全文获取类型
收费全文 | 7857篇 |
免费 | 1389篇 |
国内免费 | 829篇 |
专业分类
化学 | 5834篇 |
晶体学 | 12篇 |
力学 | 916篇 |
综合类 | 52篇 |
数学 | 2144篇 |
物理学 | 1117篇 |
出版年
2024年 | 6篇 |
2023年 | 98篇 |
2022年 | 155篇 |
2021年 | 203篇 |
2020年 | 390篇 |
2019年 | 215篇 |
2018年 | 269篇 |
2017年 | 233篇 |
2016年 | 373篇 |
2015年 | 447篇 |
2014年 | 475篇 |
2013年 | 678篇 |
2012年 | 523篇 |
2011年 | 551篇 |
2010年 | 492篇 |
2009年 | 554篇 |
2008年 | 592篇 |
2007年 | 527篇 |
2006年 | 495篇 |
2005年 | 455篇 |
2004年 | 406篇 |
2003年 | 467篇 |
2002年 | 179篇 |
2001年 | 188篇 |
2000年 | 175篇 |
1999年 | 139篇 |
1998年 | 134篇 |
1997年 | 131篇 |
1996年 | 125篇 |
1995年 | 84篇 |
1994年 | 65篇 |
1993年 | 43篇 |
1992年 | 53篇 |
1991年 | 37篇 |
1990年 | 26篇 |
1989年 | 22篇 |
1988年 | 8篇 |
1987年 | 12篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1957年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
IntroductionIsodonenanderianus (Hand . Mazz .)H .W .Li(Labiatae) ,widelydistributedinthesouthernpartsofYunnanProvince ,hasbeenusedinChinesetraditionalfolkmedicineasanti inflammatoryanddetoxifiedagent.1Previousphytochemicalinvestigationhasshownthepres enceofaser… 相似文献
72.
光学活性化合物的工业合成 总被引:9,自引:0,他引:9
本文介绍了光学活性化合物研究现状及发展趋势。并从技术和经济角度论述了工业合成光学活性化合物的可能性 相似文献
73.
Two vanadyl salen complexes having peripheral styryl substituents have been reacted with 1-methyl-3-(3-mercaptopropyl)-imidazolium chloride using azoisobutyronitrile as radical initiator. The resulting compounds contain at the same time a vanadyl salen complex and one imidazolium cation. In agreement with the expectations in view of their structure, these compounds were insoluble in conventional organic solvents, but completely miscible in imidazolium ionic liquids. These vanadyl salen complexes bonded to an imidazolium cation are highly active and reusable catalysts for the cyanosilylation of aldehydes. Moderate enantiomeric excesses were obtained using the chiral version of this complex. 相似文献
74.
I. E. Karpeiskaya L. F. Godunova E. S. Levitina M. R. Lyubeznova E. I. Klabunovskii E. S. Shpiro G. N. Baeva E. D. Lubuzh L. B. Krentsel' A. D. Litmanovich N. A. Plate 《Russian Chemical Bulletin》1992,41(10):1858-1867
Pd complexes have been obtained from linear and cross-linked copolymers ofR,S-, R-, andS-1-(4-vinylphenyl)ethylamine (1) with styrene and divinylbenzene. Reduction of these compounds gave catalysts which were active in the reductive solvolysis of -acetaminocinnamic acid azlactone (2) and hydrogenation of the solvolysis products -acetamidocinnamic acid (ACA), its esters, and its 1-phenylethylamide. The catalysts showed no enantioselective properties in the reductive hydrolysis, but were more active than the catalyst obtained in the absence of the polymer (the monomeric analog). The use of polymeric catalysts has shown that, in reductive aminolysis, the chiral nucleophile plays the dominant part in determining the stereoselectivity of the reaction, rather than the chiral ligand of the catalytic complex. The polymer matrix stabilizes the low-valent state of the palladium in the complex. In the hydrogenation of ACA and its esters, the catalyst on the cross-linked polymer is much more active than its monomeric analog, but showed no enantioselectivity. Hydrogenation of acetamidocinnamic acidR-andS-1-phenylethylamides on a chiral Pd-polymer catalyst occurred with double asymmetric induction.Deceased.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 2368–2380, October, 1992. 相似文献
75.
76.
从(-)-(1S,2R,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(I)和(-)-(1S,2S,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(Ⅱ)出发,合成了它们的醚类和取代苯甲酸酯类光学纯的衍生物。通过[α]D测定和构型分析,发现它们是含有3个手性碳(C1,C2和C4)的桥环化合物,其旋光性与构型的关系均符合可极化度多级圆球不对称性模型。 相似文献
77.
A new type of dendritic 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN)-derived Schiff-base ligands have been synthesized and applied to the titanium-catalyzed hetero-Diels-Alder reaction of Danishefsky's diene with aldehydes. These reactions afforded the corresponding 2-substituted 2,3-dihydro-4H-pyran-4-ones in quantitative yields and with excellent enantioselectivities (up to 97.2 % ee). The disposition of the dendritic wedges and the dendron size in the ligands were found to have significant impact on the enantioselectivity of the reaction. The recovered dendritic catalyst could be reused without further addition of the Ti source or a carboxylic acid additive for at least three cycles, retaining similar activity and enantioselectivity. The high stability of this type of assembled dendritic titanium catalyst may be attributed to the stabilization effect of large-sized dendron units in the catalyst molecule. The other important phenomenon observed with this catalyst system is that a higher degree of asymmetric amplification has been achieved by attachment of the dendron unit to the chiral ligand, which represents a new advantage of dendrimer catalysts for asymmetric reactions using chiral ligands of lower optical purity. 相似文献
78.
79.
潜手性Schiff碱不对称催化还原反应研究进展 总被引:3,自引:0,他引:3
对近年来潜手性Schiff碱的不对称催化氢化的发展状况按照均相、非均相及氢转移催化氢化三种类型进行了较为详尽的综述. 相似文献
80.
手性钯络合物催化下2-硝基环酮的不对称烯丙基化反应 总被引:2,自引:0,他引:2
在用氮杂冠醚改良的手性二茂铁膦与钯的络合物催化下, 2-硝基环酮可进行不对称烯丙基化反应. 讨论了配位基的形状, 反应物的构造, 碱的类型以及反应时间对反应速率和立体选择性的影响. 通过增加反应的空间位阻改进了反应的立体选择性 . 相似文献