全文获取类型
收费全文 | 5671篇 |
免费 | 721篇 |
国内免费 | 622篇 |
专业分类
化学 | 4071篇 |
晶体学 | 79篇 |
力学 | 377篇 |
综合类 | 50篇 |
数学 | 631篇 |
物理学 | 1806篇 |
出版年
2024年 | 13篇 |
2023年 | 77篇 |
2022年 | 89篇 |
2021年 | 174篇 |
2020年 | 180篇 |
2019年 | 206篇 |
2018年 | 167篇 |
2017年 | 149篇 |
2016年 | 259篇 |
2015年 | 233篇 |
2014年 | 266篇 |
2013年 | 395篇 |
2012年 | 421篇 |
2011年 | 469篇 |
2010年 | 337篇 |
2009年 | 302篇 |
2008年 | 342篇 |
2007年 | 302篇 |
2006年 | 342篇 |
2005年 | 249篇 |
2004年 | 211篇 |
2003年 | 184篇 |
2002年 | 201篇 |
2001年 | 160篇 |
2000年 | 132篇 |
1999年 | 145篇 |
1998年 | 139篇 |
1997年 | 116篇 |
1996年 | 93篇 |
1995年 | 107篇 |
1994年 | 92篇 |
1993年 | 61篇 |
1992年 | 57篇 |
1991年 | 45篇 |
1990年 | 51篇 |
1989年 | 27篇 |
1988年 | 21篇 |
1987年 | 15篇 |
1986年 | 34篇 |
1985年 | 27篇 |
1984年 | 20篇 |
1983年 | 17篇 |
1982年 | 13篇 |
1981年 | 12篇 |
1980年 | 6篇 |
1979年 | 10篇 |
1977年 | 4篇 |
1974年 | 7篇 |
1973年 | 7篇 |
1969年 | 4篇 |
排序方式: 共有7014条查询结果,搜索用时 187 毫秒
91.
92.
Dimethylformamide (DMF) acts as an efficient source of carbon monoxide and dimethylamine in the palladium-catalyzed aminocarbonylation (Heck carbonylation) of p-tolyl bromide to provide the dimethylamide. Addition of amines to the reaction mixture in excess delivers the corresponding aryl amides in good yields. The amines employed, benzylamine, morpholine, and aniline, all constitute good reaction partners. The reaction proceeds smoothly with bromobenzene and more electron-rich aryl bromides, but electron-deficient aryl bromides fail to undergo aminocarbonylation. The reactions are conducted at 180-190 degrees C for 15-20 min with microwave heating in a reaction mixture containing imidazole and potassium tert-butoxide: the latter is required to promote decomposition of the DMF solvent at a suitable rate. The beneficial effects of controlled microwave irradiation as an energy source for the rapid heating of the carbonylation reaction mixture are demonstrated. The carbonylation procedure reported herein, which relies on the in situ generation of carbon monoxide, serves as a convenient alternative to other carbonylation methods and is particularly applicable to small-scale reactions where short reaction times are desired and the direct use of carbon monoxide gas is impractical. 相似文献
93.
IntroductionInthcsclcctivcoxidationofalkanes.suchas'theoxidativccouplingofmcthanc(0CM)andthcoxidativcdch}'drogenationofcthanc(0DE)t0prcparccth}'lene.bothoxidcionsofthelatticeandtheox}'genspeciesovercataIystsuffocepla}'animportantrole.Althoughcxtcnsivcinvcstigationshavcbeengivcntothecharactcrizationofox}'gcnspccicsandthcreactionofox}'gcnspecicsx`ithalkanes,itisstilldifficulttosayt`hichoncsofox}'gcnspcciesarcthcactivcspecicsinthcactivation0falkancs.bccauscthenaturcofcatal}'stsandthecxperimcntc… 相似文献
94.
