全文获取类型
收费全文 | 4024篇 |
免费 | 724篇 |
国内免费 | 1239篇 |
专业分类
化学 | 2617篇 |
晶体学 | 123篇 |
力学 | 353篇 |
综合类 | 204篇 |
数学 | 670篇 |
物理学 | 2020篇 |
出版年
2024年 | 4篇 |
2023年 | 37篇 |
2022年 | 124篇 |
2021年 | 141篇 |
2020年 | 134篇 |
2019年 | 105篇 |
2018年 | 111篇 |
2017年 | 172篇 |
2016年 | 120篇 |
2015年 | 198篇 |
2014年 | 235篇 |
2013年 | 280篇 |
2012年 | 292篇 |
2011年 | 317篇 |
2010年 | 332篇 |
2009年 | 277篇 |
2008年 | 363篇 |
2007年 | 329篇 |
2006年 | 380篇 |
2005年 | 315篇 |
2004年 | 195篇 |
2003年 | 163篇 |
2002年 | 174篇 |
2001年 | 169篇 |
2000年 | 168篇 |
1999年 | 82篇 |
1998年 | 112篇 |
1997年 | 67篇 |
1996年 | 70篇 |
1995年 | 62篇 |
1994年 | 56篇 |
1993年 | 41篇 |
1992年 | 54篇 |
1991年 | 37篇 |
1990年 | 44篇 |
1989年 | 45篇 |
1988年 | 23篇 |
1987年 | 23篇 |
1986年 | 25篇 |
1985年 | 17篇 |
1984年 | 18篇 |
1983年 | 13篇 |
1982年 | 13篇 |
1981年 | 10篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1978年 | 7篇 |
1965年 | 4篇 |
1961年 | 3篇 |
1959年 | 5篇 |
排序方式: 共有5987条查询结果,搜索用时 375 毫秒
111.
Yuan Yuan WANG Hui SUN Juan LI Dong JIANG Li Yi DAI 《中国化学快报》2006,17(1):117-120
Room temperature ionic liquids (RTILs) as advanced, technological solvents can be designed to fit a particular application. They used as green “media and/or catalysts” for chemical synthesis have been extensively reviewed recently. RTILs1 not only show … 相似文献
112.
离子液体体系中1-丁烯二聚反应的研究 总被引:8,自引:0,他引:8
研究了在强酸性AlCl3/Et2AlCl/[BMIM]Cl型离子液体体系中过渡金属化合物对1-丁烯二聚反应的催化作用.结果表明,[BMIM]Cl对强酸性AlCl3/Et2AlCl催化剂催化1-丁烯高聚反应有明显的阻聚作用,并显著提高了1-丁烯二聚的选择性.在过渡金属化合物中,含镍化合物对1-丁烯二聚反应有最好的催化效果.在最佳反应条件下,1-丁烯的转化率可达95.1%,二聚产物C8烯的选择性为85.8%.同时,对1-丁烯二聚反应的机理进行了初步探讨. 相似文献
113.
在Polanyi吸附势理论基础上,结合程序升温脱附曲线的测定,建立了一个快速测定吸附热的新方法,详细讨论了该方法的原理,通过微机采样和数据处理,测定一条吸附热与覆盖度的曲线仅需1h左右。 相似文献
114.
Amphiphilic polypyridyl mthenium(Ⅱ) complex cis-di(isothiocyanato)(4,4'-di-tert-butyl-2,2'-bipyridyl)(4,4'- dicarboxy-2,2'-bipyridyl)ruthenium(Ⅱ)(K005) has been synthesized and characterized by cyclic voltammetry, ^1H NMR, UV-Vis, and FT-IR spectroscopies. The sensitizer sensitizes TiO2 over a notably broad spectral range due to its intense metal-to-ligand charge-transfer (MLCT) bands at 537 and 418 nm. The photophysical and photochemical studies of K005 were contrasted with those of cis-Ru(dcbpy)2(NCS)2, known as the N3 dye, and the amphiphilic ruthenium(Ⅱ) dye Z907. A reversible couple at E1/2=0.725 V vs. saturated calomel electrode (SCE) with a separation of 0.08 V between the anodic and cathodic peaks, was observed due to the Ru^Ⅱ/Ⅲ couple by cyclic voltammetry. Furthermore, this amphiphilic ruthenium complex was successfully used as sensitizers for dye-sensitized solar cells with the efficiency of 3.72% at the 100 mW·cm^-2 irradiance of air mass 1.5 simulated sunlight without optimization of TiO2 films and the electrolyte. 相似文献
115.
