全文获取类型
收费全文 | 33032篇 |
免费 | 4037篇 |
国内免费 | 6498篇 |
专业分类
化学 | 35886篇 |
晶体学 | 482篇 |
力学 | 639篇 |
综合类 | 212篇 |
数学 | 1471篇 |
物理学 | 4877篇 |
出版年
2024年 | 43篇 |
2023年 | 480篇 |
2022年 | 707篇 |
2021年 | 1212篇 |
2020年 | 1752篇 |
2019年 | 1449篇 |
2018年 | 1427篇 |
2017年 | 1330篇 |
2016年 | 1634篇 |
2015年 | 1558篇 |
2014年 | 2071篇 |
2013年 | 3356篇 |
2012年 | 1917篇 |
2011年 | 2167篇 |
2010年 | 1750篇 |
2009年 | 1964篇 |
2008年 | 2064篇 |
2007年 | 2239篇 |
2006年 | 2073篇 |
2005年 | 1927篇 |
2004年 | 1867篇 |
2003年 | 1463篇 |
2002年 | 928篇 |
2001年 | 723篇 |
2000年 | 740篇 |
1999年 | 633篇 |
1998年 | 562篇 |
1997年 | 502篇 |
1996年 | 433篇 |
1995年 | 440篇 |
1994年 | 336篇 |
1993年 | 265篇 |
1992年 | 247篇 |
1991年 | 180篇 |
1990年 | 146篇 |
1989年 | 131篇 |
1988年 | 106篇 |
1987年 | 79篇 |
1986年 | 70篇 |
1985年 | 87篇 |
1984年 | 73篇 |
1983年 | 37篇 |
1982年 | 51篇 |
1981年 | 49篇 |
1980年 | 37篇 |
1979年 | 31篇 |
1978年 | 32篇 |
1977年 | 41篇 |
1976年 | 42篇 |
1974年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
61.
Cosmic dust and our origins 总被引:1,自引:0,他引:1
J Mayo Greenberg 《Surface science》2002,500(1-3):793-822
The small solid particles in the space between the stars provide the surfaces for the production of many simple and complex molecules. Processes involving the effects of ultraviolet irradiation of the thin (hundredth micron) mantles are shown to produce a wide range of molecules and ions also seen in comets. Some of the more complex ones inferred from laboratory experiments are expected to play an important role in the origin of life. An outline of the chemical evolution of interstellar dust as observed and as studied in the laboratory is presented. Observations of comets are shown to provide substantial evidence for their being fluffy aggregates of interstellar dust as it was in the protosolar nebula, i.e. the interstellar cloud which collapsed to form the solar system. The theory that comets may have brought the progenitors of life to the earth is summarized. 相似文献
62.
We present a Darboux transformation for Tzitzeica equation associated with 3 × 3 matrix spectral problem. The explicit solution of Tzitzeica equation is obtained. 相似文献
63.
64.
The coordination polymer {[Co(phth)(phen)(H2O)]·(C2H5OH)}n (phth = phthalate, phen = 1,10-phenanthroline) with formula C22H20CoN2O6 (Mr = 467.33) was synthesized by the solvothermal method under low temperature, and its crystal structure was determined by singlecrystal X-ray diffraction. The complex belongs to monoclinic system, space group P21/n with a =12.7352(16), b = 8.8125(11), c = 18.677(2) (A), β = 102.633(2)°, V = 2045.3(4) (A)3, Z = 4, Dc =1.518 g/cm3,μ = 0.882 mm-1, F(000) = 964, S = 1.053, the final R = 0.0401 and wR = 0.0984 for 3135 observed reflections (I > 2σ(I)). Single-crystal X-ray analysis revealed that the Co(Ⅱ) ion is six-coordinated. The cobalt complex forms a one-dimensional chain structure via phthalate bridging ligand. In the cobalt complex, a 3D network structure is formed by π-π stacking interaction of 1,10-phenanthroline as well as intermolecular hydrogen bonding interactions. 相似文献
65.
1 INTRODUCTION Carbon nanotubes have many potential applica- tions due to their unique structures and properties[1~4]. Physicists have been studying their electrical, me- chanical and other properties since their discove- ries[5, 6]. Recently, chemists are interested in carbon nanotubes because their properties can be altered by chemical functionalization[7~14], and these functiona- lized nanotubes can undergo further chemical trea- tment. So the potential application range of such na- … 相似文献
66.
G.P. Romanelli D. Bennardi D.M. Ruiz G. Baronetti H.J. Thomas 《Tetrahedron letters》2004,45(48):8935-8939
Substituted coumarins are synthesized from phenols and β-ketoesters by the Pechmann reaction, using a Wells-Dawson heteropolyacid (H6P2W18O62·24H2O) as catalyst by a solvent-free procedure. This one requires low reaction times, 130 °C temperature and as little as 1 mol % of Wells-Dawson acid, obtaining good to excellent yields of coumarins. The catalyst showed to be reusable with no differences in the yields. The results are compared with those of the reactions performed in toluene solution. The presented synthetic procedure is a convenient, clean and fast alternative for synthesizing 4-substituted coumarins (17 examples). 相似文献
67.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
68.
K. C. Kumara Swamy E. Balaraman M. Phani Pavan N. N. Bhuvan Kumar K. Praveen Kumar N. Satish Kumar 《Journal of Chemical Sciences》2006,118(6):495-501
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated
acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature
of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction. 相似文献
69.
This paper is devoted to a detailed theoretical study of an ion pair SN2 reaction LiNCO+CH3F in the gas phase and in solution at the level of MP2(full)/6-31+G**//HF/6-31+G**. Two possible reaction mechanisms, inversion and retention, are discussed. There are eight possible reaction pathways. The inversion mechanism is more favorable no matter in the gas phase or in solution based on analyses of the transition structures. Methyl isocyanate should form preferentially in the gas phase and more stable methyl cyanate is the main product in solution. The retardation of the reaction in solvents was attributed to the difference in solvation in the separated reactants and in the transition state. 相似文献
70.