全文获取类型
收费全文 | 12822篇 |
免费 | 2601篇 |
国内免费 | 1573篇 |
专业分类
化学 | 16697篇 |
晶体学 | 19篇 |
力学 | 5篇 |
综合类 | 31篇 |
数学 | 7篇 |
物理学 | 237篇 |
出版年
2024年 | 31篇 |
2023年 | 250篇 |
2022年 | 352篇 |
2021年 | 512篇 |
2020年 | 967篇 |
2019年 | 666篇 |
2018年 | 648篇 |
2017年 | 439篇 |
2016年 | 807篇 |
2015年 | 912篇 |
2014年 | 994篇 |
2013年 | 1154篇 |
2012年 | 893篇 |
2011年 | 939篇 |
2010年 | 742篇 |
2009年 | 785篇 |
2008年 | 825篇 |
2007年 | 676篇 |
2006年 | 663篇 |
2005年 | 611篇 |
2004年 | 627篇 |
2003年 | 503篇 |
2002年 | 385篇 |
2001年 | 202篇 |
2000年 | 169篇 |
1999年 | 184篇 |
1998年 | 176篇 |
1997年 | 167篇 |
1996年 | 137篇 |
1995年 | 138篇 |
1994年 | 91篇 |
1993年 | 64篇 |
1992年 | 66篇 |
1991年 | 28篇 |
1990年 | 26篇 |
1989年 | 36篇 |
1988年 | 32篇 |
1987年 | 19篇 |
1986年 | 16篇 |
1985年 | 17篇 |
1984年 | 10篇 |
1983年 | 13篇 |
1982年 | 8篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1977年 | 4篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
51.
C. Devaux J.P. Chapel E. Beyou Ph. Chaumont 《The European physical journal. E, Soft matter》2002,7(4):345-352
Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization.
The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to
PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure
was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness
was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special
features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular
weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution.
Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers.
Received 20 December 2001 相似文献
52.
53.
Many natural products contain carbohydrate moieties that contribute to their biological activity. Manipulation of the carbohydrate domain of natural products through multiple glycosylations to identify new derivatives with novel biological activities has been a difficult and impractical process. We report a practical one‐pot enzymatic approach with regeneration of cosubstrates to synthesize analogues of vancomycin that contain an N‐alkyl glucosamine, which exhibited marked improvement in antibiotic activity against a vancomycin‐resistant strain of Enterococcus. 相似文献
54.
Roxana S. Timofte 《Tetrahedron letters》2004,45(1):39-42
High surface area silica pellets are excellent supports for the preparation of silica supported reagents and solid-phase basal linkers through reaction with (RO)3Si(CH2)3FG (FG=NH2, NHMe, Cl, NHC(O)NH2, OC(O)CMe(CH2), NCO, NEt2). High loadings (0.66-2.15 mmol g−1) of grafted silane materials are realised at synthetically useful loadings per pellet (ca. 0.06 mmol). Preliminary trials show that trial linker chemistry and ligand synthesis can be carried out on these materials and that these reactions can be monitored by solid state 13C NMR studies on individual pellets. 相似文献
55.
1,6-烯炔底物在过渡金属催化剂作用下的化学行为得到了广泛的研究,重点是关于过渡金属催化的1,6-烯炔环异构化反应.从反应机理角度入手,把1,6-烯炔环异构化反应按启动方式总结为三类,并对这三种方式启动的1,6-烯炔环异构化反应进行了详细地总结和阐述. 相似文献
56.
Jérémie Fournier Dit Chabert 《Tetrahedron》2004,60(14):3221-3230
Straightforward and rapid access to 2-arylbenzo[b]thiophenes has been developed. It involved a catalytic coupling of 3-activated benzo[b]thiophenes with several aryl halides in the presence of a phosphine-free palladium system. In case of fragile functional groups such as aldehydes, a quaternary ammonium was used as an additive as with the other substrates, the coupling performed better and faster in the presence of a crown ether, the best one being DCH-18-C-6, with good yields and low reaction times. This method would provide a direct access to novel structures of biological interest. 相似文献
57.
A straightforward process for the encapsulation of HbHNL under low methanol conditions has been developed. By adding a sol, prepared by hydrolysis of TMOS/MTMS at pH 2.8 with continuous removal of methanol, to a stirred solution of the enzyme in a buffer at pH 6.5, at least 65% of the activity of the free enzyme could be recovered after the encapsulation. The aquagels were successfully used in the synthesis of (S)-cyanohydrins. 相似文献
58.
59.
60.
Michael C. W. Chan Dr. 《化学:亚洲杂志》2008,3(1):18-27
The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???Hβ ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis. 相似文献