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   609篇
  免费   83篇
  国内免费   378篇
化学   974篇
晶体学   27篇
综合类   1篇
物理学   68篇
  2024年   15篇
  2023年   54篇
  2022年   121篇
  2021年   131篇
  2020年   98篇
  2019年   80篇
  2018年   44篇
  2017年   41篇
  2016年   38篇
  2015年   25篇
  2014年   31篇
  2013年   113篇
  2012年   47篇
  2011年   31篇
  2010年   21篇
  2009年   13篇
  2008年   22篇
  2007年   18篇
  2006年   16篇
  2005年   7篇
  2004年   19篇
  2003年   16篇
  2002年   11篇
  2001年   10篇
  2000年   7篇
  1999年   2篇
  1998年   3篇
  1997年   8篇
  1996年   4篇
  1995年   5篇
  1994年   2篇
  1993年   8篇
  1992年   1篇
  1991年   2篇
  1988年   1篇
  1987年   1篇
  1985年   2篇
  1983年   1篇
  1982年   1篇
排序方式: 共有1070条查询结果,搜索用时 15 毫秒
1.
The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10−3 S cm−1 at 75 °C and 80 % relative humidity).  相似文献   
2.
An efficient one-pot synthesis of a macrocyclic ligand, consisting of two 1,10-phenanthroline nuclei bridged by sulfur, is described. A spectrophotometric investigation reveals the isolated compound to be the mono-trifluoroacetate salt. Symmetrical NH- and S-bridged tetradentate ligands were also synthesized by the new method.  相似文献   
3.
New water-soluble porphycenes having sulfonic acid groups at the β-pyrrolic positions were synthesized and characterized by UV-vis, NMR, IR, and mass spectroscopy as well as elemental analyses. The series of mono- to tri-sulfonato derivatives were simply separated by the extraction method.  相似文献   
4.
5.
Ulrik Gran 《Tetrahedron》2003,59(24):4303-4308
A new macrocyclic NADH model 1 has been designed and synthesised. The new model consists of the same subunits as previously reported models. However, the present model is designed as such that the pyridine nitrogen of the nicotinamide units are not incorporated in the macrocyclic framework. Thus, properties such as solubility can easily be varied by alkylation with an appropriate agent. The macrocyclic framework was prepared in 7 steps. Methylation of the pyridine nitrogens followed by reduction gave the desired model. This model compound was found to reduce methyl benzoylformate stereoselectively in good yield with 48% enantiomeric excess.  相似文献   
6.
In this report, the stepwise synthesis of a novel rigid and functionalised macrocycle 2 based on triazine and phenylenediamine linkers, is presented. Poor recognition of the macrocycle 2 for its substrates is observed, which shows experimentally that for the meltriazine based-calix[6]arene system, the binding ability of the melamine moiety gets more benefit from the ring flexibility derived from a xylenediamine linker 1 than from a phenylenediamine linker 2.  相似文献   
7.
Macrocycle opening in derivatives of benzocrown ethers under the action of amines is affected by the nature of the heteroatoms in the macrocycle, the nature of the functional group in the benzene ring of the crown ether, and the length, branching, and number of hydrocarbon radicals at the amine nitrogen atom. A distinguishing feature of this reaction is the template effect of MeNH3 +, Me2NH2 +, Na+, and K+ ions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 687–692, March, 1996.For Part I see Ref. 1.  相似文献   
8.
A new method for synthesizing nitrogen-containing podands by nucleophilic regioselective cleavage of the macrocycle in formyl derivatives of benzocrown ethers by heating with methylamine and methylammonium chloride has been developed. This reaction is the first example of crown ether opening by a nitrogen-containing nucleophile.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 950–953, May, 1995.  相似文献   
9.
本文以2.6─二乙酰吡啶和1,3一二氨基一2一丙醇通过模板合成西佛碱大环配体H_2L(图1),并合成了它的Co(Ⅱ)、Ni(Ⅱ)及Fe(Ⅱ)的双核配合物,重点讨论了Co_2(HL)(ClO_4)_2(NO_3)·4H_2O配合物的光谱与磁性。变温磁化率数据(4─300K)通过用最小二乘法与理论方程拟合,得到磁参数为J=-1.24cm ̄(-1),θ=-0.24K,表明配合物中co(Ⅱ)-Co(Ⅱ)间存在弱的反铁磁相互作用,分子间也存在反铁磁相互作用。  相似文献   
10.
何义娟  李克丽  李倩  张鹏  艾萍  袁黎明 《色谱》2019,37(4):383-391
万古霉素和替考拉宁都属于糖肽类的大环抗生素,具有立体的环状结构和多个手性中心,是两种常见的手性识别材料,广泛应用于对映体的色谱手性分离分析。该文以万古霉素和替考拉宁为手性选择剂,哌嗪为单体,4,4'-二苯基甲烷二异氰酸酯(MDI)、1,6-己二异氰酸酯(HDI)和2,4-甲苯二异氰酸酯(TDI)为交联剂,通过界面聚合反应形成网状层包裹硅胶载体的方法制得6种高效液相色谱手性固定相,用于分离外消旋化合物,并与MDI直接交联万古霉素和替考拉宁在硅胶表面所得固定相进行了比较。结果表明,利用"网包法"和直接交联法制备的手性柱与商品万古霉素和替考拉宁柱之间具有互补性,均对不同的外消旋体有不同程度的拆分。  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