全文获取类型
收费全文 | 666篇 |
免费 | 35篇 |
专业分类
化学 | 454篇 |
晶体学 | 4篇 |
力学 | 40篇 |
数学 | 130篇 |
物理学 | 73篇 |
出版年
2024年 | 2篇 |
2023年 | 8篇 |
2022年 | 3篇 |
2021年 | 14篇 |
2020年 | 16篇 |
2019年 | 8篇 |
2018年 | 15篇 |
2017年 | 9篇 |
2016年 | 22篇 |
2015年 | 25篇 |
2014年 | 28篇 |
2013年 | 50篇 |
2012年 | 56篇 |
2011年 | 64篇 |
2010年 | 29篇 |
2009年 | 23篇 |
2008年 | 62篇 |
2007年 | 44篇 |
2006年 | 51篇 |
2005年 | 39篇 |
2004年 | 35篇 |
2003年 | 16篇 |
2002年 | 18篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 2篇 |
1997年 | 4篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1945年 | 1篇 |
1944年 | 1篇 |
1943年 | 1篇 |
1942年 | 3篇 |
1941年 | 2篇 |
排序方式: 共有701条查询结果,搜索用时 15 毫秒
11.
A highly enantioselective (up to 97.5% ee) and diastereoselective (95:5 dr trans/cis) Cu(I)-catalyzed cyclopropanation of alkenes using phenyliodonium ylide generated in situ from iodosobenzene and methyl nitroacetate is reported. The cyclopropanation took place with high enantioselectivity for a wide range of alkenes, and the reaction was performed at room temperature. 1-Nitrocyclopropyl esters are versatile building blocks to access the corresponding cyclopropane amino esters and aminocyclopropanes in two and three steps, respectively, from commercially available products. 相似文献
12.
A classical electrostatic polarization scheme using the additive distribution procedure has been applied to determine the longitudinal polarizability of an all-trans hexatriene molecule in an infinite stretched fiber. The parameters have been derived from ab initio CPHF/6-31G calculations and the electrostatic scheme has been validated via comparison with ab initio results on small clusters. Upon packing the polarizability of all-trans hexatriene increases by 7%. This small increase results from the balance between the enhancement of the polarizability due to collinear packing and the reduction associated with lateral packing. 相似文献
13.
A theoretical model of the evaporation of a pure liquid layer is developed. We focus on the influence of an inert gaseous component, in addition to vapor, on surface-tension-driven Bénard instabilities. It is assumed that the gas phase is perfectly mixed at some distance from the liquid-gas interface (given composition, pressure, and temperature). If this distance is not much larger than the liquid layer thickness, it is shown that a reduction of the full two-layer problem to a one-layer problem is possible, provided the evaporation rate is not too large. An analytical expression is given for the corresponding dimensionless heat transfer coefficient (a generalized, wavenumber-dependent Biot number) at the evaporating interface. The approach is validated through a comparison with a direct numerical resolution of the full two-layer problem. 相似文献
14.
Catalytic wet air oxidation of oleic acid on ceria-supported platinum catalyst.effect of pH 总被引:1,自引:0,他引:1
Beno?t Levasseur Benoist Renard Jacques Barbier Jr. Daniel Duprez 《Reaction Kinetics and Catalysis Letters》2006,87(2):269-279
Summary Catalytic wet air oxidation (CWAO) of oleic acid was carried out in a batch reactor on platinum supported ceria catalyst (Pt/CeO2). Oleic acid is a water insoluble linear unsaturated fatty acid of 18 carbon atoms. To increase the homogeneity of the solution
by saponification, the influence of NaOH additions in oleic acid CWAO mechanism and catalyst performances have been investigated.
The oxidation of such molecule occurs by two types of mechanisms: successive carboxy-decarboxylation which leads essentially
to CO2and/or C-C bonds splitting in the alkyl chain inducing a high formation of acetic acid. With or without NaOH, the 5%Pt/CeO2catalyst is active in the conversion of oleic acid and selective to carbon dioxide. In alkaline medium, oleic acid is initially
saponified which increases the solubility of the reactant before it to be oxidized. Finally the oxidation is slightly delayed
by the presence of NaOH. The catalyst characterizations show no significant difference before and after reaction.</o:p> 相似文献
15.
The abnormal physicochemical characteristics of ethanol solvation in water are commonly attributed to the phenomenon of hydrophobic hydration. To investigate the structural organization of hydrophobic hydration in water-ethanol mixtures, we use molecular dynamics simulations based on detailed atomic models. Induced polarization is incorporated into the potential function on the basis of the classical Drude oscillator model. Water-ethanol mixtures are simulated at 11 ethanol molar fractions, from 0.05 to 0.9. Although the water and ethanol models are parametrized separately to reproduce the vaporization enthalpy, static dielectric constant, and self-diffusion constant of neat liquids at ambient conditions, they also reproduce the energetic and dynamical properties of the mixtures accurately. Furthermore, the calculated dielectric constant for the various water-alcohol mixtures is in excellent agreement with experimental data. The simulations provide a detailed structural characterization of the mixtures. A depletion of water-water hydrogen bonding in the first hydration shell of ethanol is compensated by an enhancement in the second hydration shell. The structuring effect from the second solvation shell gives rise to a net positive hydrogen-bonding excess for ethanol molar fractions up to approximately 0.5. For larger molar fractions, the second hydration shell is not sufficiently populated to overcome the net H-bond depletion from the first shell. 相似文献
16.
