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   5755篇
  免费   939篇
  国内免费   1321篇
化学   5015篇
晶体学   99篇
力学   328篇
综合类   135篇
数学   714篇
物理学   1724篇
  2024年   14篇
  2023年   133篇
  2022年   204篇
  2021年   215篇
  2020年   283篇
  2019年   280篇
  2018年   205篇
  2017年   246篇
  2016年   316篇
  2015年   314篇
  2014年   371篇
  2013年   471篇
  2012年   516篇
  2011年   566篇
  2010年   363篇
  2009年   402篇
  2008年   411篇
  2007年   330篇
  2006年   316篇
  2005年   294篇
  2004年   219篇
  2003年   238篇
  2002年   279篇
  2001年   231篇
  2000年   161篇
  1999年   140篇
  1998年   66篇
  1997年   44篇
  1996年   57篇
  1995年   59篇
  1994年   57篇
  1993年   47篇
  1992年   24篇
  1991年   18篇
  1990年   25篇
  1989年   17篇
  1988年   9篇
  1987年   16篇
  1986年   19篇
  1985年   4篇
  1984年   5篇
  1983年   7篇
  1982年   4篇
  1981年   3篇
  1979年   2篇
  1975年   1篇
  1973年   1篇
  1959年   4篇
  1957年   5篇
  1936年   2篇
排序方式: 共有8015条查询结果,搜索用时 15 毫秒
131.
Quinoline derivatives were efficiently prepared through acid-catalyzed Friedlander reaction in ionic liquid ([bmim] [BF4]). It is shown that the proposed method is operationally simple and environmentally benign in that the reaction media and the catalyst can be recovered and be reused effectively for at least four times.  相似文献   
132.
α-Chlorocycloalkanones(Ⅳ) were synthesized from cycloalkanones via potassiumα-oxocycloalkylsulfonates(Ⅱ).A two-step mechanism was proposed to explain the formation ofⅣfromⅡ.  相似文献   
133.
KF/Al~2O~3/PEG 4000(FAP)存在下氯仿的Michael加成反应   总被引:3,自引:0,他引:3  
在KF/Al~2O~3/PEG4000(FAP)存在下,氯仿可与α,β-不饱和羰基化合物进行Michael加成反应,得到中等产率的三氯甲基化合物。  相似文献   
134.
An efficient method is reported for the synthesis of phenacyl esters by reaction of carboxylic acids with a-bromoacetophenone promoted by potassium fluoride in ionic liquid [Bmim]PF6, the yield of the reaction is almost quantitative and the products are essentially pure.  相似文献   
135.
To determine the influence of the size of the aromatic chelate ligands on the frameworks of metal tretracarboxylate polymers, two new coordination polymers [Cd(btc)0.5 (2,2′‐bpy)] ( 1 ) and [Cd(btc)0.5(phen)]·H2O ( 2 ) (H4btc = biphenyl‐3,3′,4,4′‐tetracarboxylic acid, 2,2′‐bpy = 2,2′‐bipyridine, phen = 1,10‐phenanthroline) have been synthesized under similar hydrothermal conditions. In complex 1 , the dimeric Cd2 units are linked by bridging btc4? ligand to form a 2D layered network, whereas complex 2 possesses a 3D metal‐organic framework consisting of the dimeric Cd2 units. The differences of two metal‐organic frameworks demonstrate that the size of the rigid aromatic chelate ligands have an important effect on the structures of their complexes. Additionally, the two complexes show strong fluorescence in the solid state at room temperature.  相似文献   
136.
A new compound, subglain B, was isolated from the stems of Uvaria tonkinensis var.subglabra and its structure was identified as 1S, 2R, 3S, 6R-1-benzoyloxymethylene-1,2-dihydroxy-3-benzoyloxy-6-chlorocyclohex-4-ene (1), by spectral evidences.  相似文献   
137.
甘氨酸与氯化碱金属在水中的焓相互作用参数   总被引:2,自引:0,他引:2  
氨基酸在混合溶液中的热力学性质及相互作用的研究不论对溶液化学还是生命科学都是十分重要的.对此国内已有不少的研究h,’1.利用偿效应的方法研究氨基酸与电解质间的相互作用是很有效的卜一句,但大多数的工作都是在低浓度下研究一个氨基酸分子和一个电解质离子对间的相互作用烩.本文测定了甘氨酸在水中和在LICI、NaCI、KCI的水溶液中的溶解偿,计算出甘氨酸与各个公在水中的偿对相互作用参数和三相互作用参数,并由此讨论了甘氨酸与这些盐的对分子相互作用和三分子相互作用.1实验部分试剂:甘氨酸为ARfa,K甲醇一水重结晶.LI…  相似文献   
138.
