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The reaction of spirobisilafluorene (1) with lithium in dimethoxyethane produces lithium 1-methyl-spirobisilafluorenide (2), a stable pentacoordinate silicon compound with five carbon ligands, and lithium 2-methoxyethoxide, which was identified by trapping with Ph3SiCl to give Ph3Si-OCH2CH2OCH3 (4). The X-ray crystal structure of 2 shows that the geometry at silicon is an idealized trigonal bipyramid, slightly distorted toward a square pyramid. Methanolysis of 2 cleaves a Si-aryl bond producing a methyl biphenylsilafluorene, 3. Crystal structures are reported for 3 and 4. 相似文献
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Niklas Jänsch Wisely Oki Sugiarto Marius Muth Aleksandra Kopranovic Charlotte Desczyk Matthias Ballweg Frank Kirschhöfer Dr. Gerald Brenner-Weiss Prof. Dr. Franz-Josef Meyer-Almes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(58):13249-13255
Human histone deacetylase 8 is a well-recognized target for T-cell lymphoma and particularly childhood neuroblastoma. PD-404,182 was shown to be a selective covalent inhibitor of HDAC8 that forms mixed disulfides with several cysteine residues and is also able to transform thiol groups to thiocyanates. Moreover, HDAC8 was shown to be regulated by a redox switch based on the reversible formation of a disulfide bond between cysteines Cys102 and Cys153. This study on the distinct effects of PD-404,182 on HDAC8 reveals that this compound induces the dose-dependent formation of intramolecular disulfide bridges. Therefore, the inhibition mechanism of HDAC8 by PD-404,182 involves both, covalent modification of thiols as well as ligand mediated disulfide formation. Moreover, this study provides a deep molecular insight into the regulation mechanism of HDAC8 involving several cysteines with graduated capability to form reversible disulfide bridges. 相似文献
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Korbinian Riener Alexander Pthig Mirza Cokoja Wolfgang A. Herrmann Fritz E. Kühn 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(8):643-646
In recent years, the use of copper N‐heterocyclic carbene (NHC) complexes has expanded to fields besides catalysis, namely medicinal chemistry and luminescence applications. In the latter case, multinuclear copper NHC compounds have attracted interest, however, the number of these complexes in the literature is still quite limited. Bis[μ‐1,3‐bis(3‐tert‐butylimidazolin‐2‐yliden‐1‐yl)pyridine]‐1κ4C2,N:N,C2′;2κ4C2,N:N,C2′‐dicopper(I) bis(hexafluoridophosphate), [Cu2(C19H25N5)2](PF6)2, is a dimeric copper(I) complex bridged by two CNC, i.e. bis(N‐heterocyclic carbene)pyridine, ligands. Each CuI atom is almost linearly coordinated by two NHC ligands and interactions are observed between the pyridine N atoms and the metal centres, while no cuprophilic interactions were observed. Very strong absorption bands are evident in the UV–Vis spectrum at 236 and 274 nm, and an emission band is observed at 450 nm. The reported complex is a new example of a multinuclear copper NHC complex and a member of a compound class which has only rarely been reported. 相似文献
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Haiser K Fingerhut BP Heil K Glas A Herzog TT Pilles BM Schreier WJ Zinth W de Vivie-Riedle R Carell T 《Angewandte Chemie (International ed. in English)》2012,51(2):408-411
The importance of a backbone: The mechanism of formation of Dewar lesions has been investigated by using femtosecond IR spectroscopy and ab?initio calculations of the exited state. The 4π?electrocyclization is rather slow, occurs with an unusual high quantum yield, and--surprisingly--is controlled by the phosphate backbone. 相似文献
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Chemistry of the aromatic 9-germafluorenyl dianion and some related silicon and carbon species 总被引:1,自引:0,他引:1
Liu Y Ballweg D Müller T Guzei IA Clark RW West R 《Journal of the American Chemical Society》2002,124(41):12174-12181
Dipotassio-9-germafluorenyl dianion (3b) was synthesized by reduction of 9,9-dichloro-9-germafluorene (4b) with sodium/potassium alloy in tetrahydrofuran. The X-ray crystal structure of 3b, like that for the analogous silicon compound 3a, shows C-C bond length equalization in the five-membered metallole rings and C-C bond length alternation in the six-membered benzenoid rings, indicating aromatic delocalization of electrons into the germole ring of 3b. Calculated nucleus independent chemical shift (NICS) values indicate that the five-membered ring is more aromatic than the six-membered rings in 3a and 3b. Derivatization of 3b with Me(3)SiCl gave 9,9-bis(trimethylsilyl)-9-germafluorene (5). Controlled oxidation of 3b yielded dipotassio-9,9'-digerma-9,9'-bifluorenyl dianion (6). Reaction of 6 with MeOH yielded 9,9'-digerma-9,9'-bifluorene (7). The X-ray structure of 6 indicates C-C bond length alternation in the five-membered rings. Thus dianion 6, like its silicon analogue 8, has the negative charges localized at metal atoms and no aromatic character. Dipotassio-9,9'-bifluorenyl dianion (9), the carbon analogue of 6, exhibits aromaticity with its X-ray crystal structure showing the C-C bond length equalization in both the five- and six-membered rings. Derivatization of 9 with MeI gave 9,9'-dimethyl-9,9'-bifluorene (10). The structure of 10 shows that the two fluorenyl rings are cis to each other with a torsional angle of 59 degrees and a long C-C single bond (1.60 A) connecting them. 相似文献
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Michael Schneider André Tschöpe Doris Hanselmann Thomas Ballweg Carsten Gellermann Matthias Franzreb Karl Mandel 《Particle & Particle Systems Characterization》2020,37(2):1900487
Micron-sized supraparticles, consisting of a plurality of discrete nano- and microscale functional units, are assembled and fused by means of a droplet extrusion process. By combining nano magnetite, activated carbon, and conductive carbon with a polymeric binder matrix, particles are obtained which unite good magnetic properties, electrical conductivity, and adsorber activity through the high accessible surface area of the incorporated activated carbon of about 570 m2 g−1, thereby enabling a new approach toward sustainable water treatment processes. Due to the interplay of the components, it is possible to adsorb target substances, dissolved in the water which is demonstrated by the adsorption of the model dye methylene blue. A very fast adsorption kinetic and an adsorption capacity of about 400 mg g−1 is determined. By using the developed composite particles, it is also possible to electrochemically alter substances flowing through a magnetically-stabilized fluidized-bed reactor by electrochemically charging/discharging, significantly supported by the magnetic field enabling alternatingly optimum mobility/adsorption phases with contact/charging intervals. The electrochemical conversion can be increased up to 151% depending on the applied flow-rate and electrical voltage. By applying an external magnetic field, a further increase of electrochemical conversion of up to 70% can be observed. 相似文献
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Perzlmaier K Buess M Back CH Demidov VE Hillebrands B Demokritov SO 《Physical review letters》2005,94(5):057202
Quantized spin-wave eigenmodes in single, 16 nm thick and 0.75 to 4 mum wide square permalloy islands with a fourfold closure domain structure have been investigated by microfocus Brillouin light scattering spectroscopy and time resolved scanning magneto-optical Kerr microscopy. Up to six eigenmodes were detected and classified. The main direction of the spin-wave quantization in the domains was found to be perpendicular to the local static magnetization. An additional less pronounced quantization along the direction parallel to the static magnetization was also observed. 相似文献