a consequence of immunological and molecular changes in the tumor microenvironment that could be caused by (a) immunosuppression, (b) tumor cell adaption, (c) loss of microbe-induced immunostimulation, and/or (d) stromal cell adaption. These considerations may be vital for the design of clinical plasma trials in the future.
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    Efficiency of plasma-processed air for biological decontamination of crop seeds on the premise of unimpaired seed germination
    (Hoboken, NJ : Wiley Interscience, 2021) Wannicke, Nicola; Wagner, Robert; Stachowiak, Joerg; Nishime, Thalita M.C.; Ehlbeck, Joerg; Weltmann, Klaus‐Dieter; Brust, Henrike
    In this study, the antimicrobial effect of plasma-processed air (PPA) generated by a microwave-induced nonthermal plasma was investigated for preharvest utilization using three crop species: Barley, rape, and lupine. Bacillus atrophaeus spores were chosen as a model, inoculated onto seeds, and subsequently treated with PPA at two different flow rates, different filling regimes, and gas exposure times. PPA treatment was efficient in reducing viable spores of B. atrophaeus, reaching sporicidal effects in all species at certain parameter combinations. Maximum germination of seeds was strongly reduced in barley and rape seeds at some parameter combination, whereas it had a modest effect on lupine seeds. Seed hydrophilicity was not altered. Overall, PPA investigated in this study proved suitable for preharvest applications.
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    HelixJet: An innovative plasma source for next-generation additive manufacturing (3D printing)
    (Hoboken, NJ : Wiley Interscience, 2020) Schäfer, Jan; Quade, Antje; Abrams, Kerry J.; Sigeneger, Florian; Becker, Markus M.; Majewski, Candice; Rodenburg, Cornelia
    A novel plasma source (HelixJet) for use in additive manufacturing (AM)/3D printing is proposed. The HelixJet is a capacitively coupled radio frequency plasma with a double-helix electrode configuration that generates a surprisingly stable and homogeneous glow plasma at low flow rates of argon and its mixtures at atmospheric pressure. The HelixJet was tested on three polyamide powders usually used to produce parts by laser sintering, a powder-based AM process, to form local deposits. The chemical composition of such plasma-printed samples is compared with thermally produced and laser-sintered samples with respect to differences in morphology that result from the different thermal cycles on several length scales. Plasma prints exhibit unique features attributable to the nonequilibrium chemistry and to the high-speed heat exchange.
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    Effect of cold atmospheric pressure plasma treatment of eggshells on the total bacterial count inoculated Salmonella Enteritidis and selected quality parameters
    (Hoboken, NJ : Wiley Interscience, 2021) Moritz, Maike; Wiacek, Claudia; Weihe, Thomas; Ehlbeck, Jörg; Weltmann, Klaus‐Dieter; Braun, Peggy G.
    In the European Union, foodborne outbreaks caused by Salmonella Enteritidis, related to eggs and egg products, have even been reported in 2018. Atmospheric pressure plasma is becoming increasingly important as a decontamination method. A semidirect cold atmospheric pressure plasma, the flexible electrode plasma source, was developed for treating whole hen's eggs. An average reduction of 1.16 and 0.95 log colony-forming units (CFU)/egg was achieved for the total bacterial count of clean and dirty eggs, respectively. An inactivation of 4.1 log CFU/egg Salmonella Enteritidis was achieved with artificially inoculated eggshells. Selected quality parameters and sensory properties were analysed. Overall, the present study yielded promising results for a realistic implementation of an industrial prototype plasma source.