全文获取类型
收费全文 | 7267篇 |
免费 | 832篇 |
国内免费 | 253篇 |
专业分类
化学 | 5911篇 |
晶体学 | 90篇 |
力学 | 193篇 |
综合类 | 2篇 |
数学 | 107篇 |
物理学 | 2049篇 |
出版年
2024年 | 14篇 |
2023年 | 76篇 |
2022年 | 191篇 |
2021年 | 233篇 |
2020年 | 360篇 |
2019年 | 247篇 |
2018年 | 171篇 |
2017年 | 180篇 |
2016年 | 302篇 |
2015年 | 323篇 |
2014年 | 356篇 |
2013年 | 471篇 |
2012年 | 416篇 |
2011年 | 401篇 |
2010年 | 317篇 |
2009年 | 423篇 |
2008年 | 431篇 |
2007年 | 530篇 |
2006年 | 388篇 |
2005年 | 309篇 |
2004年 | 256篇 |
2003年 | 276篇 |
2002年 | 216篇 |
2001年 | 190篇 |
2000年 | 152篇 |
1999年 | 162篇 |
1998年 | 163篇 |
1997年 | 72篇 |
1996年 | 77篇 |
1995年 | 77篇 |
1994年 | 58篇 |
1993年 | 60篇 |
1992年 | 50篇 |
1991年 | 43篇 |
1990年 | 40篇 |
1989年 | 36篇 |
1988年 | 35篇 |
1987年 | 27篇 |
1986年 | 33篇 |
1985年 | 29篇 |
1984年 | 26篇 |
1983年 | 8篇 |
1982年 | 13篇 |
1981年 | 13篇 |
1980年 | 20篇 |
1979年 | 18篇 |
1978年 | 14篇 |
1977年 | 13篇 |
1976年 | 10篇 |
1974年 | 8篇 |
排序方式: 共有8352条查询结果,搜索用时 15 毫秒
41.
J. Howard Rytting Danny R. McHan Takeru Higuchi David J. W. Grant 《Journal of solution chemistry》1986,15(8):693-703
Henry's law constants have been determined for -butyrolactone (BL), ethyl acetate (EA), and 2-methyl-3-pentanol (MEP) in mixtures of iso-octane (ISO) and toluene (TOL), for BL, EA, TOL, and ISO in cinnamaldehyde (CIN) and for TOL and ISO in each other and in BL. From these data and published vapor pressures, the activity coefficients at infinite dilution and the standard molar Gibbs free energy of transfer, G
2
0
of the solutes from dilute solution in ISO to dilute solution in each solvent medium have been calculated. The different behavior patterns of BL and EA are attributed to differences in their abilities to exist in different conformations possessing different dipole moments. For polar solutes, G
2
0
decreases with increasing polarizability of the solvent and with increasing dipole moment of the solute, suggesting increased contributions from dipole-induced dipole (Debye) interactions. The sigmoidal plot of G
2
0
against the change in pair potential energy calculated from the classical expressions suggests that G
2
0
seriously underestimates the strength of the Debye interactions in comparison with the London interactions. 相似文献
42.
A. A. Dulov L. A. Abramova E. M. Stasenko V. N. Efremov G. M. Tesakova E. Z. Golosman V. I. Yakerson 《Russian Chemical Bulletin》1994,43(9):1471-1474
The surface phase composition of alumocalcium cement-supported CuO and CuO-NiO catalysts prepared by chemical mixing has been studied using the method of thermo-vacuum curves of electric conductivity. The deactivation of these catalysts due to overheating to 800 °C under conditions of hydrogenation of oxygen is rationalized by the partial extraction of CuO (and NiO) from the stabilizing structure of the support solid solutions and by sintering of the extracted oxides and the reduced metallic phase. Complete regeneration of the CuO-NiO-talum catalysts can be achieved if a considerable amount (20%) of copper hydroxocarbonate is added.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1559–1562, September, 1994. 相似文献
43.
Chen-Xi Zhang Zhi-Liang Liu Dai-Zheng Liao Zong-Hui Jiang Shi-Ping Yan 《Journal of Molecular Structure》2003,650(1-3):21-26
A novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H2O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H2O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py. 相似文献
44.
