全文获取类型
收费全文 | 934篇 |
免费 | 56篇 |
国内免费 | 1篇 |
专业分类
化学 | 816篇 |
晶体学 | 4篇 |
力学 | 12篇 |
数学 | 42篇 |
物理学 | 117篇 |
出版年
2023年 | 13篇 |
2022年 | 34篇 |
2021年 | 28篇 |
2020年 | 24篇 |
2019年 | 32篇 |
2018年 | 21篇 |
2017年 | 7篇 |
2016年 | 31篇 |
2015年 | 40篇 |
2014年 | 36篇 |
2013年 | 54篇 |
2012年 | 90篇 |
2011年 | 78篇 |
2010年 | 37篇 |
2009年 | 36篇 |
2008年 | 44篇 |
2007年 | 32篇 |
2006年 | 49篇 |
2005年 | 33篇 |
2004年 | 32篇 |
2003年 | 13篇 |
2002年 | 14篇 |
2001年 | 13篇 |
2000年 | 14篇 |
1999年 | 13篇 |
1998年 | 16篇 |
1997年 | 8篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 12篇 |
1992年 | 15篇 |
1991年 | 11篇 |
1990年 | 7篇 |
1989年 | 12篇 |
1988年 | 7篇 |
1987年 | 5篇 |
1986年 | 11篇 |
1985年 | 7篇 |
1982年 | 4篇 |
1980年 | 5篇 |
1979年 | 2篇 |
1978年 | 6篇 |
1977年 | 4篇 |
1975年 | 2篇 |
1972年 | 2篇 |
1958年 | 1篇 |
1943年 | 1篇 |
1937年 | 2篇 |
1936年 | 4篇 |
排序方式: 共有991条查询结果,搜索用时 15 毫秒
1.
Vanessa R. Machado Louis P. Sandjo Giovanni L. Pinheiro Milene H. Moraes Mario Steindel Moacir G. Pizzolatti 《Natural product research》2018,32(3):275-281
The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by 1H NMR, 13C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC50 = 12.48 μg/mL) and the lowest cytotoxic derivative (CC50 = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase. 相似文献
2.
Christoph Elschenbroich Jrn Plackmeyer Klaus Harms Olaf Burghaus Jürgen Pebler 《无机化学与普通化学杂志》2006,632(5):819-827
Trovacene Chemistry. 13 [1] On Being Lead and Mislead in the Synthesis of Di([5]trovacenyl)ketone Di([5]trovacenyl)ketone ( 3¨ ) has been prepared from lithio‐[5]trovacene and dimethylcarbamoyl chloride and studied by X‐ray diffraction, cyclic voltammetry, magnetic susceptometry and EPR spectroscopy. Slight variation of the synthetic protocol affords an unusual trinuclear complex 5 ? that is also fully characterized. Spin‐spin exchange interaction is smaller in 3¨ than in 1,1‐di([5]trovacenylethene ( 2¨ ), which differs from 3¨ by a replacement of O for CH2. The novel trinuclear complex 5 ? , however, displays exchange coupling very similar to that observed in 1‐methoxy‐2,5,6‐tri([5]trovacenyl)benzene ( 7 ? ). In both cases, an unsymmetrical triangular arrangement of S = 1/2 centers is encountered. These findings are discussed in terms of the nature of the respective spacers. 相似文献
3.
4.
5.
6.
7.
H. F. Kauffmann H. Harms O. F. Olaj 《Journal of polymer science. Part A, Polymer chemistry》1982,20(10):2943-2967
α-Methylstyrene (α-Me-St) in bulk undergoes a variety of thermally induced processes which we investigated in detail by product-distribution analysis. The oligomeric products, shown by GC–MS coupling techniques and independent syntheses, consisted of nine dimers and nine trimers with no detectable higher oligomers or polymers. Two isomeric cyclobutanes and one of the open-chain unsaturated dimers were formed by a conventional two-step cycloaddition; a Flory-type diradical was the common intermediate. In contrast to these 2π + 2π products, the majority of the remaining oligomers could not be interpreted on the basis of π-electron interaction between closed shell molecules. Their structures, however, were compatible with a free radical process in which cumyl(MH·) and 1,4-dimethyl-1-phenyl-tetrahydronaphthalene-yl(THN·), which are consecutive products of 4π + 2π and 2π + 2π interactions, respectively, were involved in addition and transfer reactions. Because of the small rate of initiation and the obvious lack of free radical recombination products, a mechanism was suggested in which MH· and THN· radicals react predominantly in a closed sequence of elementary processes and to a rather small extent only by bimolecular free radical termination. Two sorts of stabilization steps, hydrogen transfer to monomer (RnH· + M → Rn + MH·) and hydrogen abstraction from a hypothetical 4π + 2π intermediate I (RnH· + I → RnH2 + THN·), are attributed to the high rates of unsaturated and saturated oligomer formation. 相似文献
8.
The performance of single-drop microextraction (SDME), coupled with gas chromatography/mass spectrometry, was assessed for the determination of tributyltin compounds in water and solid samples. Experimental parameters impacting the performance of SDME, such as microextraction solvent and sampling and stirring time, were investigated. Analytical results obtained by SDME were compared with those generated by conventional solid phase microextraction (SPME) and liquid-liquid extraction (LLE) for the determination of TBT in PACS-2 sediment certified reference material (CRM). 相似文献
9.
Martin R. Bryce Peter J. Skabara Adrian J. Moore Andrei S. Batsanov Judith A.K. Howard Vanessa J. Hoy 《Tetrahedron》1997,53(52):1002-17794
Reactions of tetrathiafulvalenyllithium (TTF-Li) with a range of aldehydes and ketones have been explored for the first time, to provide an efficient route to mono-functionalised TTF derivatives of general formulae TTF-CH(OH)R (R = alkyl, phenyl, tetrathiafulvalenyl and ferrocenyl) and TTF-CR(OH)R′ (R = alkyl, phenyl, R′ = alkyl, phenyl, tetrathiafulvalenyl, ferrocenyl, and R-R′ = fluorenyl). Subsequent transformations involving the reactive alcohol group of some of these compounds are reported. The structures of the three title compounds have been established by single-crystal X-ray analysis. 相似文献
10.
Comparison between capillary electrophoresis and ion-chromatography for analysis of inorganic anions
Separation and detection of some selected inorganic anions with capillary electrophoresis are shown. The anions are separated in microbore capillaries (25 m* 0.2 m) and detected with a UV-detector. Results are compared with the method of ion exchange chromatography. In consideration of the most important physical and chemical parameters an easy kind of computer simulation for such electropherograms was developed.To get optimal results of separation and UV-detection in capillary electrophoresis some parameters of the device HPE 100, i.e. loading time in the electrokinetic sample injection mode and the running voltage are varied. The behaviour of absorption in the UV region of the chosen anions as well as the influence of pH values in retention behaviour are investigated. There is a simple way to calculate the electrophoretic mobilities from known retention times. Approximate limits of detection for all anions and for each technique are given. 相似文献