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    Kaskadennutzung von Lignocellulose : LX-Verfahren trifft auf B. coagulans
    (Heidelberg : Spektrum, 2020) Schroedter, Linda; Streffer, Friedrich; Streffer, Katrin; Unger, Peter; Venus, Joachim
    Investigating alternatives for petrobased substrates, lignocellulose is an interesting yet complex feedstock that offers various possibilities for the design of new and sustainable chemical routes. The novel energy-saving LX-pretreatment was combined with thermophilic Bacillus coagulans. By this, corn straw was used in an innovative cascade obtaining biogas, lignin as well as polymerisable L-(+)-lactic acid of over 99 percents optical purity. © 2020, Die Autoren.
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    Non-leaching, Highly Biocompatible Nanocellulose Surfaces That Efficiently Resist Fouling by Bacteria in an Artificial Dermis Model
    (Washington, DC : ACS Publications, 2020) Hassan, Ghada; Forsman, Nina; Wan, Xing; Keurulainen, Leena; Bimbo, Luis M.; Stehl, Susanne; van Charante, Frits; Chrubasik, Michael; Prakash, Aruna S.; Johansson, Leena-Sisko; Mullen, Declan C.; Johnston, Blair F.; Zimmermann, Ralf; Werner, Carsten; Yli-Kauhaluoma, Jari; Coenye, Tom; Saris, Per E.J.; Österberg, Monika; Moreira, Vânia M.
    Bacterial biofilm infections incur massive costs on healthcare systems worldwide. Particularly worrisome are the infections associated with pressure ulcers and prosthetic, plastic, and reconstructive surgeries, where staphylococci are the major biofilm-forming pathogens. Non-leaching antimicrobial surfaces offer great promise for the design of bioactive coatings to be used in medical devices. However, the vast majority are cationic, which brings about undesirable toxicity. To circumvent this issue, we have developed antimicrobial nanocellulose films by direct functionalization of the surface with dehydroabietic acid derivatives. Our conceptually unique design generates non-leaching anionic surfaces that reduce the number of viable staphylococci in suspension, including drug-resistant Staphylococcus aureus, by an impressive 4-5 log units, upon contact. Moreover, the films clearly prevent bacterial colonization of the surface in a model mimicking the physiological environment in chronic wounds. Their activity is not hampered by high protein content, and they nurture fibroblast growth at the surface without causing significant hemolysis. In this work, we have generated nanocellulose films with indisputable antimicrobial activity demonstrated using state-of-the-art models that best depict an "in vivo scenario". Our approach is to use fully renewable polymers and find suitable alternatives to silver and cationic antimicrobials. © 2020 American Chemical Society.
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    Analysis of complex drugs by comprehensive two-dimensional gas chromatography and high-resolution mass spectrometry: detailed chemical description of the active pharmaceutical ingredient sodium bituminosulfonate and its process intermediates
    (Heidelberg [u.a.] : Springer, 2022) Schwalb, Lukas; Tiemann, Ole; Käfer, Uwe; Gröger, Thomas; Rüger, Christopher Paul; Gayko, Guido; Zimmermann, Ralf
    The European pharmacopeia provides analytical methods for the chemical characterization of active pharmaceutical ingredients (APIs). However, the complexity of some APIs exceeds the limitations of the currently prevailing physicochemical methods. Sodium bituminosulfonate (SBS) is described by the collection of key parameters of generalizing criteria such as dry matter, sulfur and sodium content, and neutrality, but techniques to unravel the complexity on a molecular level are lacking. We present a study based on online derivatization with tetramethylammonium hydroxide in combination with comprehensive two-dimensional gas chromatography coupled to an electron ionization high-resolution time-of-flight mass spectrometer (GC × GC-HR-ToF–MS) for the chemical description of SBS as well as its process intermediates. The application of GC × GC allowed the comprehensive description of the chemical components in the API and the process intermediates for the first time. Furthermore, it was possible to classify peaks regarding their elemental and structural composition based on accurate mass information, elution behavior, and mass fragmentation pattern. This work demonstrates not only the general applicability, advantages but also limitations of GC × GC for the characterization of APIs for complex drugs. Graphical Abstract: [Figure not available: see fulltext.]
