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991.
Wan Y Hur W Cho CY Liu Y Adrian FJ Lozach O Bach S Mayer T Fabbro D Meijer L Gray NS 《Chemistry & biology》2004,11(2):247-259
Hymenialdisine (HMD) is a sponge-derived natural product kinase inhibitor with nanomolar activity against CDKs, Mek1, GSK3beta, and CK1 and micromolar activity against Chk1. In order to explore the broader application of the pyrrolo[2,3-c]azepine skeleton of HMD as a general kinase inhibitory scaffold, we searched for additional protein targets using affinity chromatography in conjunction with the synthesis of diverse HMD analogs and profiled HMD against a panel of 60 recombinant enzymes. This effort has led to nanomolar to micromolar inhibitors of 11 new targets including p90RSK, KDR, c-Kit, Fes, MAPK1, PAK2, PDK1, PKCtheta, PKD2, Rsk1, and SGK. The synthesis of HMD analogs has resulted in the identification of compounds with enhanced and/or dramatically altered selectivities relative to HMD (28n) and in molecules with antiproliferative activities 30-fold higher than HMD (28p). 相似文献
992.
Efficient photocyclization from a low-lying triplet state is reported for a photochromic dithienylperfluorocyclopentene with Ru(bpy)3 units attached via a phenylene linker to the thiophene rings. The ring-closure reaction in the nanosecond domain is sensitized by the metal complexes. Upon photoexcitation into the lowest Ru-to-bpy 1MLCT state followed by intersystem crossing to emitting 3MLCT states, photoreactive 3IL states are populated by an efficient energy-transfer process. The involvement of these 3IL states explains the quantum yield of the photocyclization, which is independent of the excitation wavelength but decreases strongly in the presence of dioxygen. This behavior differs substantially from the photocyclization of the nonemissive dithienylperfluorocyclopentene free ligand, which occurs from the lowest 1IL state on a picosecond time scale and is insensitive to oxygen quenching. Cyclic voltammetric studies have also been performed to gain further insight into the energetics of the system. The very high photocyclization quantum yields, far above 0.5 in both cases, are ascribed to the strong steric repulsion between the bulky substituents on the dithienylperfluorocyclopentene bridge bearing the chelating bipyridine sites or the Ru(bpy)3 moieties, forcing the system to adopt nearly exclusively the reactive antiparallel conformation. In contrast, replacement of both Ru(II) centers by Os(II) completely prevents the photocyclization reaction upon light excitation into the low-lying Os-to-bpy 1MLCT state. The photoreaction can only be triggered by optical population of the higher lying 1IL excited state of the central photochromic unit, but its yield is low due to efficient energy transfer to the luminescent lowest 3MLCT state. 相似文献
993.
The compounds K0.91U1.79S6 and KU2Se6, members of the AAn2Q6 actinide family (A = alkali metal or Tl; An = Th or U; Q = S, Se, or Te), have been synthesized from US2, K2S, and S at 1273 K and U, K2Se, and Se at 1173 K, respectively. KU2Se6 shows Curie-Weiss behavior above 30 K and no magnetic ordering down to 5 K. The value of mu(eff) is 2.95(1) mu(B)/U. Its electronic spectrum shows the peaks characteristic of 5f-5f transitions. It is a semiconductor with an activation energy of 0.27 eV for electrical conduction. Both K0.91U1.79S6 and KU2Se6 crystallize in space group Immm of the orthorhombic system and are of the KTh2Se6 structure type. Both contain infinite one-dimensional linear Q-Q chains characteristic of the AAn2Q6 family. Typical of the known AAn2Q6 compounds, in KU2Se6, there are two alternating Se-Se distances of 2.703(2) and 2.855(2) A, both much longer than an Se-Se single bond. In contrast, in K0.91U1.79S6, the first sulfide of this family to be characterized structurally, there are alternating normal S2(2-) pairs 2.097(5) A in length. In K0.91U1.79S6, the formal oxidation state of U is 4+. 相似文献
994.
Mayneris J Saracibar A Goldfield EM Gonzalez M García E Gray SK 《The journal of physical chemistry. A》2006,110(16):5542-5548
The complex-forming CH + H2 --> CH2 + H reaction is studied employing a recently developed global potential energy function. The reaction probability in the total angular momentum J = 0 limit is estimated with a four-atom quantum wave packet method and compared with classical trajectory and statistical theory results. The formation of complexes from different reactant internal states is also determined with wave packet calculations. While there is no barrier to reaction along the minimum energy path, we find that there are angular constraints to complex formation. Trajectory-based estimates of the low-pressure rate constants are made and compared with experimental results. We find that zero-point energy violation in the trajectories is a particularly severe problem for this reaction. 相似文献
995.
