全文获取类型
收费全文 | 671篇 |
免费 | 29篇 |
国内免费 | 2篇 |
专业分类
化学 | 543篇 |
力学 | 2篇 |
数学 | 72篇 |
物理学 | 85篇 |
出版年
2023年 | 10篇 |
2022年 | 15篇 |
2021年 | 34篇 |
2020年 | 23篇 |
2019年 | 15篇 |
2018年 | 10篇 |
2017年 | 10篇 |
2016年 | 30篇 |
2015年 | 29篇 |
2014年 | 29篇 |
2013年 | 38篇 |
2012年 | 68篇 |
2011年 | 61篇 |
2010年 | 17篇 |
2009年 | 23篇 |
2008年 | 43篇 |
2007年 | 48篇 |
2006年 | 43篇 |
2005年 | 28篇 |
2004年 | 29篇 |
2003年 | 14篇 |
2002年 | 24篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1979年 | 2篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1969年 | 1篇 |
1967年 | 1篇 |
1908年 | 1篇 |
排序方式: 共有702条查询结果,搜索用时 15 毫秒
81.
82.
Fernando Montanari 《Tetrahedron letters》1979,20(52):5055-5058
The presence of the hydroxymethyl group allows facile functionalisation of 18-crown-6 and of [2.2.2]cryptand. A variety of lipophilic and polymer-supported macrocyclic polyethers is thus available. They are efficient and easily recyclable phase-transfer catalysts. 相似文献
83.
84.
85.
Kretz T Bats JW Losi S Wolf B Lerner HW Lang M Zanello P Wagner M 《Dalton transactions (Cambridge, England : 2003)》2006,(41):4914-4921
Cationic dinuclear Cu(II) complexes 3 and 4 have been prepared using the novel hydroquinone-based imine chelators 2,5-((i)Pr(2)NCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (1) and 2,5-(pyCH(2)CH(2)N[double bond, length as m-dash]CH)(2)-1,4-(OH)(2)-C(6)H(2) (2), respectively (py = 2-pyridyl). X-Ray quality crystals of both complexes were grown from their DMF solutions. The sterically more encumbered compound crystallizes in the form of discrete dinuclear entities with Cu(II) centres in a distorted square-planar ligand environment (one coordination site is occupied by a DMF molecule). The pyridyl derivative 4 features dinuclear hydroquinone-bridged subunits similar to 3. However, the Cu(II) ions are now six-coordinate with two DMF molecules at an axial and an equatorial position of a Jahn-Teller-distorted octahedron. Moreover, the dinuclear subunits are no longer isolated but linked with each other via bridging hydroquinone oxygen atoms which occupy the second apical position of each octahedron. The structure suggests that the magnetic properties of the resulting coordination polymer of 4 could be described by a model valid for dimerized spin chains. As a result of this analysis the antiferromagnetic coupling constants J(1)/k(B) = 9.9 K (intradimer) and J(2)/k(B) = 0.9 K (interdimer) are obtained. Both in 3 and in 4, the hydroquinone --> semiquinone transition of the central bridging unit (E degrees ' = + 0.57 V, 3; E degrees ' = + 0.51 V, 4; DMF; vs. SCE) displays features of chemical reversibility. In the case of , reduction of Cu(II) centres requires a peak potential of E(p) = - 0.42 V. 相似文献
86.
Tebben L Neumann M Kehr G Fröhlich R Erker G Losi S Zanello P 《Dalton transactions (Cambridge, England : 2003)》2006,(14):1715-1720
[3]Ferrocenophanone rac-8 was prepared by several non-Friedel-Crafts pathways starting from a Mannich-type coupling of 1,1'-diacetylferrocene followed by catalytic hydrogenation. Hydride abstraction from the resulting alpha-dimethylamino[3]ferrocenophane rac-14 with B(C6F5)3 followed by hydrolysis gave the ketone rac-8. Several variants of the Sommelet reaction, using ethylglyoxylate, formaldehyde or hexamethylenetetramine (urotropine) as the "oxidizing" reagent gave the alpha-[3]ferrocenophanone 8 in good to excellent yield. Some variants of these reactions were also used for the preparation of the pure enantiomer (R)-8. The electrochemical behaviour of 8 has been investigated and compared with related derivatives. 相似文献
87.
Corr SA O'Byrne A Gun'ko YK Ghosh S Brougham DF Mitchell S Volkov Y Prina-Mello A 《Chemical communications (Cambridge, England)》2006,(43):4474-4476
Fluorescent magnetite nanocomposites based on magnetic nanoparticles, a polyhedral octaaminopropylsilsesquioxane and a porphyrin derivative have been prepared. The intracellular uptake of the nanocomposites by macrophage and bone osteoblast cells, and their potential as MRI contrast agents, has been demonstrated. 相似文献
88.
Valli L Casilli S Giotta L Pignataro B Conoci S Borovkov VV Inoue Y Sortino S 《The journal of physical chemistry. B》2006,110(10):4691-4698
This work reports on the structural and spectroscopic properties of ethane-bridged Zn porphyrin dimers (1) in Langmuir-Sch?fer (LS) thin films by combining scanning force microscopy (SFM) with film balance, UV-vis absorption, fluorescence, and nanosecond laser flash photolysis measurements. Results show that depending on the surface pressure the Langmuir films of pure 1 can be arranged in two different condensed phases, whereas SFM of the LS films shows characteristic fractal networks constituted by nanoscopic aggregates. The spectral findings agree with a picture in which 1 is apparently present in the anti conformation but aggregated in a sort of H-type structure whose optical features resemble those of the syn conformer. This type of structure is not responsive to light stimuli. By diluting 1 in arachidic acid the porphyrin aggregation is significantly minimized with 1 exhibiting almost exclusively the anti conformation. As a result the LS films become photoresponsive, showing fluorescence emission and triplet-triplet transient absorption. 相似文献
89.
John Bargar Serena DeBeer George Hendrik Ohldag Gordon Brown 《Synchrotron Radiation News》2013,26(2):22-24
Scanning transmission X-ray microscopy (STXM) has emerged as an important technique for chemical imaging and spectromicroscopy on the <100nm spatial scale in the environmental, geological, and biomedical sciences. Much has transpired technologically and scientifically in the 20-plus year interval that zone-plate STXM technology has been in development. Yet STXM/nanoprobe facilities are few in number, beam time remains exceedingly tight, and numerous scientific, technical, and infrastructure challenges continue to present significant barriers to the widespread use of these techniques in these three areas of science. 相似文献
90.
In this article a class of subgroups of a finite group G, called Q-injectors, is introduced. If G is soluble, the Q-injectors are precisely the injectors of the Fitting sets. A characterization of nilpotent Q-injectors is given as well as a sufficient condition for the solubility of a finite group G, in terms of Q-injectors, which generalizes a well known result. 相似文献