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61.
62.
Dr. Olaf Morawski Dr. Paweł Gawryś Dr. Jarosław Sadło Prof. Andrzej L. Sobolewski 《Chemphyschem》2022,23(11):e202200077
When irradiated with violet light, hexaazatrinaphthylene (HATN) extracts a hydrogen atom from an alcohol forming a long-living hydrogenated species. The apparent kinetic isotope effect for fluorescence decay time in deuterated methanol (1.56) indicates that the lowest singlet excited state of the molecule is a precursor for intermolecular hydrogen transfer. The photochemical hydrogenation occurs in several alcohols (methanol, ethanol, isopropanol) but not in water. Hydrogenated HATN can be detected optically by an absorption band at 1.78 eV as well as with EPR (electron paramagnetic resonance) and NMR techniques. Mass spectrometry of photoproducts reveal di-hydrogenated HATN structures along with methoxylated and methylated HATN molecules which are generated through the reaction with methoxy radicals (remnants from alcohol splitting). Experimental findings are consistent with the theoretical results which predicted that for the excited state of the HATN-solvent molecular complex, there exists a barrierless hydrogen transfer from methanol but a small barrier for the similar oxidation of water. 相似文献
63.
Dirk Steinborn Olaf Gravenhorst Clemens Bruhn Dusan Miklo Michal Dunaj-Jur
o Alfred Kolbe 《无机化学与普通化学杂志》1997,623(12):1954-1958
Synthesis and Characterization of Aquapentachloroplatinates(IV) – Structure of [K(18-crown-6)][PtCl5(H2O)] The crown ether complex of the aquapentachloroplatinic acid of the composition [H13O6][PtCl5(H4O2)] · 2(18-cr-6) ( 2 ) reacts with K2CO3 and [NnBu4]OH in aqueous solution to give [K(18-cr-6)][PtCl5(H2O)] ( 5 a ) and [NnBu4][PtCl5(H2O)] · 1/2 (18-cr-6) · H2O ( 5 b ), respectively. Both compounds were characterized by microanalysis, vibrational (IR, Raman) and NMR (1H, 13C, 195Pt) spectroscopy. The X-ray structure analysis of 5 a (orthorhombic, pnma; a = 16,550(4), b = 18,044(3), c = 7,415(1) Å; Z = 4; R1 = 0,0183; wR2 = 0,0414) reveals that the crystal is threaded by chains built up of [PtCl5(H2O)]? and [K(18-cr-6)]+ units. There are tight K …? Cl contacts (d(K? Cl1)) = 3,0881(9) Å and OW? H? Ocr hydrogen bridges (d(O1 …? O2) = 2,806(3) Å) between these units. The coordination polyhedron [PtCl5O] has approximately C4v symmetry. 相似文献
64.
65.
Julia Post Vanessa Kogel Anja Schaffrath Philipp Lohmann N. Jon Shah Karl-Josef Langen Dieter Willbold Antje Willuweit Janine Kutzsche 《Molecules (Basel, Switzerland)》2021,26(6)
Amyotrophic lateral sclerosis (ALS) is a progressive neurodegenerative disease characterised by selective neuronal death in the brain stem and spinal cord. The cause is unknown, but an increasing amount of evidence has firmly certified that neuroinflammation plays a key role in ALS pathogenesis. Neuroinflammation is a pathological hallmark of several neurodegenerative disorders and has been implicated as driver of disease progression. Here, we describe a treatment study demonstrating the therapeutic potential of a tandem version of the well-known all-d-peptide RD2 (RD2RD2) in a transgenic mouse model of ALS (SOD1*G93A). Mice were treated intraperitoneally for four weeks with RD2RD2 vs. placebo. SOD1*G93A mice were tested longitudinally during treatment in various behavioural and motor coordination tests. Brain and spinal cord samples were investigated immunohistochemically for gliosis and neurodegeneration. RD2RD2 treatment in SOD1*G93A mice resulted not only in a reduction of activated astrocytes and microglia in both the brain stem and lumbar spinal cord, but also in a rescue of neurons in the motor cortex. RD2RD2 treatment was able to slow progression of the disease phenotype, especially the motor deficits, to an extent that during the four weeks treatment duration, no significant progression was observed in any of the motor experiments. Based on the presented results, we conclude that RD2RD2 is a potential therapeutic candidate against ALS. 相似文献
66.
67.
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
68.
Dr. Bjarne Kreitz Dr. Patrick Lott Prof. Dr. Felix Studt Prof. Dr. Andrew J. Medford Prof. Dr. Olaf Deutschmann Prof. Dr. C. Franklin Goldsmith 《Angewandte Chemie (International ed. in English)》2023,62(39):e202306514
The study presents an ab-initio based framework for the automated construction of microkinetic mechanisms considering correlated uncertainties in all energetic parameters and estimation routines. 2000 unique microkinetic models were generated within the uncertainty space of the BEEF-vdW functional for the oxidation reactions of representative exhaust gas emissions from stoichiometric combustion engines over Pt(111) and compared to experiments through multiscale modeling. The ensemble of simulations stresses the importance of considering uncertainties. Within this set of first-principles-based models, it is possible to identify a microkinetic mechanism that agrees with experimental data. This mechanism can be traced back to a single exchange-correlation functional, and it suggests that Pt(111) could be the active site for the oxidation of light hydrocarbons. The study provides a universal framework for the automated construction of reaction mechanisms with correlated uncertainty quantification, enabling a DFT-constrained microkinetic model optimization for other heterogeneously catalyzed systems. 相似文献
69.
Olaf Bröcker 《Journal of Geometry》2002,75(1-2):46-60
For M?bius planes Schaeffer [9] has proved that all seven
point degenerations of Miquel's Theorem characterize miquelian M?bius
planes. For Laguerre planes we have several degenerations of Miquel's
Theorem with eight and seven points. We prove that all except one of
these degenerations characterize miquelian Laguerre planes. The
remaining degeneration characterizes elation Laguerre planes.
Received 14 September 2001; revised 1 September 2002. 相似文献
70.
Moscow Institute of New Technologies, Twente University (Netherlands). Translated from Funktsional'nyi Analiz i Ego Prilozheniya, Vol. 26, No. 4, pp. 90–92, October–December, 1992. 相似文献