排序方式: 共有33条查询结果,搜索用时 15 毫秒
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Heimark L Shipkova P Greene J Munayyer H Yarosh-Tomaine T DiDomenico B Hare R Pramanik BN 《Journal of mass spectrometry : JMS》2002,37(3):265-269
A liquid chromatography/mass spectrometry (LC/MS) method for separation and characterization of ergosterol biosynthetic precursors was developed to study the effect of Posaconazole on sterol biosynthesis in fungi. Ergosterol biosynthetic precursors were characterized from their electron ionization mass spectra acquired by a normal-phase chromatography, particle beam LC/MS method. Fragment ions resulting from cleavage across the D-ring and an abundant M - 15 fragment ion were diagnostic for methyl substitution at C-4 and C-14. Comparison of the sterol profile in control and treated Candida albicans incubations showed depletion of ergosterol and accumulation of C-4 and C-14 methyl-substituted sterols following treatment with Posaconazole. These C-4 and C-14 methyl sterols are known to be incapable of sustaining cell growth. The results demonstrate that Posaconazole exerts its antifungal activity by inhibition of ergosterol biosynthesis. Furthermore, Posaconazole appears to disrupt ergosterol biosynthesis by inhibition of lanosterol 14alpha-demethylase. 相似文献
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Atanasova PP Atanasov V Köper I 《Langmuir : the ACS journal of surfaces and colloids》2007,23(14):7672-7678
Model membrane systems are gaining more and more interest both for basic studies of membrane-related processes as well as for biotechnological applications. Several different model systems have been reported among which the tethered bilayer lipid membranes (tBLMs) form a very attractive and powerful architecture. In all the proposed architectures, a control of the lateral organization of the structures at a molecular level is of great importance for an optimized preparation. For tBLMs, a homogeneous and not too dense monolayer is required to allow for the functional incorporation of complex membrane proteins. We present here an alternative approach to the commonly used self-assembly preparation. Lipids are spread on the air-water interface of a Langmuir film balance and form a monomolecular film. This allows for a better control of the lateral pressure and distribution for subsequent transfer to solid substrates. In this paper, we describe the properties of the surface monolayer, in terms of surface pressure, structure of the lipid molecule, content of lipid mixtures, temperature, and relaxations features. It is shown that a complete mixing of anchor-lipids and free lipids can be achieved. Furthermore, an increase of the spacer lengths and a decrease of the temperature lead to more compact films. This approach is a first step toward the fully controlled assembly of a model membrane system. 相似文献
4.
The potential energy surface of the reaction [(eta5-C5MenH5-n)2M]2(micro2,eta2,eta2-N2) + H2 --> [(eta5-C5MenH5-n)2M][(eta5-C5MenH5-n)2MH](micro2,eta2,eta2-NNH) at low-lying singlet and triplet electronic states of the reactants was investigated using density functional methods, for n = 0 and 4, and M = Ti, Zr, and Hf. Ground electronic states of the Ti complexes are found to be triplet states, while that for the corresponding Zr and Hf complexes are singlet states. In their singlet state, all these complexes satisfy known necessary conditions (they have a side-on-coordinated N2 molecule and appropriate frontier orbitals) for successful addition of an H2 molecule to the coordinated N2, and consequently, add of an H2 molecule with a reasonable energy barrier. Hf complexes show slightly higher reactivity than corresponding Zr complexes, and in turn, both are more reactive than their singlet-state Ti counterparts. The calculated trend in reactivity of Zr and Hf complexes is consistent with the latest experimental data (see refs 13 and 16). However, Ti complexes have the ground triplet state that lacks in appropriate frontier orbitals. As a result, H2 addition to the Ti complexes at their triplet ground states requires a larger activation barrier than the singlet state and is endothermic (lacks of driven force for reaction). On the basis of these results, we predict that the [(eta5-C5Me4H)2M]2(micro2,eta2,eta2-N2) and [(eta5-C5H5)2M]2(micro2,eta2,eta2-N2) complexes cannot react with an H2 molecule for M = Ti, while those for M = Zr and Hf can. It was shown that the difference in the B3LYP (hybrid) and PBE (nonhybrid) calculated energy gaps between the lowest closed-shell singlet and triplet states of the present complexes reduces via first- > second- > third-row transition metals; both hybrid and nonhybrid density functionals can be safely used to describe reactivity of the low-lying low-spin and high-spin states of second- and third-row transition metal complexes. 相似文献
5.
