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   4352篇
  免费   465篇
  国内免费   629篇
化学   4140篇
晶体学   15篇
力学   36篇
综合类   72篇
数学   212篇
物理学   971篇
  2024年   6篇
  2023年   36篇
  2022年   83篇
  2021年   173篇
  2020年   176篇
  2019年   131篇
  2018年   123篇
  2017年   144篇
  2016年   215篇
  2015年   188篇
  2014年   287篇
  2013年   337篇
  2012年   262篇
  2011年   302篇
  2010年   241篇
  2009年   288篇
  2008年   287篇
  2007年   298篇
  2006年   304篇
  2005年   284篇
  2004年   253篇
  2003年   197篇
  2002年   116篇
  2001年   106篇
  2000年   86篇
  1999年   80篇
  1998年   84篇
  1997年   72篇
  1996年   55篇
  1995年   49篇
  1994年   49篇
  1993年   29篇
  1992年   11篇
  1991年   18篇
  1990年   17篇
  1989年   15篇
  1988年   13篇
  1987年   7篇
  1986年   7篇
  1985年   5篇
  1984年   4篇
  1983年   1篇
  1982年   2篇
  1979年   1篇
  1978年   1篇
  1975年   1篇
  1974年   1篇
  1969年   1篇
排序方式: 共有5446条查询结果,搜索用时 382 毫秒
121.
A new chemosensor for larger guests was prepared. The new chemosensor bears hydrophobic units at the primary hydroxy side and a dansyl unit at the secondary hydroxy side of β-cyclodextrin. Due to the hydrophobic units, the new chemosensor is sensitive to large or slender guests such as SDS and insensitive to 1-adamantanol, which is a good guest for the natural β-CD.  相似文献   
122.
Two newly identified supramolecular structures arise from self-assembly of the macrocyclic 1,5,9,18,22,26- hexaaza[11.11]-p-cyclophane salts with o-nitrophenol (C28H50N6)4+·4(C6H4NO2O) (1) and with HCl (C28H52N6)6+·6Cl-·4H2O (2). In both cases two-dimensional supramolecular sheets are formed.  相似文献   
123.
Molecular imprinting is a template polymerization technique that can easily provide synthetic polymers capable of molecular recognition for given target molecules. In addition to their highly specific recognition ability, we are attempting to introduce signaling functions to molecularly imprinted polymers, enabling them to respond according to specific binding events. Some of our work regarding such signaling molecularly imprinted polymers is presented here, including molecularly imprinted polymers that induce spectral shifts of target compounds because of binding. Such compounds include hydrogen-bonding-based fluorescent imprinted polymers and metalloporphyrin-based signaling molecularly imprinted polymers.  相似文献   
124.
利用原子与表面簇合物相互作用的5参数Morse势方法(简称5-MP)系统地研究了O-Ru低指数面及Ru(1120),(1121)台阶面体系,获得了吸附几何、结合能、振动频率等临界点特性,所得相关数据与实验结果非常吻合.并且通过理论计算及原子吸附态振动指纹的遗传、遗变特性预言了氧原子在Ru(1121)台阶面的吸附.本文认为氧原子在HCP晶格的金属表面上的吸附倾向于三重位.  相似文献   
125.
党东宾   《化学研究》2006,17(4):91-95
对基于(C—H)+…X-氢键类型的阴离子识别以及识别过程所引起的光化学传感和电化学传感的研究进展进行了评述.  相似文献   
126.
The novel trimethylene-bridged clips 3 and 4 have been synthesized by using repetitive stereoselective Diels-Alder reactions of the benzo- and naphthobismethylenenorbornenes 8 and 19 as dienes and norbornadiene 9 as bisdienophile, and subsequent dehydrogenation of the primary cyclobisadducts 10 and 20 by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Clips 3 and 4 serve as receptors for a variety of electron-deficient neutral and cationic aromatic substrates, comparable to the molecular tweezers 1 and 2. The thermodynamic parameters of the complex formation, K(a) and DeltaG, were determined by (1)H NMR titration experiments and, in the case of the highly stable complex TCNB 32@4, by the use of isothermal titration microcalorimetry. The finding that clip 4 forms more stable complexes than 3 can be explained by the larger van der Waals contact surfaces of the naphthalene sidewalls in 4 compared to the corresponding benzene systems in 3. In the complexes with 4 as receptor, the plane of each aromatic substrate molecule is calculated to be oriented almost parallel to the naphthalene sidewalls. However, in the complexes of tweezers 2, the substrate is usually oriented parallel to the central naphthalene spacer unit. Due to the more open topology of 4, most complexes were calculated to consist of two or more equilibrating noncovalent conformers.  相似文献   
127.
宋冠群  林金明  屈锋  董文举 《中国化学》2003,21(10):1325-1329
IntroductionTeaisthemostwidelyconsumedbeverageinpeople’slife .Theheightenedpopularityofthisbeveragethroughouttheworldinrecentyearsmaybedueinparttotheevidenceofarelationshipbetweenteaconsumptionandpreventionofcertainformsofhumandisease .Themaincomponentsofteaarepolyphenoliccompounds ,commonlyknownascatechins ,whichrepresentagroupofcom poundsbelongingtotheflavonoidfamily .Thesecom poundsarewidelydistributedinthetealeavesandconsti tuteupto 30 %ofthedryleafweight.1Muchinteresthasbeenfocusedoncat…  相似文献   
128.
氢醌卟啉的合成及其对醌的分子识别   总被引:2,自引:0,他引:2  
利用氢醌与2-硝基卟啉直接反应,合成了2-(2’,5’—二羟基苯基)—5,10,15,20-四苯基卟啉,并利用紫外光谱、荧光光谱、电化学方法考察了它们对酯的分子识别,结果显示2—(2’,5’—二羟基苯基)-5,10,15,20-四苯基卟啉对醌具有较好的识别能力。  相似文献   
129.
Thiacalix[4]arene (5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathiacalix[4]arene) is an amphiphilic molecule comprising four p-tert-butylphenol-like groups ortho-linked by single sulfur atoms. This molecule has a high electron density area owing to the close proximity of the hydroxyl groups and sulfur atoms. We studied the applicability of this interesting compound as a selector for high-performance liquid chromatography (HPLC) thereby presumably exploiting this feature. Firstly, uniformly sized polymer particles were prepared by using a multi-step swelling and polymerization method with ethylene glycol dimethacrylate (EDMA) as a cross-linker. Methacrylic acid (MAA) was introduced onto the surface of the resulting polymer particles through a new modification method. Thiacalix[4]arene was chemically bonded through the MAA group by using 1,4-dibromobutane as a spacer to reduce steric hindrance around the MAA and the polymer particle itself. The performance of the prepared polymer-based thiacalix[4]arene-modified stationary phase was evaluated with HPLC. Specific chromatographic retention behavior was observed for catechol relative to positional isomers of xylene, cresol, and benzene-diol. Catecholamine and catechol showed specific chromatographic retention behavior.  相似文献   
130.
悬浮聚合法制备磁性分子印迹聚合物微球   总被引:8,自引:1,他引:8  
以苯胺和二甲基苯胺为模板分子、甲基丙烯酸(MAA)为功能单体、三羟甲基丙烷三丙烯酸酯(TRIM)为交联单体、Fe3O4为磁性组分,采用悬浮聚合法制备了磁性分子印迹聚合物微球(MMIPMs)。结果表明,改性Fe3O4微粒在MMIPMs中分散较好,MMIPMs在水性介质中对模板分子的选择吸附性较差,但在有机介质中有较好的选择吸附性。  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