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21.
Steffen Wolf Benedikt Sohmen Bjrn Hellenkamp Johann Thurn Gerhard Stock Thorsten Hugel 《Chemical science》2021,12(9):3350
We report on a study that combines advanced fluorescence methods with molecular dynamics (MD) simulations to cover timescales from nanoseconds to milliseconds for a large protein. This allows us to delineate how ATP hydrolysis in a protein causes allosteric changes at a distant protein binding site, using the chaperone Hsp90 as test system. The allosteric process occurs via hierarchical dynamics involving timescales from nano- to milliseconds and length scales from Ångstroms to several nanometers. We find that hydrolysis of one ATP is coupled to a conformational change of Arg380, which in turn passes structural information via the large M-domain α-helix to the whole protein. The resulting structural asymmetry in Hsp90 leads to the collapse of a central folding substrate binding site, causing the formation of a novel collapsed state (closed state B) that we characterise structurally. We presume that similar hierarchical mechanisms are fundamental for information transfer induced by ATP hydrolysis through many other proteins.We report on a study that combines advanced fluorescence methods with molecular dynamics simulations to cover timescales from nanoseconds to milliseconds for a large protein, the chaperone Hsp90. 相似文献
22.
A series ofc-axis oriented YBa2Cu3O
x
-films with different oxygen content were prepared by laser deposition. The oxygen contentx was determined by X-ray diffraction and by resonant Rutherford-back-scattering (RRBS) measurements. Thec-axis length in these films of YBa2Cu3O
x
is about 0.5% larger compared to bulk values. We describe transport measurements in magnetic fields up to 7 Tesla between room temperature andT
c
in samples with an oxygen content between the orthorhombic-to-tetragonal transition (x6.4) and full oxygenation (x7). The ratio /R
H
was investigated with respect to the two-dimensional Luttinger liquid theory and the model of the two-dimensional ionic metal. We report on deviations from the expected quadratic temperature behaviour of /R
H
, especially in films with high oxygen content. 相似文献
23.
24.
The COSMO-RS method, originally developed for the prediction of liquid-liquid and liquid-vapor equilibrium constants based on quantum chemical calculations, has been extended to solid compounds by addition of a heuristic expression for the Gibbs free energy of fusion. By this addition, COSMO-RS is now capable of a priori prediction of aqueous solubilities of a wide range of typical neutral drug and pesticide compounds. Only three parameters in the heuristic expression have been fitted on a data set of 150 drug-like compounds. On these data an rms deviation of 0.66 log-units was achieved. Later, the model was tested on a set of 107 pesticides, which have been critically selected based on two experimental data sources and by a crosscheck with an independent HQSAR model. On this data set an rms of 0.61 log-units was achieved, without any adjustments to the structurally extremely diverse pesticides. This result verifies the ability of this extended COSMO-RS to predict aqueous solubilities of drugs and pesticides of almost arbitrary structural classes. The new method is COSMO-RSol. 相似文献
25.
Haiges R Vij A Boatz JA Schneider S Schroer T Gerken M Christe KO 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):508-517
The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects. 相似文献
26.
A method is presented for the analysis of sulphonated polyphenols, acting as synthetic tanning agents, in heavily polluted tannery wastewater. It consists of ion-pair solid-phase extraction (RP-18) with tetrabutylammonium bromide followed by reversed-phase ion-pair liquid chromatography on a C18 stationary phase with UV detection. The detection limit is 15 μg/1. The influence of the wastewater matrix on extraction and the effects of pH and temperature on the HPLC separation are discussed. The procedure is not affected by the high contents of dissolved organic carbon and inorganic salts of tannery wastewater. The tannery effluents investigated contained around 40 mg/1 of sulphonated polyphenols. These compounds appear to be refractory against both anaerobic and aerobic biological wastewater treatment. They might, thus, contribute to the dissolved organic sulphur content of surface waters. 相似文献
27.
The attachment of single ions to putative adsorption sites in the tails of collagen fibers is investigated by means of molecular dynamics simulations and discussed with respect to the very early steps of apatite/collagen biomineral formation. Our studies clearly demonstrate an increased flexibility of the tails of the triple‐helical collagen protein. Apart from the termini of the backbone, several side chains were also observed to be freely accessible to ion attachment from aqueous solution. The teleopeptide was systematically scanned for suitable adsorption sites for calcium, phosphate and fluoride ions. Association of these ions was then explored from potential of mean force calculations. The resulting energy profiles reveal a variety of favorable protein‐ion bonds and hint at the suitability of the collagen tails to promote apatite aggregation. 相似文献
28.
The synthesis of two 12-nordrimanes and yahazunol was achieved via 8-oxo-12-nordrimanic acid methyl ester. The cytotoxic activity of yahazunol and seven other sesquiterpene hydroquinones and sesquiterpene quinones has been determined. 相似文献
29.
Karl Krmer Hans U. Güdel Gerd Meyer Thorsten Heuer Norman N. Edelstein Bernd Jung Lukas Keller Peter Fischer Eugeniusz Zych Janusz Drozdzynski 《无机化学与普通化学杂志》1994,620(8):1339-1345
The ternary uranium(III) halides A2UX5 (A = K, Rb; X = Cl, Br, I) have been prepared from the binary components AX and UX3 in sealed tantalum containers. According to their Guinier X-ray powder patterns, they all crystallize with the K2PrCl5/Y2HfS5 type of structure. Lattice constants for ambient temperature are reported. Single-crystal structure refinemens were undertaken for K2UI5 and Rb2UCl5. Magnetic susceptibility data were recorded with a SQUID magnetometer from liquid helium to room temperature. One-dimensional (intrachain) and three-dimensional antiferromagnetic ordering occur at low temperatures dependent upon the U3+? U3+ distance. Absorption spectra were recorded between 4 000 and 28 000 cm?1. They show f—f transitions typical for U3+ and, depending on the halide, very strong f—d transitions above 14 000 to 15 000 cm?1, respectively. 相似文献
30.