This study focuses on how intact, hydrophobic bacteria in their stationary (i.e., non-dividing) phase could adsorb onto the hexadecane–water interface and alter its mechanical properties. The two strains of bacteria used in forming the interfacial films were Acinetobacter venetianus RAG-1 and Rhodococcus erythropolis 20S-E1-c. Using the dynamic pendant drop technique, the film interfacial tension was monitored as the surface area was made to undergo transient changes. Under static conditions, both types of bacteria had no effect on the interfacial tension. When subjected to transient excitations, however, the two bacterial films exhibited clear and qualitatively similar rheological properties: they responded as two-dimensional Maxwellian materials when the interfacial areas were dilated suddenly, but appeared to be purely elastic upon rapid area compression. Such rheological behaviours are “non-linear” in that the responses of the tension to area dilation and contraction are not mirror images of one another. Despite their qualitative similarities, the two types of film had very distinct film elasticities and relaxation times. The most striking difference between the two bacterial films was revealed under continuous reduction of area, when the A. venetianus RAG-1 system displayed a “paper-like” interface, whereas the interface of the R. erythropolis 20S-E1-c system was “soap film-like”. These macroscopic observations could be explained by the surface ultrastructures of the two cell strains determined using transmission electron microscopy. 相似文献
996.
Peter G. Jones Lilian Gray 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(5):o282-o283
The crystal packing of the title compound, C8H11BrN+·Br?, involves three types of secondary interaction: a classical N—H?Br? hydrogen bond, a `weak' but short C—H?Br? interaction (normalized H?Br distance of 2.66 Å) and a cation–anion Br?Br contact of 3.6331 (4) Å. The hydrogen bonds connect two cations and two anions to form rings of graph set R(14). The Br?Br contacts link these rings to form layers parallel to the bc plane. 相似文献
997.
Colloidal chiral nematic suspensions of cellulose were prepared from dissolving grade wood pulp. On evaporation of the water, the suspension dries down to give iridescent cellulose films. The optical properties of the films may be characterized by incorporating dyes in the films, and following the ordering of the dye molecules by measurement of induced circular dichroism (ICD). Structural changes to the films, such as decreasing the chiral nematic pitch by increasing the salt content and increasing the chiral nematic order through magnetic alignment, can be monitored by measuring the changes in ICD. 相似文献
998.
Zhang C Zhang F Zhu T Cheng A Xu J Zhang Q Mohney SE Henderson RH Wang YA 《Optics letters》2008,33(21):2437-2439
Upconverted lasing in the nonlinear, two-photon absorption regime has been demonstrated, for the first time to the best of our knowledge in colloidal nanocrystal quantum dots (NQDs). Upon pulse excitation at sub-bandgap photon energies the radiative recombination of excitons in close-packed CdSe/CdS/ZnS core-shell NQDs was found to be sufficiently fast to compete with the intrinsic nonradiative Auger recombination, as confirmed by the presence of a fast decay (approximately 7 ps) in the time-resolved photoluminescence. 相似文献
999.
The thermoelectric power of the high temperature conductive phase of V6O13 was measured and its variation with temperature is explained in terms of a simple model. The model assumes a narrow band for the d′ electrons and the Seebeck coefficient is calculated in the atomic limit of the narrow band. The only fitting parameter of the theoretical expression is U — the effective Coulomb repulsion between two electrons occupying the same site. Very good agreement between theory and experiment was obtained for U = 0.075 eV. 相似文献
1000.
Bifunctional Electrocatalysts for Overall Water Splitting from an Iron/Nickel‐Based Bimetallic Metal–Organic Framework/Dicyandiamide Composite 下载免费PDF全文
Xiaojia Zhao Dr. Pradip Pachfule Shuang Li Jan Ron Justin Simke Dr. Johannes Schmidt Prof. Dr. Arne Thomas 《Angewandte Chemie (International ed. in English)》2018,57(29):8921-8926
Pyrolysis of a bimetallic metal–organic framework (MIL‐88‐Fe/Ni)‐dicyandiamide composite yield a Fe and Ni containing carbonaceous material, which is an efficient bifunctional electrocatalyst for overall water splitting. FeNi3 and NiFe2O4 are found as metallic and metal oxide compounds closely embedded in an N‐doped carbon–carbon nanotube matrix. This hybrid catalyst (Fe‐Ni@NC‐CNTs) significantly promotes the charge transfer efficiency and restrains the corrosion of the metallic catalysts, which is shown in a high OER and HER activity with an overpotential of 274 and 202 mV, respectively at 10 mA cm?2 in alkaline solution. When this bifunctional catalyst was further used for H2 and O2 production in an electrochemical water‐splitting unit, it can operate in ambient conditions with a competitive gas production rate of 1.15 and 0.57 μL s?1 for hydrogen and oxygen, respectively, showing its potential for practical applications. 相似文献