全文获取类型
收费全文 | 61622篇 |
免费 | 14801篇 |
国内免费 | 5428篇 |
专业分类
化学 | 59715篇 |
晶体学 | 773篇 |
力学 | 2248篇 |
综合类 | 288篇 |
数学 | 5009篇 |
物理学 | 13818篇 |
出版年
2024年 | 90篇 |
2023年 | 713篇 |
2022年 | 1134篇 |
2021年 | 1451篇 |
2020年 | 2651篇 |
2019年 | 3853篇 |
2018年 | 2182篇 |
2017年 | 1855篇 |
2016年 | 4749篇 |
2015年 | 5057篇 |
2014年 | 5151篇 |
2013年 | 6216篇 |
2012年 | 5619篇 |
2011年 | 4798篇 |
2010年 | 4587篇 |
2009年 | 4652篇 |
2008年 | 4304篇 |
2007年 | 3356篇 |
2006年 | 2940篇 |
2005年 | 2840篇 |
2004年 | 2313篇 |
2003年 | 1940篇 |
2002年 | 2596篇 |
2001年 | 1851篇 |
2000年 | 1700篇 |
1999年 | 790篇 |
1998年 | 352篇 |
1997年 | 326篇 |
1996年 | 260篇 |
1995年 | 232篇 |
1994年 | 165篇 |
1993年 | 191篇 |
1992年 | 152篇 |
1991年 | 118篇 |
1990年 | 95篇 |
1989年 | 71篇 |
1988年 | 76篇 |
1987年 | 55篇 |
1986年 | 64篇 |
1985年 | 61篇 |
1984年 | 40篇 |
1983年 | 29篇 |
1982年 | 21篇 |
1981年 | 16篇 |
1980年 | 14篇 |
1979年 | 21篇 |
1978年 | 12篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1975年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
972.
Reaction of α-nitro olefins with secondary amines in the presence of palladium(O) catalyst affords allylic amines. 相似文献
973.
Nonisothermal kinetics of the solid‐solid phase transition in (n‐C10H21NH3)2ZnCl4(C10Zn), (n‐C16H33NH3)2ZnCl4(C16Zn) and their binary system were determined by Kissinger and Ozawa methods from DSC measurements. The activation energy Ea of the binary system shows a waving dependence on WC10Zn%, which is caused by not only an intermediate (C10H21NH3)(n‐C16H33NH3)ZnCl4 but also three solid solution ranges (α, β, γ) in the phase diagram of C10Zn‐C16Zn. The variations of the layer d‐spacing are also convenient for the above result. 相似文献
974.
高效液相钴离子催化化学发光抑制法测定茶叶中的茶氨酸 总被引:5,自引:0,他引:5
研究了用高效液相分离、抑制化学发光测定茶叶中茶氨酸的分析方法。该法采用YWG C18(10μm,250mm×5 0mmi d )柱,以0 01mol·L-1醋酸钠 醋酸缓冲液(pH5 5)为流动相,流速为0 8mL·min-1。对茶氨酸抑制Co2+催化鲁米诺(luminol)与过氧化氢(H2O2)化学发光反应的条件进行了优化:Co2+的质量浓度为2μg·L-1,鲁米诺浓度为0 25mmol·L-1,H2O2浓度为0 5mmol·L-1。在茶氨酸的质量浓度为0 2g·L-1~5 0g·L-1时,茶氨酸抑制化学发光产生负峰的相对峰面积Y(将实际峰面积缩小至万分之一)与其质量浓度X(kg·L-1)的线性回归方程为Y=33862X+1 0605(r=0 9983)。 相似文献
975.
Zhao Y Kan ZY Zeng ZX Hao YH Chen H Tan Z 《Journal of the American Chemical Society》2004,126(41):13255-13264
Nucleic acid molecules may fold into secondary structures, and the formation of such structures is involved in many biological processes and technical applications. The folding and unfolding rate constants define the kinetics of conformation interconversion and the stability of these structures and is important in realizing their functions. We developed a method to determine these kinetic parameters using an optical biosensor based on surface plasmon resonance. The folding and unfolding of a nucleic acid is coupled with a hybridization reaction by immobilization of the target nucleic acid on a sensor chip surface and injection of a complementary probe nucleic acid over the sensor chip surface. By monitoring the time course of duplex formation, both the folding and unfolding rate constants for the target nucleic acid and the association and dissociation rate constants for the target-probe duplex can all be derived from the same measurement. We applied this method to determine the folding and unfolding rate constants of the G-quadruplex of human telomere sequence (TTAGGG)(4) and its association and dissociation rate constants with the complementary strand (CCCTAA)(4). The results show that both the folding and unfolding occur on the time scale of minutes at physiological concentration of K(+). We speculate that this property might be important for telomere elongation. A complete set of the kinetic parameters for both of the structures allows us to study the competition between the formation of the quadruplex and the duplex. Calculations indicate that the formation of both the quadruplex and the duplex is strand concentration-dependent, and the quadruplex can be efficiently formed at low strand concentration. This property may provide the basis for the formation of the quadruplex in vivo in the presence of a complementary strand. 相似文献
976.
