全文获取类型
收费全文 | 1735篇 |
免费 | 209篇 |
国内免费 | 171篇 |
专业分类
化学 | 1208篇 |
晶体学 | 19篇 |
力学 | 133篇 |
综合类 | 12篇 |
数学 | 187篇 |
物理学 | 556篇 |
出版年
2024年 | 9篇 |
2023年 | 49篇 |
2022年 | 78篇 |
2021年 | 85篇 |
2020年 | 93篇 |
2019年 | 77篇 |
2018年 | 68篇 |
2017年 | 70篇 |
2016年 | 91篇 |
2015年 | 71篇 |
2014年 | 100篇 |
2013年 | 121篇 |
2012年 | 163篇 |
2011年 | 148篇 |
2010年 | 86篇 |
2009年 | 69篇 |
2008年 | 94篇 |
2007年 | 106篇 |
2006年 | 92篇 |
2005年 | 73篇 |
2004年 | 41篇 |
2003年 | 42篇 |
2002年 | 34篇 |
2001年 | 36篇 |
2000年 | 30篇 |
1999年 | 26篇 |
1998年 | 15篇 |
1997年 | 17篇 |
1996年 | 28篇 |
1995年 | 11篇 |
1994年 | 16篇 |
1993年 | 10篇 |
1992年 | 20篇 |
1991年 | 10篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1986年 | 8篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1970年 | 1篇 |
1965年 | 1篇 |
1958年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有2115条查询结果,搜索用时 0 毫秒
1.
Li Jun Zheng Dayong Wei Ning Sun Yunfeng Liu Li Yuan Yuan Jiang Qinghua 《Chemistry of Natural Compounds》2022,58(4):650-652
Chemistry of Natural Compounds - A new quassinoid, dehydrobruceantinol B (1), was isolated from the seeds of Brucea javanica, together with two known compounds, bruceantinol (2) and bruceine A (3).... 相似文献
2.
Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(iPrNPMe2)3Fe–PMe3, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(iPrNPMe2)3Fe–PMe3 can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(iPrNPMe2)3Fe–PMe3 to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(iPrNPMe2)3Fe–PMe3 is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(iPrNPMe2)3Fe–PMe3 moves from niobium to iron. 相似文献
3.
4.
三(2-苯并咪唑亚甲基)胺硝酸镍(Ⅱ)配合物的合成及结构 总被引:5,自引:0,他引:5
三(2-苯并咪唑亚甲基)胺简称NTB与Ni(Ⅱ)的硝酸盐形成配合物C28H35N9O9S2Ni。本文报道其合成,红外光谱及晶体结构。该化合物为三斜晶系,空间P1↑-,a=9.650(3),b=12.716(2),c=14.436A,α=11.46(2),β=91.66(3),γ=97.55(2)°,V=1718(2)A^3,Z=2,F(000)=793,Dc=1.48g/cm^3,Mr=764.1 相似文献
5.
A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo. 相似文献
6.
7.
The mercuration of a series of aryliminomethylferrocenes occurred predominantly in an ortho-position of the substituted ferrocenyl ring to yield 2-mercurated ferrocenylimines. The regiospecificity of this reaction suggests that the mercury is directed into the ortho-position by coordination of the mercury to imino nitrogen with subsequent electrophilic substitution. The chromatographic and spectral properties of the 2-mercurated products show the presence of an intramolecular N → Hg coordination via the five-membered ring in these molecules, which was further confirmed by the single-crystal structure analysis of 2-chloromercuro-1-[(4-methoxyphenylimino)methyl]ferrocene. 相似文献
8.
Hu Y Houk KN Kikuchi K Hotta K Hilvert D 《Journal of the American Chemical Society》2004,126(26):8197-8205
The mechanisms by which solvents, antibodies, and albumins influence the rates of base-catalyzed reactions of benzisoxazoles have been explored theoretically. New experimental data on substituent effects and rates of reactions in several solvents, in an antibody, and in an albumin are reported. Quantum mechanical calculations were carried out for the reactions in water and acetonitrile, and docking of the transition state into a homology model of antibody 34E4 and an X-ray structure of human serum albumin was accomplished. A microenvironment made up of catalytic polar groups (glutamate in antibody 34E4 and lysine in human serum albumin) surrounded by relatively nonpolar groups is present in both catalytic proteins. 相似文献
9.
用套索冠醚N,N′-双(2-甲基吡啶)-二氮杂-18-冠-6作为固定相,涂渍在弹性石英毛细管内,测其柱效、惰性、热稳定性、平均极性及选择性等性质.其结构由元素分析、红外光谱、核磁共振及质谱分析的试验数据所证实.试验表明,它具有良好的色谱性能、中等极性,适用于对醇、卤代烃、芳香烃等各类异构体的分离,并用分子结构观点探讨了保留机理. 相似文献
10.
Ujaque G Tantillo DJ Hu Y Houk KN Hotta K Hilvert D 《Journal of computational chemistry》2003,24(1):98-110
Antibody 21D8 catalyzes the decarboxylation of 5-nitro-3-carboxybenzisoxazole. The hapten used was designed to induce an antibody binding site with anion binders for the carboxylate, plus a nonpolar environment to accelerate decarboxylation. A recent X-ray crystal structure of 21D8 has shown that the binding pocket contains an array of both polar and charged residues. Nevertheless, 21D8 is able to catalyze a reaction that involves a decrease in polarity from reactant to transition state. The origins of this phenomenon were explored using various computational strategies-quantum mechanics, theozyme models, docking, molecular dynamics, free energy perturbation, and linear interaction energy-the combination of which has produced a consistent picture of catalysis. By partially desolvating the charged carboxylate, 21D8 manages to effect "catalysis on the coastline," without burying the carboxylate in a nonpolar region of the binding pocket. The results have implications for that broad class of enzyme and antibody catalyzed reactions that involve the conversion of a substrate with a relatively localized charge into a transition state with a highly dispersed charge. 相似文献