V. Yu. Filinovskii 《Russian Journal of Electrochemistry》2006,42(12):1319-1324
Identity of mathematical problems concerning calculation of the distribution of reactants’ concentrations and the current near the surface of a nonuniform (strip) electrode and distribution of displacements and forces in the case of an elastic layer “antiplane” deformation caused by the punch action. Formulas for calculating the current at a strip electrode are derived for various ratios between the electrode width and the diffusion layer thickness by means of asymptotic methods designed for calculating problems of mechanical contact interactions. It is noted that calculations of the diffusion current for involved activity distributions at the electrode surface may benefit from asymptotic methods of mechanics of contact interactions. 相似文献
45.
Fluorogenic probes dual-labeled with reporter and quencher dyes use a change in fluorescence to monitor biochemical events (e.g., substrate binding or enzyme digestion). Such events change the reporter-quencher distance, which affects fluorescence. Recently, it is has been shown that static quenching through intramolecular dimers is an important mechanism that can sometimes be more efficient than F?rster resonance energy transfer (FRET). 相似文献
46.
碳氟链与碳氢链表面活性剂在固液界面上的吸附 总被引:1,自引:0,他引:1
全氟辛酸及其钠盐和十二烷基硫酸钠在R972上的吸附等温线均为S型或LS型,指示固液界面吸附过程中有表面疏水缔合物生成.碳氟表面活性剂的饱和吸附量显著高于碳氢表面活性剂的饱和吸附量.加电解质于液相使各体系吸附量上升.对于碳氟表面活性剂,甚至引起吸附等温线类型变化.例如,不加电解质时全氟辛酸在R972上的吸附等温线为S型,而加入HCl(c=0.05mol·dm-3)使吸附等混线变成LS型.全氟辛酸比全氟辛酸钠在R972上的吸附更强.几种表面活性剂在R972上的吸附均随温度升高而减少。应用两阶段吸附模型及通用吸附等温线公式可以很好地解释所得实验结果. 相似文献
47.
An additive procedure (SIBFA) is developed for the rapid computation of conformational energy variations in very large molecules. The macromolecule is built out of constitutive molecular fragments and the intramolecular energy is computed as a sum of interaction energies between the fragments. The electrostatic and the polarization components are calculated using multicenter multipole expansions of theab initio SCF electron density of the fragments. The repulsion component is obtained as a sum of bond and lone pair interactions.Tests of the procedure on a series of model compounds containing ether oxygens and pyridine-like nitrogens are reported and compared with the results of correspondingab initio SCF calculations. The resulting methodology is compatible with the simultaneous computation of intermolecular interactions. 相似文献
48.
49.
Manolis Stratakis Christos Raptis Nikoletta Sofikiti Constantinos Tsangarakis Giannis Kosmas Ioannis-Panagiotis Zaravinos Dimitris Kalaitzakis Dimitris Stavroulakis Constantinos Baskakis Aggeliki Stathoulopoulou 《Tetrahedron》2006,62(46):10623-10632
Depending on the nature of the substituents on the stereogenic carbon atom, the ene reaction of singlet oxygen with several chiral alkenes by confinement within thionin-supported zeolite NaY, may exhibit significant changes on facial selectivity by comparison to their photooxygenation reaction in solution. It is proposed that, apart from the conformational consequences as a result of the alkene confinement within the zeolite cavities, a synergism between Na+-π interactions and singlet oxygen-Na+ interactions plays a significant role in the transition states of ene hydroperoxidation. Within NaY, the diastereoselectivity may significantly depend on the site selectivity, as probed through specific deuterium labelling of trisubstituted alkenes bearing a gem-dimethyl group. In certain cases, a remote stereogenic centre relative to the reacting double bond may induce enhanced diastereoselection and regioselectivity. 相似文献
50.
David M. Rogers Claire Wells Melanie Joseph Vanessa J. Boddington Joseph J.W. McDouall 《Journal of Molecular Structure》1998,434(1-3):239-245
We describe a procedure which may be used to aid selection of the active space in multiconfigurational self-consistent field (MCSCF) calculations for general chemical systems. Starting from a restricted Hartree-Fock calculation, we define a hierarchy of interacting virtual orbitals for every occupied orbital. The most strongly interacting orbitals are then taken to constitute the active space in a configuration interaction (CI) calculation. The natural orbital occupation numbers obtained from the CI calculation are then used to choose the active space to be used in a subsequent MCSCF calculation. We illustrate our method on a number of systems (Li2, B2, C2, carbonyl oxide and the transition state for oxidation of H2S by dioxirane). In all these cases, ‘intuitive’ active spaces are inadequate, as are active spaces derived from the natural orbitals of unrestricted Hartree-Fock calculations. 相似文献