Mongin F Mojovic L Guillamet B Trécourt F Quéguiner G 《The Journal of organic chemistry》2002,67(25):8991-8994
The first nickel-catalyzed cross-coupling reactions between fluoroarenes and aryl organometallics using commercially available ligands are described. The nickel-catalyzed cross-coupling reactions between aryl Grignard reagents and fluoroazines and -diazines occurred in THF at room temperature using commercially available 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, or 1,1'-bis(diphenylphosphino)ferrocene as ligand. Various fluoro substrates such as pyridines, diazines (pyrazine, pyridazine), benzodiazines (quinoxaline), and quinolines were successfully involved in the reaction with phenylmagnesium halides (phenylmagnesium chloride, 2-methoxyphenylmagnesium bromide, and 4-methoxyphenylmagnesium bromide). The conditions used also allowed the cross-coupling of 4-fluorotoluene with arylmagnesium reagents. 相似文献
17.
Whitfield TW Varma S Harder E Lamoureux G Rempe SB Roux B 《Journal of chemical theory and computation》2007,3(6):2068-2082
The hydration of K(+) is studied using a hierarchy of theoretical approaches, including ab initio Born-Oppenheimer molecular dynamics and Car-Parrinello molecular dynamics, a polarizable force field model based on classical Drude oscillators, and a nonpolarizable fixed-charge potential based on the TIP3P water model. While models based more directly on quantum mechanics offer the possibility to account for complex electronic effects, polarizable and fixed-charges force fields allow for simulations of large systems and the calculation of thermodynamic observables with relatively modest computational costs. A particular emphasis is placed on investigating the sensitivity of the polarizable model to reproduce key aspects of aqueous K(+), such as the coordination structure, the bulk hydration free energy, and the self diffusion of K(+). It is generally found that, while the simple functional form of the polarizable Drude model imposes some restrictions on the range of properties that can simultaneously be fitted, the resulting hydration structure for aqueous K(+) agrees well with experiment and with more sophisticated computational models. A counterintuitive result, seen in Car-Parrinello molecular dynamics and in simulations with the Drude polarizable force field, is that the average induced molecular dipole of the water molecules within the first hydration shell around K(+) is slightly smaller than the corresponding value in the bulk. In final analysis, the perspective of K(+) hydration emerging from the various computational models is broadly consistent with experimental data, though at a finer level there remain a number of issues that should be resolved to further our ability in modeling ion hydration accurately. 相似文献
18.
19.
Zhiwei Cao Zhifeng Liu Xiaohong Wang Anfeng Shi Haishan Luo Benoît Noetinger 《国际流体数值方法杂志》2017,85(4):247-263
In this paper, a numerical method to capture the shock wave propagation in 1‐dimensional fluid flow problems with 0 numerical dissipation is presented. Instead of using a traditional discrete grid, the new numerical method is built on a range‐discrete grid, which is obtained by a direct subdivision of values around the shock area. The range discrete grid consists of 2 types: continuous points and shock points. Numerical solution is achieved by tracking characteristics and shocks for the movements of continuous and shock points, respectively. Shocks can be generated or eliminated when triggering entropy conditions in a marking step. The method is conservative and total variation diminishing. We apply this new method to several examples, including solving Burgers equation for aerodynamics, Buckley‐Leverett equation for fractional flow in porous media, and the classical traffic flow. The solutions were verified against analytical solutions under simple conditions. Comparisons with several other traditional methods showed that the new method achieves a higher accuracy in capturing the shock while using much less grid number. The new method can serve as a fast tool to assess the shock wave propagation in various flow problems with good accuracy. 相似文献
20.
S. B. Hosseini T. Beno S. Johansson U. Klement J. Kaminski K. Ryttberg 《Experimental Mechanics》2014,54(3):369-377
In this investigation, the applicability of the two-color pyrometer technique for temperature measurements in dry hard turning of AISI 52100 steel was studied, where both machined surfaces as well as cutting tools were considered. The impacts of differing hard turned surface topography on the two-color pyrometer readings was studied by conducting temperature measurements on reference samples created using cutting tools with different degrees of tool flank wear. In order to conduct measurements in a controlled environment, a specially designed furnace was developed in which the samples were heated step-wise up to 1,000 °C in a protective atmosphere. At each testing temperature, the temperatures measured by the two-color pyrometer were compared with temperatures recorded by thermocouples. For all materials and surfaces as studied here, the two-color pyrometer generally recorded significantly lower temperatures than the thermocouples; for the hard turned surfaces, depending on the surface topography, the temperatures were as much as ~20 % lower and for the CBN cutting tools, ~13 % lower. To be able to use the two-color pyrometer technique for temperature measurements in hard turning of AISI 52100 steel, a linear approximation function was determined resulting in three unique equations, one for each of the studied materials and surfaces. By using the developed approximation function, the measured cutting temperatures can be adjusted to compensate for differing materials or surface topographies for comparable machining conditions. Even though the proposed equations are unique for the hard turning conditions as studied here, the proposed methodology can be applied to determine the temperature compensation required for other surface topographies, as well as other materials. 相似文献