Short DNA analogues with bridging dimethylene sulfide, sulfoxide, and sulfone groups replacing the phosphate diesters (S-DNAs) were synthesized from building blocks prepared via two routes, both starting from D-glucose. Building blocks for RNA analogues were prepared by stereoselective introduction of nucleobase into a 2'-acylated ribose analogue. The ribose analogues were converted to deoxyribose analogues by replacement of a 3'-OH group by a thioacetyl unit, followed by photolytic deoxygenation or radical-based 2'-deoxygenation. DNA analogues joined via CH(2)(-)S-CH(2) units were prepared by S(N)2 displacement of a 6'-mesyl group on one building block using a thiolate nucleophile of another. 4,4'-Dimethoxytrityl protection and deprotection schemes were established for both the thiol and hydroxyl groups. The corresponding sulfoxide DNA analogues were obtained by oxidation with hydrogen peroxide. Sulfone DNA analogues were obtained by oxidation of the sulfide DNA with persulfate or hydrogen peroxide in the presence of a titanium silicate catalyst. The physical properties of several representative oligonucleotide analogues were examined, and interpreted in light of a "second-generation" model for DNA strand-strand recognition, a model that emphasizes the role of the polyanionic backbone in diminishing unwanted tendencies of highly functionalized molecules to form "structure" in solution. Even short sulfide-linked DNA analogues displayed association properties different from those displayed by standard DNA molecules. Complex formation observed with sulfide-linked tetramers by HPLC study in different solvents suggested that the complex is formed using hydrogen bonding. Sulfone-linked dinucleotides display Watson-Crick behavior; the tetramer, however, displayed self-structure. Self-structure and self-aggregation become more prominent as the length of the oligonucleotide analogues increases. The tendency to self-aggregate can be decreased by adding a charged sulfonate group to the 3'-end of the DNA analogue. Features of the second-generation model are important for many areas of nucleic acid chemistry, from the design of nucleic acid therapeutic agents to the search for life on other planets.  相似文献   
139.
A homodinuclear complex (NH3CH2CH2CH2NH3)2 {Na2[(C6H4O2)2] (C6H4O2H)2} (1) has been synthesized by a solution-based self-assembly route. It crystallized in monoclinic system with space group P21/c. Every sodium ion coordinates in a tetragonal prism fashion with two O atoms of a terminal chelating catecholate ligand and three O atoms from two bridging catecholate ligands. Two neighboring NaO5 tetragonal prisms are edge-shared and centrosymmetric with regard to the inversion center to form a binuclear cluster {Na2[(C6H4O2)2](C6H4OOH)2}^4- anion. The complex anions were aligned parallelly by n-n interaction and linked with the protonated 1,3-propylenediamine through hydrogen bonds which were assembled into a multi-lamellar structure with channels. The crystal exhibits rectangular geometry with an interior triangle hollow structure under optical microscopy. And the scanning electron microscopy (SEM) indicates that the wall of the tubes shows multi-lamella morphologies. Further, the transmission electron microscopy (TEM) reveals that the crystal is composed of multi-lamellar nano-tubes with diameters less than 100 nm. The molecular structure of the complex was compared with that of its isomer complex 2.  相似文献   
140.
The crystal structure of the title compound, μ‐2‐hydroxy­butane­dioato‐1κ2O4,O4′:2κ3O1,O2,O4‐nitrato‐2κO‐tris­(1,10‐phen­anthroline)‐1κ4N,N′;2κ2N,N′‐dicopper(II) nitrate tetra­hydrate, [Cu2(C4H3O5)(NO3)(C12H8N2)3](NO3)·4H2O, contains an unsymmetrical dinuclear copper complex with Cu(phen)2 and Cu(phen)(NO3) moieties (phen is 1,10‐phenanthroline) bridged by a malate (2‐hydroxy­butane­dioate) ligand, which acts as a double‐bridging and tetra­dentate ligand. As a result of this double‐bridging action, especially the direct coordination of the O atom of one carboxyl­ate group of malate to the two Cu atoms, the Cu⋯Cu distance is only 4.199 (1) Å and the two phen planes are roughly parallel [the shortest inter­planar distance is 3.28 (1) Å], exhibiting an obvious intra­molecular π–π stacking inter­action.  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