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排序方式: 共有492条查询结果,搜索用时 390 毫秒
91.
Kawatkar SP Kuntz DA Woods RJ Rose DR Boons GJ 《Journal of the American Chemical Society》2006,128(25):8310-8319
The X-ray crystal structures of mannose trimming enzyme drosophila Golgi alpha-mannosidase II (dGMII) complexed with the inhibitors mannostatin A (1) and an N-benzyl analogue (2) have been determined. Molecular dynamics simulations and NMR studies have shown that the five-membered ring of mannostatin A is rather flexible occupying pseudorotational itineraries between 2T3 and 5E, and 2T3 and 4E. In the bound state, mannostatin A adopts a 2T1 twist envelope conformation, which is not significantly populated in solution. Possible conformations of the mannosyl oxacarbenium ion and an enzyme-linked intermediate have been compared to the conformation of mannostatin A in the cocrystal structure with dGMII. It has been found that mannostatin A best mimics the covalent linked mannosyl intermediate, which adopts a 1S5 skew boat conformation. The thiomethyl group, which is critical for high affinity, superimposes with the C-6 hydroxyl of the covalent linked intermediate. This functionality is able to make a number of additional polar and nonpolar interactions increasing the affinity for dGMII. Furthermore, the X-ray structures show that the environment surrounding the thiomethyl group of 1 is remarkably similar to the arrangements around the methionine residues in the protein. Collectively, our studies contradict the long held view that potent inhibitors of glycosidases must mimic an oxacarbenium ion like transition state. 相似文献
92.
Buckner SW Fischer MJ Jelliss PA Luo R Minteer SD Rath NP Siemiarczuk A 《Inorganic chemistry》2006,45(18):7339-7347
The complex [7,10-mu-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9] has been synthesized by treatment of the complex salt [NHMe3][3,3-Cl2-3,3-(CO)2-closo-3,1,2-ReC2B9H11] with PPh3 in refluxing THF (tetrahydrofuran) and isolated as intensely colored orange-red microcrystals. Spectroscopic NMR and IR data have suggested that the product has a highly asymmetric structure with two inequivalent PPh3 ligands and a single CO ligand. Measurement of 11B NMR spectra in particular have indicated seven distinct boron vertexes, although the resulting cage degradation by removal of two BH vertexes was confirmed only following X-ray crystallographic analysis, which revealed the pentadecahedral isonido-7,8,9-ReC2B7 architecture. The 11B NMR resonances span an enormous chemical shift range (Deltadelta = 113), and this appears to be a direct consequence of the deshielding of the boron vertex directly opposite the quadrilateral |ReCCB| aperture. The new complex has been shown by electrochemical measurements to undergo a reversible one-electron oxidation. Digitally simulated cyclic voltammograms support a proposed square scheme (E(1/2) = 0.58, 0.69 V vs ferrocene) involving a reversible isonido-closo transition of the metallacarborane cage. Most unusually for a metallacarborane complex, ambient temperature solutions in CH2Cl2 and DMF have been shown to be intensely turquoise-blue fluorescent (lambda(em) = 442 nm, Phi = 0.012). Fluorescence spectroscopy measurements in MeTHF (2-methyltetrahydrofuran) glass at 77 K have indicated that the likely cause of such a broad emission is dual fluorescence (lambda(em) = 404, 505 nm), with both emissions displaying vibronic structure. Following excited-state lifetime decay analysis, the emissive behavior has been accredited to metal-perturbed 1IL states, with the lower energy emission arising from a slight geometric distortion of the initially excited complex. 相似文献
93.
The tetraphosphine DPPEPM reacts with [PtMe2(cod)] to produce [PtMe2(DPPEPM-PP)] (1) in near quantitative yield. On standing in solution, the free P atoms become oxidized to give [PtMe2(DPPEPM(O)2-PP)] (1a), which has been characterized by X-ray crystallography. In contrast, reactions of DPPEPM with [MCl2(cod)] (M = Pd, Pt) yield ionic products of the form [M(DPPEPM-PP)2]MCl4 (3, 4). When a solution of the platinum complex was allowed to stand, crystals of [Pt(μ-Cl)(μ-DPPEPM)2]Cl3 (5) were obtained. In a third set of reactions, treatment of [PtClR(cod)] (R = Me, Ph) or [PdClMe(cod)] with DPPEPM gives species of the type [MR(DPPEPM-PPP)]Cl (6-8), in which one of the internal P atoms is uncoordinated. Reactions of [PtR2(DPPEPM-PP)] with or [MCl2(cod)] (M = Pd, Pt), or of [PtR(DPPEPM-PPP)]Cl with [MCl2(cod)], lead to unsymmetrical bimetallic complexes. [PtMe2(μ-DPPEPM)PdCl2] (11) and [PtClPh(μ-DPPEPM)PdCl2] (14) have been characterized crystallographically. Trimetallic complexes of the form [{PtR2(μ-DPPEPM)}2M][MCl4] (M = Pd, Pt, 15-17) are produced by reaction of [PtR2(DPPEPM-PP)] with [MCl2(cod)]. 相似文献
94.
