全文获取类型
收费全文 | 16640篇 |
免费 | 1387篇 |
国内免费 | 5272篇 |
专业分类
化学 | 18179篇 |
晶体学 | 438篇 |
力学 | 496篇 |
综合类 | 166篇 |
数学 | 1686篇 |
物理学 | 2334篇 |
出版年
2024年 | 20篇 |
2023年 | 133篇 |
2022年 | 227篇 |
2021年 | 387篇 |
2020年 | 422篇 |
2019年 | 393篇 |
2018年 | 381篇 |
2017年 | 476篇 |
2016年 | 564篇 |
2015年 | 476篇 |
2014年 | 733篇 |
2013年 | 1338篇 |
2012年 | 1561篇 |
2011年 | 938篇 |
2010年 | 784篇 |
2009年 | 1026篇 |
2008年 | 1195篇 |
2007年 | 1247篇 |
2006年 | 1179篇 |
2005年 | 1167篇 |
2004年 | 1073篇 |
2003年 | 892篇 |
2002年 | 816篇 |
2001年 | 638篇 |
2000年 | 612篇 |
1999年 | 585篇 |
1998年 | 539篇 |
1997年 | 474篇 |
1996年 | 450篇 |
1995年 | 457篇 |
1994年 | 404篇 |
1993年 | 301篇 |
1992年 | 331篇 |
1991年 | 261篇 |
1990年 | 193篇 |
1989年 | 161篇 |
1988年 | 107篇 |
1987年 | 81篇 |
1986年 | 80篇 |
1985年 | 58篇 |
1984年 | 46篇 |
1983年 | 22篇 |
1982年 | 26篇 |
1981年 | 12篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 5篇 |
1972年 | 2篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 281 毫秒
31.
Jack Harrowfield Dominique Matt 《Journal of inclusion phenomena and macrocyclic chemistry》2004,50(3-4):133-150
The problems involved in identifying and quantifying labile interactions considered to influence complex compound structures are highlighted through the assessment of four different families of metal complexes for which extensive crystallographic data are available. Modification of the charge distribution within a ligand molecule as a result of coordination is one factor with a number of ramifications. A detailed analysis of evidence for both intra- and inter-molecular attractions in dimethylsulfoxide complexes of metal perchlorates is used to provide a basis for the consideration of weak interactions between complex ions involving forces including phenyl-group attractions, hydrogen bonding and cavity inclusion. 相似文献
32.
Introduction In the previous studies on the oxidation reaction,peroxydisulfate was widely used as an oxidizingagent.1-5 One of the advantages of this oxidant lies in itsstability in a wide range of pH values. The reaction be-tween Fe(CN)5L3- (L=N-aromatic heterocyclic li-gands) and S2O8 2- has been proved to proceed throughan outer-sphere electron transfer mechanism.5 For a re-action [(Eq. (1)] to be under an outer-sphere mechanismthe steps involved are the formation of a reactant … 相似文献
33.
XiaoMinSUN DaChengFENG ZhengTingCAI 《中国化学快报》2004,15(6):749-752
For the Na I2 collision system, theoretical study is performed on the QCISD(T) level by using ab initio method. The ab initio potential energy surfaces are got and on them the long-lived complexes are found and optimized. These results verify the crossed molecule beam experimental phenomenon and the detailed geometry structures are given for the first time. The role of the complexes in the reaction path is also described in detail. 相似文献
34.
FengSHI HongYangLI XiaoJunPENG RongZHANG XiaoQiangCHEN JiangLiFAN LiChengSUN 《中国化学快报》2004,15(12):1407-1410
As photosensitizer for solar cell, a new ruthenium (Ⅱ) complex with four ester groups had been synthesized, in which a phenol substituted by {[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)amino]methyl} is covalently linked to ruthenium (Ⅱ) tris-bipyridine. The structures of the new compounds were confirmed by NMR and ESI-MS spectra. The electrochemical and photochemical properties were also studied. 相似文献
35.
Continuous dependence on a modelling parameter is established for solutions of a problem for a complex Ginzburg–Landau equation. A homogenizing boundary condition is also used to discuss the continuous dependence results. We derive a priori estimates that indicate that solutions depend continuously on a parameter in the governing differential equation. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
36.
The association of complex formation with static quenching in CT systems was investigated. Evaluation of the data made evident
that the inner filter effect must be allowed for. Time-resolved and temperature-dependent stationary measurements of fluorescence
led to the separation of dynamic and static quenching components. The static quenching constant is discussed with respect
to the equilibrium constant of complex formation determined by absorption spectroscopy. 相似文献
37.
Benjamin S. Hsiao Rong-Ming Ho Stephen Z. D. Cheng 《Journal of Polymer Science.Polymer Physics》1995,33(17):2439-2447
Unique crystallization and melting behavior in poly(aryl ether ketone ketone) containing alternated terephthalic and isophthalic moieties were studied by time-resolved synchrotron x-ray methods. Recently, this material has been shown to exhibit three polymorphs (forms I, II, and III). In this work, we further investigated their distinctive thermal properties and found that form I is the dominating and the most thermally stable phase while form II is favored by fast nucleation conditions and is the least stable phase. On the other hand, form III represents a minor intermediate phase that usually coexists with form I and can be transferred from form II and to form I. Structural and morphological changes in form I have been followed by simultaneous wide-angle x-ray diffraction (WAXD)/small-angle x-ray scattering (SAXS) measurements during cold- or melt-crystallization and subsequent melting. In all cases, a larger dimensional change was found in the crystallographic a-axis than the b-axis during heating and cooling. This may be due to the greater lateral stress variation with respect to temperature along the a direction of the primary lamellae which is induced by either the formation of secondary lamellae or the preferential chain-folding direction in poly(aryl ether ketone ketone)s. During the phase transitions of form II ← III in the cold-crystallized specimen and form III ← I in the melt-crystallized samples, lamellar variables (long period, lamellar thickness, and invariant) obtained from SAXS remain almost constant. This indicates that the density distribution in the long spacing is independent of the melting in form II or III. For melt-crystallization, the corresponding changes in unit-cell dimensions and lamellar morphology during the annealing-induced low endotherm are most consistent with the argument that these changes are due to the melting of thin lamellar population. © 1995 John Wiley & Sons, Inc. 相似文献
38.
F. Rubio F. García H. D. Burrows A. A. C. C. Pais A. J. M. Valente M. J. Tapia J. M. García 《Journal of polymer science. Part A, Polymer chemistry》2007,45(9):1788-1799
The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H2O and D2O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H2O and D2O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007 相似文献
39.
Utpal Majumder 《Tetrahedron letters》2005,46(42):7209-7211
The scope and limitations of the Takai-Utimoto reagent to induce the cyclization of olefinic-esters is described. Critical is the steric environment about both the ester and the olefin. Mechanistically, these results support the hypothesis that cyclized product comes from an olefin metathesis, carbonyl-olefination sequence. 相似文献
40.