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    Blend Structure and n-Type Thermoelectric Performance of PA6/SAN and PA6/PMMA Blends Filled with Singlewalled Carbon Nanotubes
    (Basel : MDPI, 2021-4-28) Krause, Beate; Liguoro, Alice; Pötschke, Petra
    The present study investigates how the formation of melt-mixed immiscible blends based on PA6/SAN and PA6/PMMA filled with single walled nanotubes (SWCNTs) affects the thermoelectric (TE) properties. In addition to the detailed investigation of the blend morphology with compositions between 100/0 wt.% and 50/50 wt.%, the thermoelectric properties are investigated on blends with different SWCNT concentrations (0.25–3.0 wt.%). Both PA6 and the blend composites with the used type of SWCNTs showed negative Seebeck coefficients. It was shown that the PA6 matrix polymer, in which the SWCNTs are localized, mainly influenced the thermoelectric properties of blends with high SWCNT contents. By varying the blend composition, an increase in the absolute Seebeck coefficient, power factor (PF), and figure of merit (ZT) was achieved compared to the PA6 composite which is mainly related to the selective localization and enrichment of SWCNTs in the PA6 matrix at constant SWCNT loading. The maximum PFs achieved were 0.22 µW/m·K2 for PA6/SAN/SWCNT 70/30/3 wt.% and 0.13 µW/m·K2 for PA6/PMMA/SWCNT 60/40/3 wt.% compared to 0.09 µW/m·K2 for PA6/3 wt.% SWCNT which represent increases to 244% and 144%, respectively. At higher PMMA or SAN concentration, the change from matrix-droplet to a co-continuous morphology started, which, despite higher SWCNT enrichment in the PA6 matrix, disturbed the electrical conductivity, resulting in reduced PFs with still increasing Seebeck coefficients. At SWCNT contents between 0.5 and 3 wt.% the increase in the absolute Seebeck coefficient was compensated by lower electrical conductivity resulting in lower PF and ZT as compared to the PA6 composites.
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    A Review on Nano Ti-Based Oxides for Dark and Photocatalysis: From Photoinduced Processes to Bioimplant Applications
    (Basel : MDPI, 2023) Querebillo, Christine Joy
    Catalysis on TiO2 nanomaterials in the presence of H2O and oxygen plays a crucial role in the advancement of many different fields, such as clean energy technologies, catalysis, disinfection, and bioimplants. Photocatalysis on TiO2 nanomaterials is well-established and has advanced in the last decades in terms of the understanding of its underlying principles and improvement of its efficiency. Meanwhile, the increasing complexity of modern scientific challenges in disinfection and bioimplants requires a profound mechanistic understanding of both residual and dark catalysis. Here, an overview of the progress made in TiO2 catalysis is given both in the presence and absence of light. It begins with the mechanisms involving reactive oxygen species (ROS) in TiO2 photocatalysis. This is followed by improvements in their photocatalytic efficiency due to their nanomorphology and states by enhancing charge separation and increasing light harvesting. A subsection on black TiO2 nanomaterials and their interesting properties and physics is also included. Progress in residual catalysis and dark catalysis on TiO2 are then presented. Safety, microbicidal effect, and studies on Ti-oxides for bioimplants are also presented. Finally, conclusions and future perspectives in light of disinfection and bioimplant application are given.
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    Combined toxicity of gas plasma treatment and nanoparticles exposure in melanoma cells in vitro
    (Basel : MDPI, 2021) Bekeschus, Sander
    Despite continuous advances in therapy, cancer remains a deadly disease. Over the past years, gas plasma technology emerged as a novel tool to target tumors, especially skin. Another promising anticancer approach are nanoparticles. Since combination therapies are becoming increas-ingly relevant in oncology, both gas plasma treatment and nanoparticle exposure were combined. A series of nanoparticles were investigated in parallel, namely, silica, silver, iron oxide, cerium oxide, titanium oxide, and iron-doped titanium oxide. For gas plasma treatment, the atmospheric pressure argon plasma jet kINPen was utilized. Using three melanoma cell lines, the two murine non-metastatic B16F0 and metastatic B16F10 cells and the human metastatic B-Raf mutant cell line SK-MEL-28, the combined cytotoxicity of both approaches was identified. The combined cytotoxicity of gas plasma treatment and nanoparticle exposure was consistent across all three cell lines for silica, silver, iron oxide, and cerium oxide. In contrast, for titanium oxide and iron-doped titanium oxide, significantly combined cytotoxicity was only observed in B16F10 cells.
