全文获取类型
收费全文 | 931篇 |
免费 | 23篇 |
国内免费 | 241篇 |
专业分类
化学 | 980篇 |
力学 | 29篇 |
综合类 | 1篇 |
数学 | 28篇 |
物理学 | 157篇 |
出版年
2024年 | 10篇 |
2023年 | 74篇 |
2022年 | 23篇 |
2021年 | 29篇 |
2020年 | 34篇 |
2019年 | 30篇 |
2018年 | 21篇 |
2017年 | 26篇 |
2016年 | 20篇 |
2015年 | 26篇 |
2014年 | 29篇 |
2013年 | 70篇 |
2012年 | 45篇 |
2011年 | 56篇 |
2010年 | 38篇 |
2009年 | 50篇 |
2008年 | 60篇 |
2007年 | 70篇 |
2006年 | 58篇 |
2005年 | 62篇 |
2004年 | 48篇 |
2003年 | 33篇 |
2002年 | 32篇 |
2001年 | 25篇 |
2000年 | 38篇 |
1999年 | 22篇 |
1998年 | 11篇 |
1997年 | 15篇 |
1996年 | 18篇 |
1995年 | 17篇 |
1994年 | 14篇 |
1993年 | 12篇 |
1992年 | 10篇 |
1991年 | 20篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1988年 | 14篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 1篇 |
排序方式: 共有1195条查询结果,搜索用时 15 毫秒
91.
92.
93.
94.
A. G. Taranto J. W. de M. Carneiro F. G. de Oliveira M. T. de Araujo C. R. Correa 《Journal of Molecular Structure》2002,580(1-3):207-215
Artemisinin is a sesquiterpene lactone with an endoperoxide function that is essential for its antimalarial activity. Endoperoxides are supposed to act on heme leading to the reduction of the peroxide bond and production of radicals, which can be responsible for killing the parasite. The geometries of artemisinin, radical anions and neutral species generated by rearrangement after reduction of the peroxide bond were fully optimized with the AM1 and PM3 semi-empirical methods, in order to characterize the intermediates formed during the process. Among the radicals calculated along the pathway for reductive decomposition of artemisinin, the secondary radical centered on carbon C4 has the highest stability when compared to other radicals that can be achieved either by hydrogen migration to the original O-centered radical or by homolytic break of C–C bond. This suggests that the C4-centered radical may be the species responsible for killing the parasite, as has been indicated previously in experimental studies. 相似文献
95.
Zhonghua Ji Jingjian Li Gu Yuan Shengmin Cai Jia Liu Chang Liu 《Journal of Electroanalytical Chemistry》2004,570(2):265-273
Polyamides containing N-methyl pyrroles and N-methyl imidazoles are a type of small molecule that can bind and recognize the bases of DNA with high affinity and specificity. Five polyamides were studied at glassy carbon electrode in acetate buffer by cyclic and differential pulse voltammetry to clarify their redox pathways. The polyamide electrochemical responses are compared by peak currents and peak potentials. The slopes of the three anodic Ep vs. pH plots of a typical polyamide are linear and show 0.059, 0.057, 0.056 V per pH in acid media, respectively, which correspond to a mechanism involving the equal number of electrons and protons. A possible mechanism for the redox pathway of various polyamides is proposed: the oxidation product of imidazole ring is acylamide and the results of in situ UV–Vis spectroscopy at Pt web electrode support the proposed mechanism. electrospray ionization mass spectroscopy (ESI-MS) indicates that one or two oxygen atoms are added into polyamide molecule after electrochemical oxidation. 相似文献
96.
By controlling the amount of catalyst 1-methyl-3-(2-(sulfooxy)ethyl)-1H-imidazol-3-ium chloride, two new intermediates of Tröger's bases (11, 1,6-dimethyl-3-(4-methylphenyl)-1,4-dihydroquinazolin-3-ium tetrafluoroborate and 12, 8-methyl-2,5-bis-(4-methylphenyl)-3,5,6,7-tetrahydropyrimido[5,6,1-ij]quinazoline-2-ium tetrafluoroborate) were simply obtained from the one-pot reaction of aromatic amine and formaldehyde in ionic liquid at ambient temperature. These results support the mechanism for Tröger's base formation supposed by Fernando Coelho and co-workers. However, the crystal structure of 12 and correlative quantum chemistry calculation results are not reconciled with their report. 相似文献
97.
The oxidative cleavage of the known anti-psoriasis drug 1 to give 2 has been reported previously. Due to the importance of accessing medium-sized ring containing systems via oxidative cleavage, this reaction has been revisited revealing additional information about the structure of 2. Alternative reaction products were identified when the reaction was carried out in the presence of water. The conversion of 1 to 2 has also been carried out using ruthenium tetroxide. A detailed variable temperature NMR and computational study of the restricted rotation of the N-aryl ring in 2 is presented. 相似文献
98.
密闭系统中微波辅助萃取机制探讨 总被引:9,自引:2,他引:9
通过与普通加热萃取虎杖中白藜芦醇的产率进行对比 ,对密闭系统中微波辅助萃取的机理进行了探讨。结果表明 ,微波辅助萃取与普通加热萃取二者的活化能相差不大 ,分别为30.06和30.32kJ·mol-1。但微波辅助萃取的表观速率常数约是普通加热萃取的20倍。并且还利用电子扫描显微镜对样品微结构进行了观察 ,研究表明 ,细胞内极性成分如水吸收了微波能后压力迅速增加导致细胞结构的破坏是MAE快速高效的关键 ,由于细胞的破坏 ,萃取剂和萃取目标化合物更容易通过细胞壁 ,加速了扩散速度 ,进而加速了萃取速度。 相似文献
99.
100.
SHI Zuoqing XU Mancai LIN Xue XU Mingcheng FAN Yunge SHI Rongfu YANG Yizhong HE Binglin 《Chinese Journal of Reactive Polymers》2000,(1)
1 INTRODUCTIONPhenol and many substitUted phenols, such as nitrophenols, chlorophenols and aminophenolset al, are the common organic pollutantS existing in wane water of many chemical plants.Treatment of the wastewater containing phenols is an important project for environmentprotection and has been studied by various methods, such as dialysis ['l, microbial degradation ['1,oxidation l'l, extracting with solvents I4] and adsorption with polymeric adsorbents IS]. Theadsorption method is v… 相似文献