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871.
Franziska Karcher Matthias Uhl Tanja Geng Timo Jacob Rolf Schuster 《Angewandte Chemie (International ed. in English)》2023,62(22):e202301253
The formation of an appropriate solid electrolyte interphase (SEI) at the anode of a sodium battery is crucially dependent on the electrochemical stability of solvent and electrolyte at the redox potential of Na/Na+ in the respective system. In order to determine entropic contributions to the relative stability of the electrolyte solution, we measure the reaction entropy of Na metal deposition for diglyme (DG) and propylene carbonate (PC) based electrolyte solutions by electrochemical microcalorimetry at single electrodes. We found a large positive reaction entropy for Na+ deposition in DG of ΔR 234 J mol−1 K−1 (c.f.: ΔR 83 J mol−1 K−1), which signals substantial entropic destabilization of Na+ in DG by about 0.73 eV, thus increasing the stability of solvent and electrolyte relative to Na+ reduction. We attribute this strong entropic destabilization to a highly negative solvation entropy of Na+, due to the low dielectric constant and high freezing entropy of DG. 相似文献
872.
Dr. Michael Holtmannspötter Eike Wienbeuker Dr. Timo Dellmann Isabelle Watrinet Prof. Dr. Ana J. Garcia-Sáez Prof. Dr. Kai Johnsson Dr. Rainer Kurre Prof. Dr. Jacob Piehler 《Angewandte Chemie (International ed. in English)》2023,62(18):e202219050
Self-labeling enzymes (SLE) such as the HaloTag have emerged as powerful tools in high and super-resolution fluorescence microscopy. Newly developed fluorogenic SLE substrates enable imaging in the presence of excess dye. To exploit this feature for reversible labeling, we engineered two variants of HaloTag7 with restored dehalogenase activity. Kinetic studies in vitro showed different turnover kinetics for reHaloTagS (≈0.006 s−1) and reHaloTagF (≈0.055 s−1). Imaging by confocal and stimulated emission depletion microscopy yielded 3-5-time enhanced photostability of reHaloTag labeling. Prominently, single molecule imaging with reHaloTags enabled controlled and stable labeling density over extended time periods. By combination with structured illumination, simultaneous visualization of single molecule diffusion and organellar dynamics was achieved. These applications highlight the potential of reHaloTag labeling for pushing the limits of advanced fluorescence microscopy techniques. 相似文献
873.
Timo Fuchs Valentín Briega-Martos Jakub Drnec Natalie Stubb Isaac Martens Federico Calle-Vallejo Prof. David A. Harrington Serhiy Cherevko Prof. Olaf M. Magnussen 《Angewandte Chemie (International ed. in English)》2023,62(34):e202304293
The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO4 by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO2 and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage. 相似文献
874.
875.
We give an algorithm to find the approximate solution of the linear-quadratic optimal control problem for stable weakly regular linear systems. This algorithm can be understood as a generalization of the Newton-Kleinman method known from the finite-dimensional theory. The central characteristic of our approach is the possibility to solve problems with unbounded control and observation operators, which is motivated by partial differential equations with boundary control and observation. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
876.
Dr. Anže Zupanc Joseph Install Prof. Marjan Jereb Prof. Timo Repo 《Angewandte Chemie (International ed. in English)》2023,62(5):e202214453
Noble metals exhibit broad arrange of applications in industry and several aspects of human life which are becoming more and more prevalent in modern times. Due to their limited sources and constantly and consistently expanding demand, recycling of secondary and waste materials must accompany the traditional mineral extractions. This Minireview covers the most recent solvometallurgical developments in regeneration of Pd, Pt, Rh, Ru, Ir, Os, Ag and Au with emphasis on sustainability and selectivity. Processing—by selective oxidative dissolution, reductive precipitation, solvent extraction, co-precipitation, membrane transfer and trapping to solid media—of eligible multi-metal substrates for recycling from waste printed circuit boards to end-of-life automotive catalysts are discussed. Outlook for possible future direction for noble metal recycling is proposed with emphasis on sustainable approaches. 相似文献
877.
Mahdi A. Mohammed Ahmed Fetoh Tamer Awad Ali Magdy M. Youssef Gaber M. Abu El-Reash 《应用有机金属化学》2023,37(1):e6910
Sodium4-hydroxy-3-([2-picolinoylhydrazineylidene]methyl)benzenesulfonate (NaH2PH) was synthesized as a novel water-soluble ligand, by the condensation of picolinohydrazide with sodium 3-formyl-4-hydroxybenzenesulfonate. The (NaH2PH) ligand and its isolated Co (II), Fe (III), Hg (II), and Pd (II) complexes were analyzed by elemental analysis and characterized by spectroscopic (Fourier transform infrared spectroscopy, UV–visible, powder XRD, 1H NMR,13C NMR, MS) and magnetic measurements. By comparing IR spectra of both ligand and the metal complexes, one can assume that the (NaH2PH) ligand behaves as a bi-negative tetradentate (ONNO) in [Co (NaPH)(H2O)2].3H2O, and a mono-negative tridentate (ONO) in [Fe (NaPH)Cl2(H2O)] complex, whereas in [Hg2(NaPH)Cl2(H2O)] complex, (NaH2PH) coordinates as a bi-negative pentadentate (ONNNO) ligand via deprotonated OH group of phenolic ring (C=N)Py and (C=N*) coordinated to one of Hg (II) ion and the oxygen atom of enolic group and (C=N)az group with the another Hg (II) ion. Moreover, (NaH2PH) acts as bi-negative tridentate (ONO) ligand in [Pd (NaPH)(H2O)].2H2O complex. The geometries of complexes were suggested based on the UV–visible spectra, magnetic measurements and confirmed by applying discrete Fourier transform (DFT) optimization studies. The thermal fragmentation of both [Pd (NaPH)(H2O)].2H2O and [Co (NaPH)(H2O)2].3H2O complexes was performed, and the kinetic and thermodynamic parameters were computed using the Coats–Redfern and Horowitz–Metzger methods. The redox behavior of divalent ions of cobalt and mercury were discussed by the cyclic voltammetry technique in the presence and absence of (NaH2PH) ligand. Biological potencies of the ligand and its metal complexes were evaluated as antioxidants (ABTS and DPPH), anticancer, DNA, and antimicrobial (Staphylococcus aureus and Bacillus subtilis as Gram (+) bacteria, Escherichia coli and Pseudomonas aeruginosa as Gram (−) bacteria, and Candida albicans as fungi). 相似文献
878.
879.
Timo V. Laine Kristian Lappalainen Jonas Liimatta Erkki Aitola Barbro Lfgren Markku Leskel 《Macromolecular rapid communications》1999,20(9):487-491
Three pyridylimine based complexes of NiII and CoII were reacted with methylaluminoxane (MAO) and tested as catalysts in ethylene polymerization. The two nickel catalysts produced mainly methyl branched polymers with good to moderate activity, while the cobalt compound showed only marginal activity. Reaction conditions strongly affect the polymer properties, such as molecular weight, melting temperature, degree of branching, and chain end unsaturation type. 相似文献
880.
In order to facilitate model reduction by balanced truncation, we introduce state space transformations that can be used to construct an ℓ2-balanced realization of a regular, linear input-ouput map with nuclear Hankel-operator directly from the system generators of an arbitrary, given realization. These balancing transformations are based on factors of the Gramians and, for infinite-dimensional systems, they are usually unbounded operators. Subsequently the ℓ2-balanced realization can be truncated in a non-trivial way to obtain an approximating, finite-dimensional model. (© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献