Enantiomers of the orthometalated dirhodium compound cis-Rh2(C6H4PPh2)2(OAc)2(HOAc)2 (R-1 and S-1) were prepared from carboxylate exchange reactions of the resolved diasteroisomers of cis-Rh2(C6H4PPh2)2(protos)2(H2O)2 (protos = N-4-methylphenylsulfonyl-l-proline anion) and acetic acid. These compounds react with excess Me3OBF4 in CH3CN, producing the enantiomers of [cis-Rh2(C6H4PPh2)2(CH3CN)6](BF4)2 (R-2 and S-2) which have six labile and replaceable CH3CN ligands in equatorial and axial positions. Reactions of R-2 and S-2 with tetraethylammonium salts of the linear dicarboxylic acids, terephthalic acid (HO2CC6H4CO2H), oxalic acid (HO2CCO2H), and 4,4'-diphenyl-dicarboxylic acid (HO2CC6H4C6H4CO2H) afford the enantiopure triangular supramolecules [cis-Rh2(C6H4PPh2)2(O2CC6H4CO2)(py)2]3, RRR-3 and SSS-3, Rh6(cis-C6H4PPh2)6(O2CCO2)3(py)5(CH2Cl2), RRR-4 and SSS-4, and Rh6(cis-C6H4PPh2)6(O2CC6H4C6H4CO2)3(py)4(CH2Cl2)2, RRR-5 and SSS-5, respectively. The absolute structures of each of the enantiomers of 1, 3, 4, and 5 were determined by X-ray diffraction analyses. The enantiomers of 3, 4, and 5 were found to be enantiomorphically isostructural, whereas R-1 and S-1 crystallized in different space groups. In 4 and 5, CH2Cl2 molecules coordinate to rhodium atoms in the axial positions. The 1H and 31P[1H] NMR spectra of all compounds are reported. The triangular compounds are redox-active, and their electrochemistry is also discussed. An assay of the catalytic activity/selectivity performance of the triangles for typical metal carbene transformation, using the model intermolecular cyclopropanation of styrene with ethyl diazoacetate in both homogeneous and heterogeneous phases, show that these chiral triangles are very active and have remarkable selectivity when compared with simple Rh2 paddle-wheel catalysts with chiral amidate ligands. 相似文献
116.
117.
Yang X Jones RA Lynch V Oye MM Holmes AL 《Dalton transactions (Cambridge, England : 2003)》2005,(5):849-851
Near infrared luminescence is observed in tetrametallic [Zn2Yb2L2(mu-OH)2Cl4].2MeCN which is obtained from the Zn3 Schiff-base complex [Zn3L2(NO3)2].MeOH, (H2L =N,N'-bis(5-bromo-3-methoxysalicylidene)propylene-1,3-diamine). 相似文献
118.
A major issue with the electrolytic conductivity measurement for pure water is the lack of standard or reference methods.
A primary method traceable to SI and suitable for pure-water conductivity measurement was developed at the Physikalisch-Technische
Bundesanstalt (PTB), Germany, as the base for the calibration method for the conductivity measuring devices at the low conductivity
level. This paper provides a novel method to calculate the bulk resistance of pure water using impedance measured at a single
frequency, which is one of the key procedures for the primary methods. 相似文献
119.
Reactions of Pd3(OAc)6 with lithium salts of mononegative bidentate N,N-ligands, L, of various types, such as formamidinates, benzamidinates, triazinates, and guanidinates, were investigated in a search for ways to obtain Pd2(4+) compounds that could serve as precursors to paddlewheel complexes with a metal-metal bond and a Pd2(5+) core. It was found that the reactions are complex and that either square planar mononuclear or dinuclear species may be formed depending on the reaction conditions or the method of isolation. For Pd2L4 compounds, alpha and beta isomers were sometimes obtainable. In the alpha isomer, all N,N-ligands serve as bridges, whereas in the beta isomer, two ligands bridge the Pd2(4+) unit and each of the other two chelate to a metal atom. Electrochemistry shows that the paddlewheel compounds Pd2(TolNC(H)NTol)4, Pd2(PhNC(Ph)NPh)4, and Pd2(PhNC(Ph)NPh)3(OAc) and the orthometalated complex cis-Pd2[eta2-C6H4NC(Ph)N(H)Ph]2(mu-OAc)2 have reversible oxidation waves between 0.70 and 0.92 V vs Ag/AgCl, which makes them good candidates for chemical oxidation. 相似文献
120.