全文获取类型
收费全文 | 30013篇 |
免费 | 4884篇 |
国内免费 | 4067篇 |
专业分类
化学 | 21692篇 |
晶体学 | 381篇 |
力学 | 2154篇 |
综合类 | 280篇 |
数学 | 3812篇 |
物理学 | 10645篇 |
出版年
2024年 | 78篇 |
2023年 | 493篇 |
2022年 | 800篇 |
2021年 | 928篇 |
2020年 | 1060篇 |
2019年 | 1079篇 |
2018年 | 886篇 |
2017年 | 847篇 |
2016年 | 1369篇 |
2015年 | 1368篇 |
2014年 | 1605篇 |
2013年 | 2133篇 |
2012年 | 2465篇 |
2011年 | 2471篇 |
2010年 | 1879篇 |
2009年 | 1822篇 |
2008年 | 1953篇 |
2007年 | 1712篇 |
2006年 | 1614篇 |
2005年 | 1510篇 |
2004年 | 1262篇 |
2003年 | 1092篇 |
2002年 | 1207篇 |
2001年 | 1058篇 |
2000年 | 768篇 |
1999年 | 763篇 |
1998年 | 686篇 |
1997年 | 552篇 |
1996年 | 551篇 |
1995年 | 461篇 |
1994年 | 449篇 |
1993年 | 318篇 |
1992年 | 274篇 |
1991年 | 254篇 |
1990年 | 216篇 |
1989年 | 134篇 |
1988年 | 133篇 |
1987年 | 119篇 |
1986年 | 117篇 |
1985年 | 98篇 |
1984年 | 68篇 |
1983年 | 57篇 |
1982年 | 48篇 |
1981年 | 47篇 |
1980年 | 29篇 |
1979年 | 25篇 |
1978年 | 18篇 |
1976年 | 11篇 |
1975年 | 9篇 |
1973年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
851.
Zhen‐Yu Li Ping Chen Hong‐Gui Xu Shu‐Ying Peng Yi‐Ming Yang Zhong‐Zhen Zhao Yue‐Wei Guo 《Helvetica chimica acta》2007,90(7):1353-1359
Five new polycyclic Daphniphyllum alkaloids, macropodumines F ( 1 ) and G ( 2 ), 17‐oxoyuzurimine ( 3 ), and macropodumines H ( 4 ) and I ( 5 ), were isolated from the leaves of D. macropodum Miq ., collected in Sichuan Province, China. The structures and relative configurations of the new compounds – as well as of four known, related alkaloids – were elucidated on the basis of in‐depth spectroscopic and mass‐spectrometric analyses, by chemical derivatization, and by comparison of spectroscopic data with those of known compounds. 相似文献
852.
通过4,4’-一氧二(异氰酸苯酯)与异丙醇加成反应,合成标题化合物 4,4’-一氧二(苯胺灵)(Ⅰ) (C20H24N2O5, Mr=372.41),并用X射线衍射、红外光谱、13C核磁共振、电子轰击质谱和元素分析对标题化合物进行表征. 晶体属于三斜晶系,空间群为P1晶体学参数为: a=0.85107(17), b=0.91164(18), c=1.45701(3) nm, α=80.44(3)°, β=85.25(3)°, γ=62.88(3)°, V=0.9922(3) nm3, Z=2, Dc=1.247 g•cm-3, μ(Mo Kα)=0.90 cm-1, F(000)=396.两个苯环平面之间的夹角为62.06° (0.06°). 晶体结构经全矩阵最小二乘法修正,最终偏离因子R=0.0520, wR=0.1434(对可观察点).此化合物应具有广谱的生物活性. 相似文献
853.
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step. 相似文献
854.
Yueping?Fang Xiaogang?Wen Shihe?YangEmail author Qi?Pang Lu?Ding Jiannong?Wang Weikun?Ge 《Journal of Sol-Gel Science and Technology》2005,36(2):227-234
Uniform ZnO nanorods arrays are grown directly from and on Zn foils in pure water under hydrothermal conditions at a relatively
low temperature. The nanorods are 80–200 nm in diameter and ∼ 1 μm in length, which grow on the Zn foil along the [001] direction.
By changing the pure water to a urea solution, a Zn compound ([Zn5(OH)6(CO3)2], a precursor of ZnO nanoflowers film, is created by self-assembly. The ZnO nanoflowers film can be easily obtained by heating
the [Zn5(OH)6(CO3)2] compound in N2 at 350∘C for 5–6 hours. Possible growth processes of the ZnO nanorods arrays and the [Zn5(OH)6(CO3)2] nanoflowers are discussed. Photoluminescence properties of the as-prepared ZnO nanostructures have been measured. The ZnO
nanorods array synthesized using our method has minimal defects so that only band-gap emission is observed. However, the ZnO
nanoflowers film, obtained by heating the [Zn5(OH)6(CO3)2] nanoflower precursor in N2, is polycrystalline and displays strong defect-related emission. 相似文献
855.