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    Towards the Growth of Hexagonal Boron Nitride on Ge(001)/Si Substrates by Chemical Vapor Deposition
    (Basel : MDPI, 2022) Franck, Max; Dabrowski, Jaroslaw; Schubert, Markus Andreas; Wenger, Christian; Lukosius, Mindaugas
    The growth of hexagonal boron nitride (hBN) on epitaxial Ge(001)/Si substrates via high-vacuum chemical vapor deposition from borazine is investigated for the first time in a systematic manner. The influences of the process pressure and growth temperature in the range of 10−7–10−3 mbar and 900–980 °C, respectively, are evaluated with respect to morphology, growth rate, and crystalline quality of the hBN films. At 900 °C, nanocrystalline hBN films with a lateral crystallite size of ~2–3 nm are obtained and confirmed by high-resolution transmission electron microscopy images. X-ray photoelectron spectroscopy confirms an atomic N:B ratio of 1 ± 0.1. A three-dimensional growth mode is observed by atomic force microscopy. Increasing the process pressure in the reactor mainly affects the growth rate, with only slight effects on crystalline quality and none on the principle growth mode. Growth of hBN at 980 °C increases the average crystallite size and leads to the formation of 3–10 well-oriented, vertically stacked layers of hBN on the Ge surface. Exploratory ab initio density functional theory simulations indicate that hBN edges are saturated by hydrogen, and it is proposed that partial de-saturation by H radicals produced on hot parts of the set-up is responsible for the growth.
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    Biomass Alginate Derived Oxygen-Enriched Carbonaceous Materials with Partially Graphitic Nanolayers for High Performance Anodes in Lithium-Ion Batteries
    (Basel : MDPI, 2022) Sun, Xiaolei; Chen, Yao; Li, Yang; Luo, Feng
    Lithium-ion batteries with high reversible capacity, high-rate capability, and extended cycle life are vital for future consumer electronics and renewable energy storage. There is a great deal of interest in developing novel types of carbonaceous materials to boost lithium storage properties due to the inadequate properties of conventional graphite anodes. In this study, we describe a facile and low-cost approach for the synthesis of oxygen-doped hierarchically porous carbons with partially graphitic nanolayers (Alg-C) from pyrolyzed Na-alginate biopolymers without resorting to any kind of activation step. The obtained Alg-C samples were analyzed using various techniques, such as X-ray diffraction, Raman, X-ray photoelectron spectroscopy, scanning electron microscope, and transmission electron microscope, to determine their structure and morphology. When serving as lithium storage anodes, the as-prepared Alg-C electrodes have outstanding electrochemical features, such as a high-rate capability (120 mAh g−1 at 3000 mA g−1) and extended cycling lifetimes over 5000 cycles. The post-cycle morphologies ultimately provide evidence of the distinct structural characteristics of the Alg-C electrodes. These preliminary findings suggest that alginate-derived carbonaceous materials may have intensive potential for next-generation energy storage and other related applications.
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    Biocompatible magnetic fluids of co-doped iron oxide nanoparticles with tunable magnetic properties
    (Basel : MDPI, 2020) Dutz, Silvio; Buske, Norbert; Landers, Joachim; Gräfe, Christine; Wende, Heiko; Clement, Joachim H.
