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1.
The effects of solvent and temperature on the complexation of adamantyl mannoside with β-cyclodextrin and 6-O-monotosyl-6-deoxy-β-cyclodextrin were explored experimentally and by means of molecular dynamics simulations. Efficient binding was observed only in hydrogen-bonded solvents, which indicated solvophobically driven complexation. The stability of the inclusion complex was considerably higher in aqueous media. A pronounced temperature dependence of ΔrH and ΔrS, resulting in perfect enthalpy–entropy compensation, was observed in water. The complexation thermodynamics was in line with classical rationale for the hydrophobic effect at lower temperatures and the nonclassical explanation at higher temperatures. This finding linked cyclodextrin complexation thermodynamics with insights regarding the effect of temperature on the hydration water structure. The complexation enthalpies and entropies were weakly dependent on temperature in organic media. The signs of ΔrH and ΔrS were in accordance with the nonclassical hydrophobic (solvophobic) effect. The structures of the optimized product corresponded to those deduced spectroscopically, and the calculated and experimentally obtained values of ΔrG were in very good agreement. This investigation clearly demonstrated that solvophobically driven formation of cyclodextrin complexes could be anticipated in structured solvents in general. However, unlike in water, adamantane and the host cavity behaved solely as structure breakers in the organic media explored so far.  相似文献   
2.
This paper introduces a new framework for implicit restarting of the Krylov–Schur algorithm. It is shown that restarting with arbitrary polynomial filter is possible by reassigning some of the eigenvalues of the Rayleigh quotient through a rank‐one correction, implemented using only the elementary transformations (translation and similarity) of the Krylov decomposition. This framework includes the implicitly restarted Arnoldi (IRA) algorithm and the Krylov–Schur algorithm with implicit harmonic restart as special cases. Further, it reveals that the IRA algorithm can be turned into an eigenvalue assignment method. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
3.
A study of first-year undergraduate students′ interpretational difficulties with first-order ordinary differential equations (ODEs) in modelling contexts was conducted using a diagnostic quiz, exam questions and follow-up interviews. These investigations indicate that when thinking about such ODEs, many students muddle thinking about the function that gives the quantity to be determined and the equation for the quantity's rate of change, and at least some seem unaware of the need for unit consistency in the terms of an ODE. It appears that shifting from amount-type thinking to rates-of-change-type thinking is difficult for many students. Suggestions for pedagogical change based on our results are made.  相似文献   
4.
Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O-H covalent bonds within a single water molecule adsorbed on the MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on the MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the first-order electronic-phase transition temperature.  相似文献   
5.
In this paper, an advanced method of one-step functionalization of single and multi walled carbon nanotubes (SWCNTs and MWCNTs) using γ-irradiation was described. Two synthesis procedures, related with different reduction species, were employed. For the first time, poly(vinyl alcohol) PVA is successfully utilized as a source to reduce silver (Ag) metal ions without having any additional reducing agents to obtain Ag nanoparticles on CNTs. The decoration of carbon nanotubes with Ag nanoparticles takes place through anchoring of (PVA) on nanotube's surface. Optical properties of as-prepared samples and mechanism responsible for the functionalization of carbon nanotubes were investigated using UV-vis and FTIR spectroscopy, respectively. Decorated carbon nanotubes were visualized using microscopic techniques: transmission electron microscopy and scanning tunneling microscopy. Also, the presence of Ag on the nanotubes was confirmed using energy dispersive X-ray spectroscopy. This simple and effective method of making a carbon nanotube type of composites is of interest not only for an application in various areas of technology and biology, but for investigation of the potential of radiation technology for nanoengineering of materials.  相似文献   
6.
We have performed rigorous quantum five-dimensional (5D) calculations and analysis of the translation-rotation (T-R) energy levels of one H(2), D(2), and HD molecule inside the small dodecahedral (H(2)O)(20) cage of the structure II clathrate hydrate, which was treated as rigid. The H(2)- cage intermolecular potential energy surface (PES) used previously in the molecular dynamics simulations of the hydrogen hydrates [Alavi et al., J. Chem. Phys. 123, 024507 (2005)] was employed. This PES, denoted here as SPC/E, combines an effective, empirical water-water pair potential [Berendsen et al., J. Phys. Chem. 91, 6269 (1987)] and electrostatic interactions between the partial charges placed on H(2)O and H(2). The 5D T-R eigenstates of HD were calculated also on another 5D H(2)-cage PES denoted PA-D, used by us earlier to investigate the quantum T-R dynamics of H(2) and D(2) in the small cage [Xu et al., J. Phys. Chem. B 110, 24806 (2006)]. In the PA-D PES, the hydrogen-water pair potential is described by the ab initio 5D PES of the isolated H(2)-H(2)O dimer. The quality of the SPC/E and the PA-D H(2)-cage PESs was tested by direct comparison of the T-R excitation energies calculated on them to the results of two recent inelastic neutron scattering (INS) studies of H(2) and HD inside the small clathrate cage. The translational fundamental and overtone excitations, as well as the triplet splittings of the j=0-->j=1 rotational transitions, of H(2) and HD in the small cage calculated on the SPC/E PES agree very well with the INS results and represent a significant improvement over the results computed on the PA-D PES. Our calculations on the SPC/E PES also make predictions about several spectroscopic observables for the encapsulated H(2), D(2), and HD, which have not been measured yet.  相似文献   
7.
The efficient synthesis of new amidino, N-isopropylamidino, 2-imidazolinyl substituted benzothiazoles and 2-aminothiophenoles by the Pinner reaction is described. The novel ring opening of benzothiazole with ammonia and ethylenediamine was found, and a plausible reaction mechanism proposed. The ring opening with ethylenediamine is selective and applicable to compounds bearing hydrolytically and amonolytically unstable substituents. Different amidino-substituted 2-aminothiophenoles were isolated in zwitterionic and disulfide form and their structures were determined by X-ray crystal structure analysis.  相似文献   
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A new derivation of the self-consistent dynamically screened nonlocal Coulomb potential near a planar surface is presented, based on the integral equation approach. The exact solution is obtained without restrictions on the dynamical response of the solid (e.g. RPA in metals), the type of surface potential or electronic density profile, and without additional matching or boundary conditions. This makes the present approach particularly useful e.g. in the general discussion of model-independent screening phenomena at metal surfaces. The application to the calculation of matrix elements for electron and ion excitation of collective modes and electron-hole pairs is formulated, and the connection with the previous results discussed.  相似文献   
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