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41.
X-ray absorption spectroscopy (XAS) and small angle x-ray scattering (SAXS) were utilized to study the effect of fluoride (F(-)) anion in aqueous solutions. XAS spectra show that F(-) increases the number of strong H-bonds, likely between F(-) and water in the first hydration shell. SAXS data show a low-Q scattering intensity increase similar to the effect of a temperature decrease, suggesting an enhanced anomalous scattering behavior in F(-) solutions. Quantitative analysis revealed that fluoride solutions have larger correlation lengths than chloride solutions with the same cations but shorter compared to pure water. This is interpreted as an increased fraction of tetrahedral low-density structures in the solutions due to the presence of the F(-) ions, which act as nucleation centers replacing water in the H-bonding network and forming stronger H-bonds, but the presence of the cations restricts the extension of strong H-bonds.  相似文献   
42.
We present extensive simulations on the TIP4P∕2005 water model showing significantly enhanced small-angle scattering (SAS) in the supercooled regime. The SAS is related to the presence of a Widom line (T(W)) characterized by maxima in thermodynamic response functions and Ornstein-Zernike correlation length. Recent experimental small-angle x-ray scattering data [Huang et al., J. Chem. Phys. 133, 134504 (2010)] are excellently reproduced, albeit with an increasing temperature offset at lower temperatures. Assuming the same origin of the SAS in experiment and model this suggests the existence of a Widom line also in real supercooled water. Simulations performed at 1000 bar show an increased abruptness of a crossover from dominating high-density (HDL) to dominating low-density (LDL) liquid and strongly enhanced SAS associated with crossing T(W), consistent with a recent determination of the critical pressure of TIP4P∕2005 at 1350 bar. Furthermore, good agreement with experimental isothermal compressibilities at 1000, 1500, and 2000 bar shows that the high pressure supercooled thermodynamic behavior of water is well described by TIP4P∕2005. Analysis of the tetrahedrality parameter Q reveals that the HDL-LDL structural transition is very sharp at 1000 bar, and that structural fluctuations become strongly coupled to density fluctuations upon approaching T(W). Furthermore, the tetrahedrality distribution becomes bimodal at ambient temperatures, an observation that possibly provides a link between HDL-LDL fluctuations and the structural bimodality in liquid water indicated by x-ray spectroscopic techniques. Computed x-ray absorption spectra are indeed found to show sensitivity to the tetrahedrality parameter.  相似文献   
43.
Rats, germfree and conventional, were dosed with 14C-labelled benzo[a]pyrene. Faeces and urine were collected. Metabolites in faeces were effectively extracted with a new method using a combination of solvents and solid sorbents. Metabolites in urine were extracted with octadecylsilane-bonded silica. The metabolites were fractionated into groups by chromatography on a cation exchanger (SP-LH-20 or SP-Sephadex C-25) and an anion exchanger (TEAP-LH-20). Some of the groups were further purified by column chromatography and analysed by HPLC and TLC. The analyses show a complex pattern of metabolism. A large part of the metabolites (9-24% depending on animal type and route of excretion) had amphoteric properties, e.g. like glutathione and cysteine conjugates. The abundance of conjugates sensitive to beta-glucuronidase and sulphatase was low. The relative amount of acidic conjugates in faeces was much higher in the germfree than in the conventional rats indicating the influence of the intestinal flora on the metabolism. The results support the view that the mercapturic acid pathway is a quantitatively important metabolic route for benzo[a]pyrene in rats. The methods of extraction and group fractionation were designed to be generally applicable to the analysis of lipophilic xenobiotics and their metabolites.  相似文献   
44.
Summary A series of apomorphine congeners has been studied with respect to their ability to mimic the structural requirements of the dopamine pharmacophore in the potent and stereoselective dopamine receptor agonist (R)-apomorphine. Conformational energies of the mimicking structures calculated by molecular mechanics (MMP2) correlate well with the observed biological activities.  相似文献   
45.
A phenomenological method has been used to derive a nonlinear constitutive relationship that can be used in conjunction with any eddy-viscosity model utilizing the elliptic relaxation method. While retaining the merits of the elliptic relaxation to model near-wall turbulence, the new model also enables the turbulence anisotropy to be faithfully predicted in wall-bounded flows.  相似文献   
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The decay of103Ru to103Rh has been studied using a double-focussing spectrometer for the electron and negaton spectra and a Ge(Li) detector for gamma-ray measurements. TheL-conversion groups of the 40, 53, and 497 keV transitions were resolved at high resolution and unambigous multipolarity assignments were obtained for these transitions. The level scheme proposed resembles in principle that suggested by previous investigators. One essential difference is the doublet character of the state around 0.65 MeV. Tentative spin-parity values have been assigned to all levels from the deduced multipolarities and logft values.  相似文献   
50.
Summary The properties of chloroform as a liquid stationary phase in reversed-phase liquid chromatography have been investigated. Stable systems and complete pore filling of the support were obtained. Uncharged acids were slightly adsorbed by the support. Amines in the cationic form showed tailing, which can be attributed to adsorption on the support material. The influence of several reversed-phase supports on retention and peak symmetry has been studied. Little difference was found for uncharged acids, but retention and peak shape of the cations was dependent on the specific support. Also on the poly(styrene-divinylbenzene) copolymer PRP-1 cations gave tailing peaks. The results indicate that the surface of reversed-phase supports is heterogeneous. From this and other studies it can be concluded that only certain reversed-phase silicas, such as -Bondapak, are suitable supports for cationic solutes. In liquid-liquid chromatography polar solutes only obey a liquid-liquid distribution model if the liquid stationary phase molecules contains a hydrophobic group, as well as a polar function.Presented in part at the 7th and 9th International Symposiums on Column Liquid Chromatography, Baden-Baden, FRG, May 1983, and Edinburgh, UK, July 1985, respectively.  相似文献   
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