全文获取类型
收费全文 | 4654篇 |
免费 | 1109篇 |
国内免费 | 704篇 |
专业分类
化学 | 5820篇 |
晶体学 | 12篇 |
力学 | 82篇 |
综合类 | 10篇 |
数学 | 166篇 |
物理学 | 377篇 |
出版年
2024年 | 2篇 |
2023年 | 51篇 |
2022年 | 82篇 |
2021年 | 137篇 |
2020年 | 287篇 |
2019年 | 132篇 |
2018年 | 190篇 |
2017年 | 133篇 |
2016年 | 287篇 |
2015年 | 358篇 |
2014年 | 340篇 |
2013年 | 446篇 |
2012年 | 387篇 |
2011年 | 360篇 |
2010年 | 335篇 |
2009年 | 347篇 |
2008年 | 406篇 |
2007年 | 335篇 |
2006年 | 317篇 |
2005年 | 286篇 |
2004年 | 260篇 |
2003年 | 322篇 |
2002年 | 91篇 |
2001年 | 85篇 |
2000年 | 81篇 |
1999年 | 55篇 |
1998年 | 39篇 |
1997年 | 73篇 |
1996年 | 70篇 |
1995年 | 60篇 |
1994年 | 22篇 |
1993年 | 19篇 |
1992年 | 23篇 |
1991年 | 8篇 |
1990年 | 13篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1983年 | 4篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
排序方式: 共有6467条查询结果,搜索用时 15 毫秒
71.
Lennartson A Vestergren M Håkansson M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(6):1757-1762
The crystal structures of [Pr(dbm)3H2O] (1), [Sm(dbm)3H2O] (2), and [Er(dbm)3H2O] (3) have been determined (dbm=dibenzoylmethane). They display seven-coordinate propeller-shaped molecules, which are chiral and crystallize as conglomerates in space group R3. Analysis of the crystal structures reveals supramolecular interactions, including formation of a quadruple helix, which explain how stereochemical information can be transferred between stacks of molecules. A method to quantify the ee in bulk samples of stereochemically labile compounds by using solid-state CD spectroscopy is described. Using this method, it has been shown that compounds 1-3 undergo total spontaneous resolution directly after synthesis, forming a microcrystalline reaction product that is essentially enantiopure. The resolution of bulk quantities of seven-coordinate complexes (without chiral or polydentate ligands) is thus reported for the first time. Because the crystallization starts without seeding, the overall preparation may be regarded as absolute asymmetric synthesis. 相似文献
72.
手性胺醇稀土配合物的合成、荧光性质及其催化芳香酮的不对称氢化反应 总被引:2,自引:0,他引:2
合成了三种新的含C2-对称轴的手性胺醇(PhOHCHCH2)2NCH2C6H4R (R=OCH3, L1; R=CH3, L2; R=Cl, L3), 将其与无水氯化稀土LnCl3•4THF (Ln=La, Sm, Gd)反应生成了九个新的胺醇类稀土配合物LLnCl•2THF (L=L1, L2, L3; Ln=La, Sm, Gd). 用元素分析、热重分析、红外和紫外光谱等手段对它们进行了表征. 荧光光谱显示一些配合物具有荧光性能. 原位催化芳香酮的不对称氢化反应表明: L1/SmCl3•4THF体系催化苯乙酮不对称氢化反应的转化率达71%, 相应的对映体过量值达32%. 相似文献
73.
The first histidine catalyzed direct aldol reactions of ketones with nitrobenzaldehydes in water and in poly(ethylene glycol) (PEG) were reported. It reveals that histidine is a good aldol catalyst for synthesis of β-hydroxylketones in water and in PEG, giving good to excellent yields of the respective products. Better enantioand regioselectivity were achieved using low molecular weight PEG as the media. The results show that histidine and PEG-200 or -300 may constitute a promising environmentally benign system for asymmetric synthesis of β-hydroxylketones. 相似文献
74.
Teng-Kuei Yang Dong-Sheng Lee Tsung-Fan Teng Ting-Ting Jong Mei-Yueh Chien 《中国化学会会志》1991,38(4):401-403
Introducing two chiral auxiliaries, sulfoxide and menthol, into an acrylate would have either matched or mismatched pair systems. The presence of chiral menthol in α-sulfinylacrylates can change the diastereoselectivity from 24% d.e. to a single diastereomer by manipulation of the double asymmetric strategy. 相似文献
75.
A new method for the preparation of the synthon (±)-2,6,7,7a-tetrahydro-1β-hydroxy-4-formyl-7aβ-methylindene (1,a) for the
total synthesis of steroids in both (±) and (+) forms, starting from the known β-ketoester, (±)-methyl 1β-t-butoxy-5,6,7,7a-tetrahydro-7aβ-methyl-5-keto-4-indancarboxylate (2,a) has been described. An alternative route to (1,a) has
been investigated. Although the compound, (±)-1β-hydroxy-5,6,7,7a-tetrahydro-7aβ-methyl-5-keto-4-methoxymethylindan (2,b)
could not be prepared, interesting pathways leading to two unexpected products, (±)-5,6,7,7a-tetrahydro-4,7a-dimethyl-5H-indene-1,5-dione
and (±)-2,6-diketo-3-methyltricyclo-(5,2,1,0)decan-8-ol (3 and 4), were encountered during an attempted annelation reaction
of the ketone, N-diethylamino-5-methoxypentan-3-one (6), with 2-methylcyclopentan-1,3-dione (5). Trapping of the intermediate,
(±)-3a,4,5,6,7,7a-hexahydro-3a-hydroxy-4-methylene-7a-methylindene-1,5-dione (7), through the formation of the adduct, (±)-3a,4,5,6,7,7a-hexahydro-3a-hydroxy-4-(1′,
3′-diketo-2′-methylcyclopentano-2′-methylene)-7a-methylindene-1,5-dione (8), established the mechanism of the formation of
the products (3 and 4). 相似文献
76.
本文综述了近年来四氧化锇催化烯烃不对称双羟化及其反应机理的研究进展。Sharpless等对烯烃双羟化机理的透彻研究导致了不对称双羟化方法的优化。 相似文献
77.
Keum SR Roh HJ Choi YK Lim SS Kim SH Koh K 《Magnetic resonance in chemistry : MRC》2005,43(10):873-876
(1)H and (13)C NMR spectra of symmetric and asymmetric bis-spiropyrans, Series 1-3, were completely assigned. Especially, the (1)H assignment of asymmetric spiropyrans was achieved by utilizing (1)H-(1)H COSY and nOe experiments. All of the carbons in the dye molecules were investigated through a combination of heteronuclear 2D-shift correlation spectroscopy (HETCOR), together with an attached proton test (APT). 相似文献
78.
The asymmetric 1,2-addition of trimethylsilyl cyanide to aldehyde SAMP-hydrazones in the presence of titanium tetrachloride and diethylether in dichloromethane at −100°C up to room temperature, removal of the chiral auxiliary and acid hydrolysis affords α-amino acids in high enantiomeric excesses (ee=94-97%). 相似文献
79.
80.