全文获取类型
收费全文 | 2953篇 |
免费 | 70篇 |
国内免费 | 288篇 |
专业分类
化学 | 2898篇 |
晶体学 | 18篇 |
力学 | 5篇 |
综合类 | 1篇 |
数学 | 19篇 |
物理学 | 370篇 |
出版年
2024年 | 13篇 |
2023年 | 91篇 |
2022年 | 13篇 |
2021年 | 33篇 |
2020年 | 38篇 |
2019年 | 75篇 |
2018年 | 68篇 |
2017年 | 76篇 |
2016年 | 75篇 |
2015年 | 68篇 |
2014年 | 112篇 |
2013年 | 181篇 |
2012年 | 127篇 |
2011年 | 183篇 |
2010年 | 157篇 |
2009年 | 200篇 |
2008年 | 166篇 |
2007年 | 212篇 |
2006年 | 215篇 |
2005年 | 237篇 |
2004年 | 220篇 |
2003年 | 92篇 |
2002年 | 55篇 |
2001年 | 74篇 |
2000年 | 78篇 |
1999年 | 54篇 |
1998年 | 54篇 |
1997年 | 45篇 |
1996年 | 44篇 |
1995年 | 43篇 |
1994年 | 30篇 |
1993年 | 29篇 |
1992年 | 24篇 |
1991年 | 27篇 |
1990年 | 26篇 |
1989年 | 9篇 |
1988年 | 15篇 |
1987年 | 12篇 |
1986年 | 11篇 |
1985年 | 3篇 |
1984年 | 10篇 |
1983年 | 1篇 |
1982年 | 4篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有3311条查询结果,搜索用时 15 毫秒
81.
Application of mono (6A-N-ethylenediamine-6A-deoxy) perphenylcarbamoylated β-cyclodextrin (β-CD) bonded stationary phase (CSP) in micro-high performance liquid chromatography (micro-HPLC) and pressurized capillary electrochromatography (p-CEC) was firstly presented. A series of racemic α-amidophosphonates were resolved in reversed- and normal-phase modes on this CSP. The investigated chromatographic parameters include retention factor (k′), separation factor (α) and resolution (Rs) of solutes. In addition, the structural variation of the solutes and the experimental factors affecting chiral separations have been examined, including the percentage of alcohol modifier, the linear velocity (u) of the mobile phase, electrical field strength, etc. Baseline separation was achieved for most of the entities. Hydrophobic interaction, steric effect and π-π interaction contribute to the possible mechanism. Comparative results indicate that higher Rs value up to 3.1 was found in micro-HPLC, higher efficiency up to 29,970 in p-CEC. 相似文献
82.
Lämmerhofer M 《Journal of chromatography. A》2005,1068(1):3-30
Enantiomer separations by CE employing nonaqueous conditions are reviewed. The general focus of this article is directed towards solvent effects on chiral recognition and the separation mechanism. After a general discussion of solvent effects on the individual processes involved in CE enantiomer separation, specifics for various selector classes are discussed together with a few applications of enantioselective nonaqueous CE. 相似文献
83.
Mercedes Amat Marta Huguet Oriol Bassas Joan Bosch Josefa Badia Juan Aguilar 《Tetrahedron letters》2004,45(28):5355-5358
Cyclocondensation of (R)-phenylglycinol with appropriately γ-substituted δ-oxo acid derivatives provides bicyclic lactams from which the enantioselective synthesis of 1-deoxy-d-gulonojirimycin has been reported. 相似文献
84.
在Pd(PPh3)4催化下,将单体(S)-6,6′-二溴-2,2′-二正丁氧基-1,1′-联萘[(S)-M-1]和(R)-6,6′-二溴-2,2′-二正丁氧基-1,1′-联萘[(R)-M-1]分别与2,5-二(4-三正丁基锡基苯)-1,3,4-噁二唑(M-2)通过Stille交叉耦合反应合成了手性高分子P-1与P-2,并用1HNMR、13CNMR、FTIR、UV、热分析、荧光光谱、GPC和CD等分析方法进行了表征.手性高分子P-1和P-2都能发射较强的蓝色荧光;在高分子侧链上引入丁氧基后使得手性高分子的溶解性能增强,并具有良好的成膜性能;在高分子主链引入亲电子的噁二唑生色团能使其特别适合于作为空穴电子传输层,对氧和热特别稳定,是一类潜在的光电高分子材料. 相似文献
85.
三菲咯啉合铁手性配合物键合DNA的立体选择性 总被引:2,自引:1,他引:2
应用光谱法研究了手性金属配合物[Fe(phen)3]^2+与小牛胸腺DNA的作用,确定了△型异构体对B型右手螺旋DNA有优先键合的立体选择性。 相似文献
86.
88.
Gengliang Yang Zhiwei Li Dexian Wang Zhefeng Zhang Erdong Liu Yi Chen 《Chromatographia》2002,56(7-8):515-518
Summary A high-performance liquid chromatographic method was developed for the chiral separation of a new anti-diabetic agent, N-(trans-4-isopropylcyclohexylcarbonyl)-D-phenylalanine,
and its L-enantiomer. The separation was performed on a Sumichiral OA-3300 column. Optimized mobile phase was 0.025 mol.L−1 ammonium acetate in methanol solution. UV detection was at 210 nm. Baseline chiral separation was obtained within 12 minutes.
The detection limits are 80 pg for the D-enantiomer and 120 pg for the L-enantiomer. RSD of the method was below 1% (n=5). 相似文献
89.
使用手性冠醚及手性柱的HPCE和HPLC法拆分伯胺类药物对映体的对比研究 总被引:3,自引:0,他引:3
报道了在缓冲液中添加 1 8-冠 - 6 -四甲酸 (1 8C6 H4 )的高效毛细管电泳法(HPCE)对 8个含氨基的药物进行拆分 ,低 p H值 (2 .0 6 )和较高浓度的 Tris缓冲液(2 0 mmol· L- 1)可加快手性分离。用手性柱 Crownpak CR(+)的高效液相色谱(HPLC)法对与前相同的 8个含氨基药物进行拆分 ,甲醇浓度增大 ,分离度 RS值有所减小。实验结果还表明 ,使用 HPCE法拆分的各物质 RS值大于使用 HPLC法拆分相应物质的 RS值。 相似文献
90.
The structure and phase behavior of liquid crystalline polymers (LCPs) having a common chiral side chain mesogen but different main chain structures have been investigated using small-angle X-ray scattering (SAXS). While the low molecular weight chiral side chain mesogen by itself exhibits ferroelectricity, the SAXS data of the side chain LCP with a flexible polyacrylate backbone contains a bilayered superstructure peak that is indicative of antiferroelectric order. The combined LCP with a nonpolar main chain mesogen also has a bilayered superstructure, but has a different structural organization in the proposed antiferroelectric phase compared to the side chain LCP. Further changes in the phase behavior and structural organization occur when a polar group is introduced into the main chain mesogen. A ferrielectric phase has been proposed to explain the observation of a trilayered superstructure in the corresponding SAXS data. The influence of the chemical structure and connectivity on the phase behavior and superstructure formation in the chiral LCPs is discussed. 相似文献