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- 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.
- ItemBioinspired Polydopamine Coating as an Adhesion Enhancer Between Paraffin Microcapsules and an Epoxy Matrix(Washington, DC : ACS Publications, 2020) Fredi, Giulia; Simon, Frank; Sychev, Dmitrii; Melnyk, Inga; Janke, Andreas; Scheffler, Christina; Zimmerer, CordeliaMicroencapsulated phase change materials (PCMs) are attracting increasing attention as functional fillers in polymer matrices, to produce smart thermoregulating composites for applications in thermal energy storage (TES) and thermal management. In a polymer composite, the filler–matrix interfacial adhesion plays a fundamental role in the thermomechanical properties. Hence, this work aims to modify the surface of commercial PCM microcapsules through the formation of a layer of polydopamine (PDA), a bioinspired polymer that is emerging as a powerful tool to functionalize chemically inert surfaces due to its versatility and great adhesive potential in many different materials. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) evidenced that after PDA coating, the surface roughness increased from 9 to 86 nm, which is beneficial, as it allows a further increase in the interfacial interaction by mechanical interlocking. Spectroscopic techniques allowed investigating the surface chemistry and identifying reactive functional groups of the PDA layer and highlighted that, unlike the uncoated microcapsules, the PDA layer is able to react with oxirane groups, thereby forming a covalent bond with the epoxy matrix. Hot-stage optical microscopy and differential scanning calorimetry (DSC) highlighted that the PDA modification does not hinder the melting/crystallization process of the paraffinic core. Finally, SEM micrographs of the cryofracture surface of epoxy composites containing neat or PDA-modified microcapsules clearly evidenced improved adhesion between the capsule shell and the epoxy matrix. These results showed that PDA is a suitable coating material with considerable potential for increasing the interfacial adhesion between an epoxy matrix and polymer microcapsules with low surface reactivity. This is remarkably important not only for this specific application but also for other classes of composite materials. Future studies will investigate how the deposition parameters affect the morphology, roughness, and thickness of the PDA layer and how the layer properties influence the capsule–matrix adhesion.
- ItemDNAzymes as Catalysts for l-Tyrosine and Amyloid β Oxidation(Washington, DC : ACS Publications, 2020) Köhler, Tony; Patsis, Panagiotis A.; Hahn, Dominik; Ruland, André; Naas, Carolin; Müller, Martin; Thiele, JulianSingle-stranded deoxyribonucleic acids have an enormous potential for catalysis by applying tailored sequences of nucleotides for individual reaction conditions and substrates. If such a sequence is guanine-rich, it may arrange into a three-dimensional structure called G-quadruplex and give rise to a catalytically active DNA molecule, a DNAzyme, upon addition of hemin. Here, we present a DNAzyme-mediated reaction, which is the oxidation of l-tyrosine toward dityrosine by hydrogen peroxide. With an optimal stoichiometry between DNA and hemin of 1:10, we report an activity of 101.2 ± 3.5 μUnits (μU) of the artificial DNAzyme Dz-00 compared to 33.0 ± 1.8 μU of free hemin. Exemplarily, DNAzymes may take part in neurodegeneration caused by amyloid beta (Aβ) aggregation due to l-tyrosine oxidation. We show that the natural, human genome-derived DNAzyme In1-sp is able to oxidize Aβ peptides with a 4.6% higher yield and a 33.3% higher velocity of the reaction compared to free hemin. As the artificial DNAzyme Dz-00 is even able to catalyze Aβ peptide oxidation with a 64.2% higher yield and 337.1% higher velocity, an in-depth screening of human genome-derived DNAzymes may identify further candidates with similarly high catalytic activity in Aβ peptide oxidation.
- ItemOptical Anisotropy and Momentum-Dependent Excitons in Dibenzopentacene Single Crystals(Washington, DC : ACS Publications, 2022) Graf, Lukas; Liu, Fupin; Naumann, Marco; Roth, Friedrich; Debnath, Bipasha; Büchner, Bernd; Krupskaya, Yulia; Popov, Alexey A.; Knupfer, MartinHigh-quality single crystals of the organic semiconductor (1,2;8,9)-dibenzopentacene were grown via physical vapor transport. The crystal structure─unknown before─was determined by single-crystal X-ray diffraction; polarization-dependent optical absorption measurements display a large anisotropy in the ac plane of the crystals. The overall Davydov splitting is ∼110 meV, which is slightly lower than that in the close relative pentacene (120 meV). Momentum-dependent electron energy-loss spectroscopy measurements show a clear exciton dispersion of the Davydov components. An analysis of the dispersion using a simple 1D model indicates smaller electron- and hole-transfer integrals in dibenzopentacene as compared to pentacene. The spectral weight distribution of the excitation spectra is strongly momentum-dependent and demonstrates a strong momentum-dependent admixture of Frenkel excitons, charge-transfer excitons, and vibrational modes.
- ItemHigh-Performance, Lightweight, and Flexible Thermoplastic Polyurethane Nanocomposites with Zn2+-Substituted CoFe2O4 Nanoparticles and Reduced Graphene Oxide as Shielding Materials against Electromagnetic Pollution(Washington, DC : ACS Publications, 2021-10-11) Anju; Yadav, Raghvendra Singh; Pötschke, Petra; Pionteck, Jürgen; Krause, Beate; Kuřitka, Ivo; Vilcakova, Jarmila; Skoda, David; Urbánek, Pavel; Machovsky, Michal; Masař, Milan; Urbánek, Michal; Jurca, Marek; Kalina, Lukas; Havlica, JaromirThe development of flexible, lightweight, and thin high-performance electromagnetic interference shielding materials is urgently needed for the protection of humans, the environment, and electronic devices against electromagnetic radiation. To achieve this, the spinel ferrite nanoparticles CoFe2O4 (CZ1), Co0.67Zn0.33Fe2O4 (CZ2), and Co0.33Zn0.67Fe2O4 (CZ3) were prepared by the sonochemical synthesis method. Further, these prepared spinel ferrite nanoparticles and reduced graphene oxide (rGO) were embedded in a thermoplastic polyurethane (TPU) matrix. The maximum electromagnetic interference (EMI) total shielding effectiveness (SET) values in the frequency range 8.2-12.4 GHz of these nanocomposites with a thickness of only 0.8 mm were 48.3, 61.8, and 67.8 dB for CZ1-rGO-TPU, CZ2-rGO-TPU, and CZ3-rGO-TPU, respectively. The high-performance electromagnetic interference shielding characteristics of the CZ3-rGO-TPU nanocomposite stem from dipole and interfacial polarization, conduction loss, multiple scattering, eddy current effect, natural resonance, high attenuation constant, and impedance matching. The optimized CZ3-rGO-TPU nanocomposite can be a potential candidate as a lightweight, flexible, thin, and high-performance electromagnetic interference shielding material.