Determination of enantiomeric purity is most often done under overload conditions, which leads to deformed peaks. In general, the best resolutions are obtained when the small peak appears before the large peak in the electropherogram. To be able to determine the R(+)-impurity in the S(-)-form as well as the S(-)-impurity in the R(+)-form the elution orders have to be reversed. The present paper describes reversal of enantiomeric elution order for the basic analyte propranolol and the acidic analyte ibuprofen. For propranolol, a charged heptakis-(6-sulfo)-beta-cyclodextrin (CD) is used in the background electrolyte. For ibuprofen, a mix of the charged heptakis-(6-sulfo)-beta-CD and the uncharged heptakis-(2,3,6-tri-O-methyl)-beta-CD is used in the background electrolyte. The use of a coated capillary and reversal of the polarity shift the elution order, buffer composition is unchanged in both cases. The enantiomers of propranolol and ibuprofen are well separated on both the coated and uncoated capillaries. Detection limits of enantiomer impurities are investigated using spiked samples of both propranolol and ibuprofen. 相似文献
95.
Dispersion of MoO3, NiO, ZnO on rutile TiO2 with low specific surface area was studied with Mercury Porosimeter, SEM, XPS and Ammonia Extraction method. The dispersion thresholds of MoO3, NiO, ZnO on three rutile TiO2 carriers were obtained with XPS, and com-pared with those on anatase TiO2 with high specific surf are area. Ammonia Extraction method was used to identify the surface oxide species interarting with support surface in different strength and it was found that the proportions of oxides that can not be extracted by ammonia extraction are different for MoO3, NiO and ZnO which are supported on rutile TiO2. 相似文献
96.
A series of chiral aromatic imides and diimides were synthesized and their electrochemical, absorption, fluorescent, and chiroptical properties were examined for their potential application as molecular chiroptical switches. These compounds exhibit strong UV-vis absorptions, and can be electrochemically reduced to radical anions that absorb in the near infrared (NIR) region. Further reduction to the dianionic states results in new absorptions in the visible region. The changes in circular dichroism upon redox switching were apparent in the UV-vis region but were absent in the NIR region. 相似文献
97.
Three lanthanide coordination polymers were prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. [Pr2(mBDC)3(phen)(H2O)]n·0.5nH2O (1) (mBDC=isophthalate, phen=1,10-phenanthroline) exhibits two kinds of metal environments (coordination numbers 7 and 8). In complex 1, mBDC ligands adopt the tetradentate (bridging and bridging) coordination mode and connect Pr ions into an undulating layer, and a 3D supramolecular structure is formed via hydrogen bonds between adjacent layers. [Tb4(mBDC)6(phen)]n (2) has three types of metal environments (coordination numbers 6, 7 and 8) and is composed of a 3D network formed by mBDC linking Tb ions via tetradentate (bridging and bridging) and pentadentate (bridging/chelating and bridging) coordination modes. There are two kinds of small quadrilateral channels along the a-axis. [Er4(mBDC)6(phen)]n (3) is isostructural to complex 2. 相似文献
98.
99.
杂多化合物的酸催化特性及其在有机合成反应中的应用 总被引:12,自引:0,他引:12
杂多化合物在各个研究领域中的实际应用日趋广泛。特别是在催化领域内,对杂多化合物催化性能和研究越来越引起人们的关注。本文对在均相和非均相体系中杂多化合物的酸催化的最新研究成果和应用进行了综述,对杂多化合物的酸行为进行了简要的概括,并介绍了作者在这方面的工作。 相似文献
100.
Li BS Kang SZ Cheuk KK Wan L Ling L Bai C Tang BZ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(18):7598-7603
In the present work, we investigated self-assembling of a poly(phenylacetylene) carrying L-valine pendants (PPA-Val) in a water/methanol solution, upon evaporation of the solution on mica, and on the water surface. With intercalation of a fluorescence probe of Ru(phen)2(dppx)2+ (phen = 1,10-phenanthroline, dppx=7,8-dimethyldipyridophenazine) into the hydrophobic cavities associated by the PPA-Val chains, their helical structures were directly detected in solution with an in situ fluorescence microscope. Helical aggregates were observed with AFM upon evaporation of the solvents, suggesting that the helical structures in the solution are the building blocks of the helical aggregates. Self-assembling structures of PPA-Val on the water surface were, however, very different from that formed upon evaporation of its THF solution on the mica surface. The polymer chains associated into a monolayer of extended fibers on the water surface, whereas superhelical fibers formed on the mica surface. Water molecules play a critical role in inducing the polymer to form diverse morphological structures in its bulk solution and on its surface. In solution, the isotropic hydrophobic effect drove the polymer chains to form superhelical aggregates, while on the water surface, the hydrophobic effect concentrated mainly on the lateral part of the polymer, thus giving a monolayer of extended fibers. 相似文献