Four dinuclear and trinuclear Cu(I) complexes that contain 2-(2'-pyridyl)benzimidazolyl derivative ligands including 1,4-bis[2-(2'-pyridyl)benzimidazolyl]benzene (1,4-bmb), 1,3-bis[2-(2'-pyridyl)benzimidazolyl]benzene (1,3-bmb), 1,3,5-tris[2-(2'-pyridyl)benzimidazolyl]benzene (tmb), and 4,4'-bis[2-(2'-pyridyl)benzimidazolyl]biphenyl (bmbp) have been synthesized. The formulas of these complexes are [Cu(2)(1,4-bmb)(PPh(3))(4)][BF(4)](2) (1), [Cu(2)(1,3-bmb)(PPh(3))(4)][BF(4)](2) (2), [Cu(3)(tmb)(PPh(3))(6)][BF(4)](3) (3), and [Cu(2)(bmbp)(PPh(3))(4)][BF(4)](2) (4), respectively. The crystal structures of 2-4 have been determined by single-crystal X-ray diffraction analyses. The Cu(I) ions in the complexes have a distorted tetrahedral geometry. For 3, two structural isomers (syn and anti) resulted from two different orientations of the three 2-(2'-pyridyl)benzimidazolyl chelating units were observed in the crystal lattice. Variable-temperature (1)H NMR experiments established the presence of syn and anti isomers for 1-3 in solution which interconvert at ambient temperature. Complexes 1-4 have a weak MLCT absorption band in the 350-450 nm region and display a yellow-orange emission when irradiated by UV light. One unexpected finding is that the yellow-orange emission of complexes 1-4 has a very long decay lifetime (approximately 200 micros) at 77 K. An electroluminescent (EL) device using 4 as the emitter and PVK as the host was fabricated. However, the long decay lifetime of the copper complexes may limit their applications as phosphorescent emitters in EL devices. 相似文献
856.
Yuehai ShenJianxun Wen 《Journal of fluorine chemistry》2002,113(1):13-15
A new and efficient route has been developed to synthesize 17β-(1-methyl-3-perfluoroalkyl)propyl-3β-androsterol (1) in nine steps from hyodeoxycholic acid via selective addition of 1-perfluoroalkyl iodide to 24-norchola-5,22-dien-3β-ol. From (1), the first series of steroidal liquid crystalline aliphatic esters (smectic A) with fluorocarbon side chains has been prepared. 相似文献
857.
1—酰基—4—氯环己烷与取代芳烃的区域与立体选择性反应 总被引:2,自引:0,他引:2
从环己烯合成了1-酰基-4-氯环己烷,发现在其在AlCl3催化与苯,氯苯,溴苯等优先生成反式1-芳基-4-酰基环己烷,与联苯反应时选择性较差。 相似文献
858.
核糖核酸酶A在DAB-环乙烷溶液中的活性和构象 总被引:1,自引:0,他引:1
The activity and conformation of ribonuclerse A (RNaseA) solubilized in cyclohexane via dodecylammonium butyrate(DAB) reverse micelles were investigated. The activity of RNaseA was studied using the cytidine 2’,3’ -phosphate as the substrate, and it was found that kcat increases significantly with respect to that in water attended by an increased Km•FT-IR spectra of RNaseA in reverse micellar solution were investigated as a function of w0(= [H2O]/ [DAB]), and it was noted that the structure of RNaseA became losser in reverse micelles campared to that in aqueous solution. The relation between activity and conformation was discussed. 相似文献
859.
研究了一系列聚芳醚砜的H2、CO2、O2、N2和CH4气体透过性能,讨论了其气体透过的温度依赖性。与双酚A聚砜(PSF)相比,几种新型聚芳醚砜的气体透过系数和气体选择系数同时有所提高。通过聚合物的分子链段活动性和自由体积数据系列变化,讨论了气体透过速率与分子结构的关系。 相似文献
860.
复合氨基酸微量元素螯合物制备新工艺的研究 总被引:19,自引:0,他引:19
本文报道了以废羽毛为原料,采用矿物质硫酸盐的制备与中和脱酸、螯合反应结合的新工艺,以金属盐类作催化剂和硫酸水解法,制得了复合氨基酸微量元素螯合物。复合氮基酸生成率为71.7%,微量元素螯合率达到98%以上。该工艺简单易行,生产成本低。 相似文献