全文获取类型
收费全文 | 3762篇 |
免费 | 624篇 |
国内免费 | 545篇 |
学科分类
数理化 | 4931篇 |
出版年
2024年 | 2篇 |
2023年 | 63篇 |
2022年 | 81篇 |
2021年 | 109篇 |
2020年 | 148篇 |
2019年 | 149篇 |
2018年 | 142篇 |
2017年 | 116篇 |
2016年 | 157篇 |
2015年 | 177篇 |
2014年 | 186篇 |
2013年 | 263篇 |
2012年 | 301篇 |
2011年 | 351篇 |
2010年 | 232篇 |
2009年 | 214篇 |
2008年 | 279篇 |
2007年 | 189篇 |
2006年 | 188篇 |
2005年 | 178篇 |
2004年 | 157篇 |
2003年 | 158篇 |
2002年 | 192篇 |
2001年 | 159篇 |
2000年 | 110篇 |
1999年 | 90篇 |
1998年 | 73篇 |
1997年 | 45篇 |
1996年 | 91篇 |
1995年 | 68篇 |
1994年 | 49篇 |
1993年 | 31篇 |
1992年 | 30篇 |
1991年 | 30篇 |
1990年 | 28篇 |
1989年 | 16篇 |
1988年 | 14篇 |
1987年 | 15篇 |
1986年 | 9篇 |
1985年 | 15篇 |
1984年 | 3篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1974年 | 1篇 |
1957年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有4931条查询结果,搜索用时 31 毫秒
41.
Bakhtar Ullah Yuli Zhou Jingwen Chen Zongbi Bao Yiwen Yang Qiwei Yang Qilong Ren Zhiguo Zhang 《Tetrahedron letters》2019,60(4):348-351
Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N-aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experimental investigations demonstrated that thiourea acts as a radical initiator by abstracting hydroxyl radical (OH) from tert-butyl hydroperoxide (TBHP) directly instead of non-covalent hydrogen bondings (H-bondings) activation. The use of thiourea as a radical initiator offers a new avenue for innovative chemical transformations in organocatalyzed radical chemistry. 相似文献
42.
采用温和条件下的溶胶-凝胶技术,成功制备了阴离子交换-反相混合模式硅胶基质毛细管电色谱整体柱.通过调整反应液中不同前体的比例,优化了整体柱的制备条件.通过扫瞄电镜,对柱床进行了表征和分析.实验发现,所制备的整体柱电渗流的方向和大小可随流动相pH值的改变而改变,在酸性和中性条件下,具有从阴极流向阳极的电渗流;当流动相pH值升至约7.5时,电渗流方向发生了反转(由阳极流向阴极).在优化的实验条件下,用所制备的整体柱对所考察的酸性(中性)化合物实现了快速分离,并获得了高达160,000 N/m的柱效. 相似文献
43.
Guo Hua GAO Jin Bao GAO Wen Juan ZHOU Liang LU Ming Yuan HE 《中国化学快报》2006,17(10):1293-1296
Since much more attention has been paid to the sustainable development, many researchers try to improve conventional chemical process and find new and more, environmentally friendly routes1. Aqueous-phase reactions are of interest as environ- mentally ben… 相似文献
44.
A New Asterosaponin from the Starfish Culcita novaeguineae 总被引:1,自引:0,他引:1
HaiFengTANG YangHuaYI LingLI PengSUN DaZhengZHOU BaoShuLIU 《中国化学快报》2005,16(5):619-622
A new asterosaponin named novaeguinoside A, along with a known saponin, asteronyl pentaglycoside sulfate, was isolated from the starfish Culcita novaeguineae. The new compound was identitied to be sodium 6α-O-{β-D-fucopyranosyl-(1→2)-β-D-fucopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-xylopyranosyl-(1→3)-[β-D-quinovopyranosyl}-5α-pregn-9(11)-en-20-one-3β-yl-sulfate by extensive spectral analysis and chemical evidence. 相似文献
45.
46.
47.
Determination of Gossypol in Trace Level by Flow Injection Analysis with Chemiluminescence Detection
Bing Chun XUE Er Bao LIU College of Chemistry Life Sciences Tianjin Normal University Tianjin 《中国化学快报》2006,17(1):57-60
Gossypol, [1, 1′, 6, 6′, 7,7′-hexahydroxyl-5,5′-diisopropyl-3,3′-dimethyl-(2,2′-binaphtha- lene)-8,8′-dicarboxaldehyde] is a polyphenolic yellow compound naturally occurring in various parts of cotton plants1. The compound has been associated with 相似文献
48.
Hu H Qiao M Xie F Fan K Lei H Tan D Bao X Lin H Zong B Zhang X 《The journal of physical chemistry. B》2005,109(11):5186-5192
The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface. 相似文献
49.
In the present paper, we describe a microfluidics-based sensing system for nonelectroactive anions under negative separation electric field by mounting a single carbon fiber disk working electrode (WE) in the end part of a poly(dimethylsiloxane) microchannel. In contrast to work in a positive separation electric field described in our previous paper (Anal. Chem. 2004, 76, 6902-6907), here the electrochemical reduction reaction at the WE is not coupled with the separation high-voltage (HV) system, whereas the electrochemical oxidation reaction at the WE is coupled with the separation HV system. The electroactive indicator is the carbon fiber WE itself but not dissolved oxygen. This provides a convenient and sensitive means for the determination of nonelectroactive anions by amperometry. The influences of separation voltage, detection potential, and the distance between the WE and the separation channel outlet on the response of the detector have been investigated. The present detection mode is successfully used to electrochemically detect F-, Cl-, SO4(2-), CH3COO-, H2PO4-. Based on the preliminary results, a detection limit of 2 microM and a dynamic range up to three orders of magnitude for Cl- could be achieved. 相似文献
50.