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271.
A procedure for the Raman spectra calculation of vitreous and molten silicates was presented in this paper. It includes molecular dynamics MD simulation for the generation of equilibrium configurations, Wilson's GF matrix method for the calculations of eigenfrequencies and corresponding vectors, electro-optical parameters method (EOPM) for the Raman intensity calculations, and the bond polarizability model (BPM) for the determination of polarizability and polarizability derivative. One of the most important characteristics of this procedure is the achievement of the partial Raman spectra of five tetrahedral units, as well as the total spectral envelope. In this paper, the calculation was carried out for the vitreous and molten calcium silicates with different compositions and at various temperatures. It is worthwhile to note that the calculation is based on statistical configurations distribution in the space and so it is not needed to artificially adjust the full width at half maximum (FWHM) of spectra. It was also tested through the good agreement of the calculated spectra with the experimental, including some regularity of spectral properties. According to the calculation, the symmetrical stretching of whole tetrahedral units, to which the stretching of Si-O(nb) bond gives the main contribution to intensity, is proven to be the dominance in the high-frequency range (800-1200 cm(-1)) and the symmetrical bending of Si-O(b)-Si, to which the stretching of Si-O(b) bond exhibits the main contribution, is the dominance in the medium-frequency range (400-700 cm(-1)). As the first theoretical results, the Raman scattering coefficient of each Q(i) was found little change along with the variation of composition and temperature. 相似文献
272.
Guo Zhijun Niu Yanning Zhang Weiguang Tan Minyu 《Journal of Radioanalytical and Nuclear Chemistry》2004,262(2):331-337
N,N,N',N',N',N'-Hexaethyl-2,2′,2'-(nitrilotrisethyleneoxy-2-benzyloxy)tris(acetamide) (L3) has been prepared and characterized
by using IR, 1H NMR and positive-ion FAB mass spectra. The extraction of Th4+ and UO2
2+ with N,N,N',N',N',N'-hexaethyl-2,2',2'- (nitrilo-trisethyleneoxy)tris(acetamide) (L1), N,N,N',N',N',N'-hexaisopropyl-2,2',2'-(nitrilotrisethyleneoxy)tris(acetamide)
(L2), and L3 was studied at 20±1 °C as a function of diluent, concentration of free extractant in organic phase and concentration
of picrate in aqueous phase. It was found that the extracting powers of L1 and L2 for Th4+ are almost identical. The extracting power of L2 for UO22+ was slightly higher than that of L1. The difference in terminal
groups (ethyl or isopropyl) of the extractants (L1 and L2) with same backbone has a little effect on the extracting power
for both Th4+ and UO22+. The extracting powers of L3 for both Th4+ and UO22+ were larger than those of L1 and L2. The extractants
(L1 and L3) having the same terminal group (ethyl) with different backbones have obviously different extracting powers for
Th4+ or UO22+. The extracting powers of all three extractants L1, L2, and L3 for Th4+ were larger than those for UO22+. The
compositions of extracted species in organic phase were predominantly ThL(Pic)3NO3 and UO2L(Pic)NO3, respectively (L denotes
L1, L2 and L3).
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
273.
274.
Rate constants (k's) of the thermal cyclodimerization of ten meta-substituted trifluorostyrenes (m-Y-TFS's) have been measured in the temperature range 110–160°C. On the basis of these k's and the σmb values derived from 19F NMR data the spin-delocalization substituent constant σ˙m values of these ten meta-substituents have been calculated. The averaged σ˙m values are: m-Et, 0.09; m-t-Bu, 0.11; m-F, 0.03; m-Cl,?0.05; m-Br, 0.12: m-CF3, ?0.07; m-OMe, 0.10; m-NO2, ?0.002; m-CN, 0.11 and m-CO2Me, 0.08. Both the smallness of these values and the nonexistence of correlation between Hammett-Type polar σX and these σ˙m values support our belief that the σj?J approach is reliable and trustworthy. 相似文献
275.
276.
蔗糖酯分子在碱性条件下,加热水解为蔗糖和硬酯酸,在pH>10的NH_3·N_2O-(NH_3)_3C_6H_5O_7体系中,于示波极谱仪上,峰电位─0.91V处出现一灵敏度高和稳定性好的极谱图,其浓度从0.02~0.28mg/mL与峰电流呈线性关系,最低检出限为0.004mg/mL,相对标准偏差为1.3%。 相似文献
277.
278.
The conversion of phosphoenolpyruvate (PEP) to phosphonopyruvate (P-pyr) is catalyzed by PEP mutase via a dissociative mechanism. In this work, we investigate the uncatalyzed reaction using ab initio methods, density functional theory, and the semiempirical MNDO/d method. Comparisons of geometries and relative energies of stationary points (minima and transition states) with density functional results indicate that the semiempirical method is reasonably accurate. Solvent effects are examined using implicit solvent models, including the recently extended smooth conductor-like screening model. Due to the large negative charge carried by the system, solvation is found to drastically alter the location and energy of stationary points along the dissociative reaction pathways. The influence of substituting a nonbridging phosphoryl oxygen by sulfur (thio effects) was also investigated. Implications of these results for the enzymatic reaction are discussed. 相似文献
279.
This work examines the curing kinetics, thermal properties, and decomposition kinetics of diglycidyl ether of bisphenol A (DGEBA) epoxies with three different curing agents, 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-naphthalenediol (ODOPN), bisphenol A (BPA), and bisphenol S (BPS). The differential scanning calorimetry curing study reveals that the curing kinetics of the DGEBA/ODOPN epoxy is first order, independent of the scan rate. The ODOPN-containing epoxy, unlike the conventional BPA one, includes a phosphorus-containing bulky pendant aromatic group and results in an increase in the glass-transition temperature of 83 K, the char yield increases by a factor of 3, and the limiting oxygen index values increase from 23 to 27. For the BPS system, the glass-transition temperature increased slightly, and both the char yield and the limiting oxygen index value increased insignificantly when the test was conducted in air. Finally, the thermogravimetric analysis decomposition study in N2 from Ozawa's analysis demonstrates that the DGEBA/BPS epoxy has the highest activation energy, followed by the regular DGEBA/BPA system, and lastly the DGEBA/ODOPN has the lowest activation energy. The low activation energy for the ODOPN system is attributed to the initial decomposition of the phosphorus compound in the formation of an insulating layer. 相似文献
280.
Microporous activated carbons prepared from palm shell by thermal activation and their application to sulfur dioxide adsorption 总被引:2,自引:0,他引:2
Textural characterization of activated carbons prepared from palm shell by thermal activation with carbon dioxide (CO(2)) gas is reported in this paper. Palm shell (endocarp) is an abundant agricultural solid waste from palm-oil processing mills in many tropical countries such as Malaysia, Indonesia, and Thailand. The effects of activation temperature on the textural properties of the palm-shell activated carbons, namely specific surface area (BET method), porosity, and microporosity, were investigated. The activated carbons prepared from palm shell possessed well-developed porosity, predominantly microporosity, leading to potential applications in gas-phase adsorption for air pollution control. Static and dynamic adsorption tests for sulfur dioxide (SO(2)), a common gaseous pollutant, were carried out in a thermogravimetric analyzer and a packed column configuration respectively. The effects of adsorption temperature, adsorbate inlet concentration, and adsorbate superficial velocity on the adsorptive performance of the prepared activated carbons were studied. The palm-shell activated carbon was found to have substantial capability for the adsorption of SO(2), comparable to those of some commercial products and an adsorbent derived from another biomass. 相似文献