Chemical Constituents of Ailanthus triphysa 总被引:2,自引:0,他引:2
Two new compounds,8(14),15-isopimaradiene-2α,3α,19-triol(1),and 6α,7β-dihydroxy-17(20)-cis-5α-pregna-16-one(2),together with four known copounds,a oxygenated rare phyllocladane,phyllocladan-16α,19-diol(3),kaempferol-3-0-β-D-galactopyranosied,kaempferol-3-0-α-L-rhamnopyranoside and scopoletin, were isolated from the leaves of Ailanthus tripysa.Structures of 1-3 were elucidated on the basis of spectroscopic data as compared with related compounds. 相似文献
977.
Thecurrentsurgeofinterestinthefield0fnon-linearoptics(NL0)isderivedbothfromaquestforafundamentalunderstanding0fthenon-linearprocess,anditSimPortanceinthetechn0logyofphotonics.Amongnon-linearphen0mena,thethird-ordernon-linearophcsoccuPyanimPortantp0sihonbecauseitprovidesthemechanicsforophcalswitching,ophcallogic,andreal-hmeholograPhy"'.0rganicmaterialwithextendednconjugahonsandlargeRdelocalizahonsarewellknownastheimPortantmaterialsofachievinglargethird-ordernonlinearihes3.ForexamPle,thiosen… 相似文献
978.
SynthesisandMagnetismof2┐Hydroxy┐1,3┐propylene┐bis(oxamato)┐bridgedCoⅡCuⅡCoⅡComplexesMIAOMing-ming,CHENGPeng,LIAODai-zhengJIA... 相似文献
979.
The synthesis, characterization and crystal structure analysis of the ammonium salt of the dioxovanadium(V) complex NH4[VO2(salhyph)] with the tridentate Schiff base ligand derived from salicylaldehyde and benzoic acid hydrazide (H2salhyph) is reported. NH4[VO2(salhyph)] crystallizes in the monoclinic space group Pn with a = 708.8(2), b = 1444.3(3), c = 717.1(2) pm and β = 101.09(2)°. The vanadium atom of the dioxovanadium(V) moiety has a distorted square‐pyramidal coordination geometry. Extensive hydrogen bonding is observed between the ammonium cation and the oxygen atoms coordinated to the vanadium atom yielding to a two‐dimensional network, where the complex anions are arranged in a bilayer. Additional crystal packing within the bilayer appears to be controlled mostly by π stacking between the aromatic rings of the ligand. The reactions of NH4[VO2(salhyph)] with several proton acidic compounds including water, methanol, and proton acids lead to neutral monooxovanadium(V) and dioxovanadium(V) complexes ([VO2(Hsalhyph)], [V2O3(salhyph)2] and [VO(OMe)(salhyph)(HOMe)]). 相似文献
980.
Two new charge-transfer hybrids with one or two ferrocenyl units covalently attached to a hexamolybdate cluster through an extended pi-conjugated bridge have been prepared using Pd-catalyzed coupling reactions on monoiodo- or diiodo-functionalized cluster substrates in over 60% yields. These hybrids have been characterized by (1)H NMR, FTIR, electrospray ionization mass spectrometry, and X-ray diffraction. The electronic spectra of these hybrids show a broad absorption tail extending beyond 550 nm, indicating the existence of charge-transfer transition from the ferrocenyl donor to the cluster acceptor. The observation of the clear charge-transfer transition indicates the contribution of charge-transfer resonance to the ground state in both 2a and 2b even though the donor-acceptor separation distance of 11.29 A is rather long, signaling a through-bond charge-transfer nature made possible by the organic pi-conjugated bridge. Cyclic voltammetry studies reveal a one-electron oxidation wave and a one-electron reduction wave for the hybrid with one ferrocenyl unit. For the one with two ferrocenyl units, a lower reduction potential and a two-electron oxidation wave are observed, indicating negligible electronic interactions between the two ferrocenyl units. 相似文献