On the influence of electric boundary conditions on dynamic SIFs in piezoelectric materials 总被引:1,自引:0,他引:1
Tsviatko Rangelov Petia Dineva Dietmar Gross 《Archive of Applied Mechanics (Ingenieur Archiv)》2010,80(9):985-996
Dynamic stress intensity factors (SIFs) for a straight crack in a piezoelectric material under time-harmonic L- and SH-wave
loading are determined for different electric boundary conditions. Impermeable, permeable and limited permeable cracks are
compared. The problem is formulated and numerically solved using a nonhypersingular traction-based boundary integral equation
method where the fundamental solution is obtained by Radon transform. A parametric study in the frequency domain shows the
dependence of the SIFs on the choice of the electrical boundary conditions at the crack faces. 相似文献
6.
Tsviatko Rangelov Yonko Stoynov Petia Dineva 《International Journal of Solids and Structures》2011,48(20):2987-2999
Dynamic anti-plane fracture problem of an exponentially graded linear magnetoelectroelastic plane with a finite impermeable crack subjected to time-harmonic SH-waves is solved. Directions of wave propagation and material inhomogeneity are chosen in an arbitrary way. The fundamental solution for the coupled system of partial differential equations with variable coefficients is derived in a closed form by the hybrid usage of both an appropriate algebraic transformation for the displacement vector and the Radon transform. The formulated boundary-value problem is solved by a nonhypersingular traction boundary integral equation method (BIEM). The collocation method and parabolic approximation for the unknown generalized crack opening displacements are used for the numerical solution of the posed problem. Quarter point elements placed next to the crack-tips ensure properly modeling the singular behavior of the field variables around the crack tip. Fracture parameters as stress intensity factor, electric field intensity factor and magnetic field intensity factor are computed. Intensive simulations reveal the sensitivity of the generalized intensity factors (GIF) at the crack-tips to the material inhomogeneity, characteristics of the incident wave, coupling effects, wave-material and wave-crack interaction phenomena. 相似文献
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Metabolomics, also referred to in the literature as metabonomics, is a relatively new systems biology tool for drug discovery
and development and is increasingly being used to obtain a detailed picture of a drug’s effect on the body. Metabolomics is
the qualitative assessment and relative or absolute quantitative measurement of the endogenous metabolome, defined as the
complement of all native small molecules (metabolites less than 1,500 Da). A metabolomics study frequently involves the comparative
analysis of sample sets from a normal state and a perturbed state, where the perturbation can be of any nature, such as genetic
knockout, administration of a drug, or change in diet or lifestyle. Advances in mass spectrometry (MS) technologies including
direct introduction or in-line chromatographic separation modes, ionization techniques, mass analyzers, and detection methods
have provided powerful tools to assess the molecular changes in the metabolome. This review focuses on advances in MS pertaining
to the analytical data generation for the main metabolomics methods, namely, fingerprinting, nontargeted, and targeted approaches,
as they are applied to pharmaceutical drug discovery and development. 相似文献
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Ji Y Bobadova-Parvanova P Larson C Samartzis PC Morokuma K Lin JJ Ching TT Chaudhuri C Lee SH Wodtke AM 《The Journal of chemical physics》2006,124(24):241106