    Magnetite (Fe3O4) particles with a diameter around 10 nm have a very low coercivity (Hc) and relative remnant magnetization (Mr/Ms), which is unfavorable for magnetic fluid hyperthermia. In contrast, cobalt ferrite (CoFe2O4) particles of the same size have a very high Hc and Mr/Ms, which is magnetically too hard to obtain suitable specific heating power (SHP) in hyperthermia. For the optimization of the magnetic properties, the Fe2+ ions of magnetite were substituted by Co2+ step by step, which results in a Co doped iron oxide inverse spinel with an adjustable Fe2+ substitution degree in the full range of pure iron oxide up to pure cobalt ferrite. The obtained magnetic nanoparticles were characterized regarding their structural and magnetic properties as well as their cell toxicity. The pure iron oxide particles showed an average size of 8 nm, which increased up to 12 nm for the cobalt ferrite. For ferrofluids containing the prepared particles, only a limited dependence of Hc and Mr/Ms on the Co content in the particles was found, which confirms a stable dispersion of the particles within the ferrofluid. For dry particles, a strong correlation between the Co content and the resulting Hc and Mr/Ms was detected. For small substitution degrees, only a slight increase in Hc was found for the increasing Co content, whereas for a substitution of more than 10% of the Fe atoms by Co, a strong linear increase in Hc and Mr/Ms was obtained. Mössbauer spectroscopy revealed predominantly Fe3+ in all samples, while also verifying an ordered magnetic structure with a low to moderate surface spin canting. Relative spectral areas of Mössbauer subspectra indicated a mainly random distribution of Co2+ ions rather than the more pronounced octahedral site-preference of bulk CoFe2O4. Cell vitality studies confirmed no increased toxicity of the Co-doped iron oxide nanoparticles compared to the pure iron oxide ones. Magnetic heating performance was confirmed to be a function of coercivity as well. The here presented non-toxic magnetic nanoparticle system enables the tuning of the magnetic properties of the particles without a remarkable change in particles size. The found heating performance is suitable for magnetic hyperthermia application. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
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    Surface-Dependent Osteoblasts Response to TiO2 Nanotubes of Dfferent Crystallinity
    (Basel : MDPI, 2020) Khrunyk, Yuliya Y.; Belikov, Sergey V.; Tsurkan, Mikhail V.; Vyalykh, Ivan V.; Markaryan, Alexandr Y.; Karabanalov, Maxim S.; Popov, Artemii A.; Wysokowski, Marcin
    One of the major challenges of implantology is to design nanoscale modifications of titanium implant surfaces inducing osseointegration. The aim of this study was to investigate the behavior of rat osteoblasts cultured on anodized TiO2 nanotubes of different crystallinity (amorphous and anatase phase) up to 24 days. TiO2 nanotubes were fabricated on VT1–0 titanium foil via a two-step anodization at 20 V using NH4F as an electrolyte. Anatase-phase samples were prepared by heat treatment at 500 °C for 1 h. VT1–0 samples with flat surfaces were used as controls. Primary rat osteoblasts were seeded over experimental surfaces for several incubation times. Scanning electron microscopy (SEM) was used to analyze tested surfaces and cell morphology. Cell adhesion and proliferation were investigated by cell counting. Osteogenic differentiation of cells was evaluated by qPCR of runt-related transcription factor 2 (RUNX2), osteopontin (OPN), integrin binding sialoprotein (IBSP), alkaline phosphatase (ALP) and osteocalcin (OCN). Cell adhesion and proliferation, cell morphology and the expression of osteogenic markers were affected by TiO2 nanotube layered substrates of amorphous and anatase crystallinity. In comparison with flat titanium, along with increased cell adhesion and cell growth a large portion of osteoblasts grown on the both nanostructured surfaces exhibited an osteocyte-like morphology as early as 48 h of culture. Moreover, the expression of all tested osteogenic markers in cells cultured on amorphous and anatase TiO2 nanotubes was upregulated at least at one of the analyzed time points. To summarize, we demonstrated that amorphous and anodized TiO2 layered substrates are highly biocompatible with rat osteoblasts and that the surface modification with about 1500 nm length nanotubes of 35 ± 4 (amorphous phase) and 41 ± 8 nm (anatase phase) in diameter is sufficient to induce their osteogenic differentiation. Such results are significant to the engineering of coating strategies for orthopedic implants aimed to establish a more efficient bone to implant contact and enhance bone repair. © 2020 by the author. Licensee MDPI, Basel, Switzerland.