Lucas Kambanis Timothy S. Chisholm Sameer S. Kulkarni Richard J. Payne 《Chemical science》2021,12(29):10014
The development of an iterative one-pot peptide ligation strategy is described that capitalises on the rapid and efficient nature of the diselenide–selenoester ligation reaction, together with photodeselenisation chemistry. This ligation strategy hinged on the development of a novel photolabile protecting group for the side chain of selenocysteine, namely the 7-diethylamino-3-methyl coumarin (DEAMC) moiety. Deprotection of this DEAMC group can be effected in a mild, reagent-free manner using visible light (λ = 450 nm) without deleterious deselenisation of selenocysteine residues, thus enabling a subsequent ligation reaction without purification. The use of this DEAMC-protected selenocysteine in iterative DSL chemistry is highlighted through the efficient one-pot syntheses of 60- and 80-residue fragments of mucin-1 as well as apolipoprotein CIII in just 2–4 hours.A method for the rapid one-pot iterative assembly of proteins via diselenide–selenoester ligation (DSL) chemistry is described that capitalises on a novel coumarin-based photolabile protecting group for selenocysteine. 相似文献
95.
Using the Nikiforov–Uvarov (NU) method, the energy levels and the wave functions of an electron confined in a two-dimensional (2D) pseudoharmonic quantum dot are calculated under the influence of temperature and an external magnetic field inside dot and Aharonov–Bohm (AB) field inside a pseudodot. The exact solutions for energy eigenvalues and wave functions are computed as functions of the chemical potential parameters, applied magnetic field strength, AB flux field, magnetic quantum number and temperature. Analytical expression for the light interband absorption coefficient and absorption threshold frequency are found as functions of applied magnetic field and geometrical size of quantum pseudodot. The temperature dependence energy levels for GaAs semiconductor are also calculated. 相似文献
96.
Massless Dirac fermions in monolayer graphene exhibit total transmission when normally incident on a scalar potential barrier, a consequence of the Klein paradox originally predicted by O Klein for relativistic electrons obeying the 3 + 1 dimensional Dirac equation. For bilayer graphene, charge carriers are massive Dirac fermions and, due to different chiralities, electron and hole states are not coupled to each other. Therefore, the wavefunction of an incident particle decays inside a barrier as for the non-relativistic Schr?dinger equation. This leads to exponentially small transmission upon normal incidence. We show that, in the presence of magnetic barriers, such massive Dirac fermions can have transmission even at normal incidence. The general consequences of this behavior for multilayer graphene consisting of massless and massive modes are mentioned. We also briefly discuss the effect of a bias voltage on such magnetotransport. 相似文献
97.
We approximately solve the Dirac equation for a new suggested generalized inversely quadratic Yukawa potential including a Coulomb-like tensor interaction with arbitrary spin-orbit coupling quantum number ${\kappa}$ . In the framework of the spin and pseudospin (p-spin) symmetry, we obtain the energy eigenvalue equation and the corresponding eigenfunctions, in closed form, by using the parametric Nikiforov–Uvarov method. The numerical results show that the Coulomb-like tensor interaction, ?T/r, removes degeneracies between spin and p-spin state doublets. The Dirac solutions in the presence of exact spin symmetry are reduced to Schr?dinger solutions for Yukawa and inversely quadratic Yukawa potentials. 相似文献
98.
Roshnee SahooAjaya K. Nayak K.G. Suresh A.K. Nigam 《Journal of magnetism and magnetic materials》2012,324(7):1267-1271
The effect of Ge substitution on the magnetic, magnetocaloric and transport properties of Ni45Co5Mn38Sb12−xGex (x=0-3) has been investigated. The decrease in the exchange interaction brought by Ge substitution can be seen from the reduction in the magnetization of austenite phase and the increase in the martensitic transition temperature. The magnetocaloric effect and the magnetoresistance values are found to be quite sensitive to small changes in Sb/Ge ratio. Taking into account various properties, the present series seems to be a promising multifunctional system. 相似文献
99.
100.
M. S. Raghu K. Basavaiah P. J. Ramesh Sameer A. M. Abdulrahman K. B. Vinay 《Journal of Applied Spectroscopy》2012,79(1):131-138
A sensitive, precise, and cost-effective UV-spectrophotometric method is described for the determination of pheniramine maleate
(PAM) in bulk drug and tablets. The method is based on the measurement of absorbance of a PAM solution in 0.1 N HCl at 264 nm.
As per the International Conference on Harmonization (ICH) guidelines, the method was validated for linearity, accuracy, precision,
limits of detection (LOD) and quantification (LOQ), and robustness and ruggedness. A linear relationship between absorbance
and concentration of PAM in the range of 2–40 μg/ml with a correlation coefficient (r) of 0.9998 was obtained. The LOD and
LOQ values were found to be 0.18 and 0.39 μg/ml PAM, respectively. The precision of the method was satisfactory: the value
of relative standard deviation (RSD) did not exceed 3.47%. The proposed method was applied successfully to the determination
of PAM in tablets with good accuracy and precision. Percentages of the label claims ranged from 101.8 to 102.01% with the
standard deviation (SD) from 0.64 to 0.72%. The accuracy of the method was further ascertained by recovery studies via a standard
addition procedure. In addition, the forced degradation of PAM was conducted in accordance with the ICH guidelines. Acidic
and basic hydrolysis, thermal stress, peroxide, and photolytic degradation were used to assess the stability-indicating power
of the method. A substantial degradation was observed during oxidative and alkaline degradations. No degradation was observed
under other stress conditions. 相似文献