Accurate thermochemical data of small molecules are invaluable to the progress of every aspect of chemistry, especially in the atmosphere, combustion and industry. In this work, photofragmentation translational spectroscopy and 1st principles electronic structure theory reveal the literature value of the heat of formation of chlorine-isocyanate to be in error by more than 40 kcalmol. We report a revised experimental value for D0(Cl-NCO) = 51+/-3 kcal/mol which leads to a Delta Hf (ClNCO) = 8.5+/-3 kcal/mol. High level ab initio (CCSD(T)) electronic structure calculations extrapolated to the complete basis set limit give D0(Cl-NCO) = 6.3 kcal/mol, in good agreement with experiment. In light of the present results, the destabilization of azides relative to isoelectronic isocyanates has been evaluated empirically for three pairs of related molecules. It is found to be 90-110 kcal/mol, and has been attributed mainly to the weakening of the N-NN bond relative to the N-CO bond. Electronic structure calculations employing decomposition analysis suggest that, compared to homopolar N2, the (+delta)CO(-delta) pi polarity provides better orbital interaction (charge transfer) and electrostatic attraction and results in a closer encounter and larger stabilization between the fragments and that this is the origin of isoelectronic destabilization of azides relative to the isocyanates. 相似文献
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Petia M. Vlahovska 《PAMM》2007,7(1):1101601-1101602
Surfactants modify interfacial properties and significantly affect drop behavior in flow. We study the dynamics of a drop, which is covered with a monolayer of insoluble surfactant, in linear viscous flows, both unbounded and in the presence of a wall. The effect of viscosity contrast is included. Analytical results in a form of expansions for weak flows and high viscosity drops are developed. Numerical results with three-dimensional boundary integral simulations are used to explore large deformations. The results show that surfactant generally enhances drop deformation, certainly under small-deformation conditions. The steady-state drop shape and surfactant distribution are independent of viscosity contrast in straining flows (e.g. hyperbolic, axisymmetric strain). The drop shape and surfactant distribution are insensitive to viscosity contrast under small deformation conditions for any linear flow; the effect of the rotational component at higher-order. The theory quantifies the effect of surfactant on drop migration away from a bounding wall as well as the rheology of dilute emulsions. It predicts non-Newtonian features such as shear thinning viscosity and normal stress. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
10.
Bratsos I Urankar D Zangrando E Genova-Kalou P Košmrlj J Alessio E Turel I 《Dalton transactions (Cambridge, England : 2003)》2011,40(19):5188-5199
The 1,4-disubstituted 1,2,3-triazole ligand prepared by click chemistry 1-(2-picolyl)-4-phenyl-1H-1,2,3-triazole (ppt) was investigated as novel chelating ligand for Ru(II) complexes with potential antitumor activity. The preparation and structural characterization, mainly by NMR spectroscopy in solution and by X-ray crystallography in the solid state, of four new Ru(II) complexes is reported: two isomeric Ru-dmso compounds, trans,cis-[RuCl(2)(dmso-S)(2)(ppt)] (1) and cis,cis-[RuCl(2)(dmso-S)(2)(ppt)] (2), and two half-sandwich Ru-[9]aneS(3) coordination compounds, [Ru([9]aneS(3))(dmso-S)(ppt)][CF(3)SO(3)](2) (3) and [Ru([9]aneS(3))Cl(ppt)][CF(3)SO(3)] (4). In all compounds ppt firmly binds to ruthenium in a bidentate fashion through the pyridyl nitrogen atom and the triazole N2, thus forming a puckered six-membered ring. The chemical behavior in aqueous solution of the water-soluble complexes 3 and 4 was studied by UV-Vis and NMR spectroscopy and compared to that of the previously described organometallic analogue [Ru(η(6)-p-cymene)Cl(ppt)][Cl] (5) in view of their potential antitumor activity. Compounds 3-5 were tested also in vitro for cytotoxic activity against two human cancer cell lines, one sensitive and one resistant to cisplatin, in comparison with cisplatin. Compound 4, the one that aquates faster, was found to be more cytotoxic than cisplatin against human lung squamose carcinoma cell line (A-549). 相似文献