首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1641篇
  免费   89篇
  国内免费   171篇
化学   1649篇
晶体学   14篇
力学   1篇
综合类   2篇
数学   23篇
物理学   212篇
  2024年   2篇
  2023年   10篇
  2022年   9篇
  2021年   20篇
  2020年   27篇
  2019年   21篇
  2018年   15篇
  2017年   18篇
  2016年   36篇
  2015年   24篇
  2014年   108篇
  2013年   114篇
  2012年   76篇
  2011年   144篇
  2010年   124篇
  2009年   129篇
  2008年   107篇
  2007年   138篇
  2006年   124篇
  2005年   137篇
  2004年   136篇
  2003年   109篇
  2002年   47篇
  2001年   20篇
  2000年   28篇
  1999年   20篇
  1998年   16篇
  1997年   18篇
  1996年   20篇
  1995年   13篇
  1994年   24篇
  1993年   14篇
  1992年   16篇
  1991年   6篇
  1990年   6篇
  1989年   4篇
  1988年   3篇
  1987年   6篇
  1986年   2篇
  1985年   1篇
  1984年   2篇
  1983年   1篇
  1981年   3篇
  1980年   1篇
  1979年   1篇
  1973年   1篇
排序方式: 共有1901条查询结果,搜索用时 31 毫秒
21.
The reaction of cyclobutanone with an alkyne in the presence of a nickel(0) catalyst formally achieves intermolecular alkyne insertion between the carbonyl carbon and the α-carbon of a cyclobutanone, providing a six-membered carbocyclic skeleton.  相似文献   
22.
Force mapping with the atomic force microscope (AFM) allows the simultaneous acquisition of topography and probe-sample interaction data. For example, AFM probes functionalised with an antigen can be employed to map the spatial distribution of recognition events on a substrate functionalised with its specific antibody. However, to date this method has been limited to the detection of single receptor-ligand species. Were the detection of multiple receptor-ligand interactions possible, force mapping would offer great scope as a sensitive tool for bioassay and screening applications. We have developed an immobilisation strategy, which allows two different molecular species (in this case human serum albumin and the β subunit of human chorionic gonadotropin) to be present simultaneously on an AFM probe. Single point force spectroscopy results have revealed the ability of such probes to discriminate between their corresponding recognition points (anti-HSA and anti-βhCG IgG antibodies). As a control, force measurements were re-recorded in the presence of the known antigen (free in solution) for each antibody species and a marked decrease in the frequency of specific interaction is observed. As an additional control interactions between anti-βhCG IgG and the multifunctional probe are taken in the presence of free βhCG (“true” antigen) and free HSA (“false” antigen). It is shown that measurements recorded in the presence of a non-related protein species results in no change in either the force observed or the frequency of specific interactions, further confirmation that the specificity of force observed is due to the separation of antibody-antigen complex.  相似文献   
23.
The cyclic voltammetric behaviour of Eu3+/Eu2+ couple at hanging mercury drop electrode (HMDE) has been studied in chloride, bromide, iodide, thiocyanate and EDTA supporting electrolytes. The apparent rate constant and transfer coefficient for these systems have been calculated at various voltage scan rates, without using the data for standard or formal potential. The values have been compared with those obtained by earlier workers through other electrochemical methods.  相似文献   
24.
在77K下测定了Eu(TTA)3·1/2(4,4′-bipyN2O2)配合物的激发光谱、发光光谱和时间分辨光谱。光谱数据表明,在标题配合物中存在化学环境不同的两种Eu3+格位,但它们的局部对称性都属于C2V点群,这可能表明该配合物的激发态电子结构稍有不同  相似文献   
25.
A single-crystal X-ray diffraction study of the terminally protected tetrapeptide Boc-β-Ala-Aib-Leu-Aib-OMe 1 (Aib: α-aminoisobutyric acid; β-Ala: β-Alanine) reveals that it adopts a new type of double turn structure which self-associates to form a unique supramolecular helix through intermolecular hydrogen bonds. Scanning electron microscopic studies show that peptide 1 exhibits amyloid-like fibrillar morphology in the solid state.  相似文献   
26.
As part of a programme directed towards the synthesis of the marine toxins, the spirolides and gymnodimine, a convenient synthesis of the key bicyclic spiroimine ring systems has been developed. The method involves double alkylation of a simple lactam, Grubbs ring closing metathesis of the resultant dialkylated lactam then reduction of the lactam to an imine.  相似文献   
27.
A new series of group 6 carbonyl complexes of N-[(2-pyridyl)methyliden]-α (or β)-aminonaphthalene (α/β-NaiPy) are described in this work. The complexes are formulated as cis-[M(CO)4(α/β-NaiPy)] by elemental, mass and other spectroscopic data. The complexes show emission spectra at room temperature and their quantum yield lies between 0.4 and 0.5. All the complexes exhibit negative solvatochromism. Cyclic voltammetry shows metal centred oxidation and ligand reductions.  相似文献   
28.
Jessica L. Bender 《Tetrahedron》2004,60(34):7277-7285
Dibenzoylmethane (dbm) initiators with one and two alcohol sites were used to generate dbm end-functionalized and dbm-centered poly(ε-caprolactone) macroligands (dbmPCL and dbmPCL2) with low polydispersities (∼1.1). Chelation of polymeric ligands to metal ions (Eu3+, Fe3+, Ni2+ and Cu2+) produced metal-centered star polymers, which were characterized by UV-vis and fluorescence spectroscopy, as well as gel permeation chromatography.  相似文献   
29.
K. Surendra 《Tetrahedron letters》2006,47(13):2133-2136
A new and convenient procedure for the synthesis of homoallylic alcohols directly from aromatic acetals and dioxolanes has been developed with very good yields under biomimetic conditions using a Zn-mediated Barbier-type allylation in the presence of β-cyclodextrin in water.  相似文献   
30.
铕(Ⅲ)┐β┐二酮┐4,5┐二氮芴┐9┐酮三元配合物的合成成义祥徐端钧*徐元植(浙江大学化学系杭州310027)关键词铕,β-二酮,二氮芴酮,三元配合物,合成,荧光光谱1997-03-31收稿,1997-07-15修回噻吩甲酰三氟丙酮(TTA)和苯甲...  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号