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   1579篇
  免费   328篇
  国内免费   211篇
化学   1074篇
晶体学   43篇
力学   113篇
综合类   16篇
数学   201篇
物理学   671篇
  2024年   3篇
  2023年   37篇
  2022年   57篇
  2021年   72篇
  2020年   79篇
  2019年   70篇
  2018年   63篇
  2017年   68篇
  2016年   82篇
  2015年   81篇
  2014年   111篇
  2013年   105篇
  2012年   148篇
  2011年   161篇
  2010年   112篇
  2009年   114篇
  2008年   117篇
  2007年   76篇
  2006年   91篇
  2005年   65篇
  2004年   47篇
  2003年   49篇
  2002年   54篇
  2001年   35篇
  2000年   16篇
  1999年   25篇
  1998年   25篇
  1997年   26篇
  1996年   20篇
  1995年   10篇
  1994年   15篇
  1993年   13篇
  1992年   5篇
  1991年   6篇
  1990年   4篇
  1989年   10篇
  1988年   7篇
  1987年   4篇
  1986年   5篇
  1985年   13篇
  1984年   4篇
  1983年   2篇
  1982年   1篇
  1976年   1篇
  1975年   1篇
  1974年   1篇
  1973年   4篇
  1972年   1篇
  1969年   1篇
  1961年   1篇
排序方式: 共有2118条查询结果,搜索用时 15 毫秒
31.
The pervaporation and vapor permeation performance of symmetrical and asymmetrical polycarbonate membranes, prepared via a dry-phase inversion and wet-phase inversion methods, respectively, were studied by measuring the permeation rate and separation factor. It was found that the polymer concentration effect on the pervaporation performance for the symmetrical polycarbonate membrane was lower than that for the asymmetrical polycarbonate membrane. Compared with pervaporation, vapor permeation has a significantly increased separation factor with a decreased permeation rate for the symmetrical polycarbonate membrane. Water molecules preferentially dissolve into the symmetrical polycarbonate membrane and diffuse easily through the membrane.  相似文献   
32.
An extended family of aryl-substituted alkaline earth metal silylamides M{N(2,4,6-Me3C6H2)(SiMe3)}donor(n) was prepared using alkane elimination (Mg), salt elimination (Ca, Sr, Ba), and direct metalation (Sr, Ba). Three different donors, THF, TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine), and PMDTA (PMDTA = N,N,N',N',N'-pentamethyldiethylenetriamine) were employed to study their influence on the coordination chemistry of the target compounds, producing monomeric species with the composition M{N(2,4,6-Me3C6H2)(SiMe3)}2(THF)2 (M = Mg, Ca, Sr, Ba), M{N(2,4,6-Me3C6H2)(SiMe3)}2TMEDA (M = Ca, Ba), and M{N(2,4,6-Me3C6H2)(SiMe3)}2PMDTA (M = Sr, Ba). For the heavier metal analogues, varying degrees of agostic interactions are completing the coordination sphere of the metals. Compounds were characterized using IR and NMR spectroscopy in addition to X-ray crystallography.  相似文献   
33.
滕启文  吴师 《中国化学》2006,24(3):419-422
Equilibrium geometries of 16 possible isomers for C74(BN)2 were studied by INDO series of methods, to indicate that the most stable three geometries are those where boron and nitrogen atoms substitute carbon atoms located at the same hexagon near the longest axis of C78 (C2v) to form B-N-B-N unit. Electronic spectra of C74(BN)2 were investigated with INDO/CIS method. The reason for the red shift of UV absorptions for C74(BN)2 compared with those of C78 (C2v) was discussed. IR spectra for 9,8,28,29-C74(BN)2 and 28,29,30,31-C74(BN)2 were calculated on the basis of AM1 geometries.  相似文献   
34.
A new anthraquinone glycoside, rubiayannone‐A ( 1 ), and a new coumarin, rubilatin‐A ( 2 ), together with twenty‐two known compounds were isolated and characterized from the roots of Rubia ustulata. A new anthraquinone, 2‐carbomethoxyanthraquinone ( 3 ), and rubiayannone‐A, 2‐formylanthraquinone were obtained from the roots of R. yunnanensis. The structures of those compounds were elucidated by spectroscopic methods. The antiplatelet aggregation activity of the isolated compounds 1, 4~6 were also discussed.  相似文献   
35.
IntroductionDAisoneofessentialparticipantsintheneuro transmissionprocessinmammaliancentralnervoussys tem .AlossofDA containingneuronsmayresultinsomeseriousdiseasesuchasParkinsonism .1Sinceitsdiscov eryinthe 195 0s ,DAhasbeenofinteresttoneuroscien tistsandchem…  相似文献   
36.
Herein, we demonstrate that silica films with perpendicular macroporous channels and accessible ordered mesopores can be conveniently prepared. The hierarchical macroporous–mesoporous silica films are synthesized by using zinc oxide nanorod array as macroporous template and CTAB surfactant as mesoporous template. In basic surfactant-containing solution, ordered mesoporous silica shells homogeneously grow on the zinc oxide nanorod array. The growth of the mesostructures do not require any chemical modification for the zinc oxide nanorod, which opens a new way for preparing hierarchical silica films with perpendicular mesochannels. The prepared hierarchical macroporous–mesoporous silica films possess a uniform thickness of 2 mm, large perpendicular macropores with a length of 1.8 mm and a width of 80 nm, and accessible ordered mesopores. Separation experiment demonstrates that this macroporous–mesoporous film can effectively separate biomolecules with different sizes.  相似文献   
37.
Two mutants of the zinc finger protein, ZNF191 (243–368) I323W and R327W, are successfully obtained by site-directed mutagenesis. The fluorescence spectrum is used to study the interaction between these two mutants and the oligonucleotides. The influence of the mutation on the interaction has been studied using ethidium bromide (EB) as the fluorescence probe. The binding constants of the I323W-DNA and R327W-DNA have been calculated and the possible binding models have been discussed.  相似文献   
38.
Modified octaphyrins with 34pi electrons have been synthesized and characterized following a simple synthetic methodology. An acid-catalyzed alpha,alpha coupling of tetrapyrranes containing furan, thiophene and selenophene rings resulted in the formation of the respective octaphyrins in relatively good yield. Solution studies by (1)H NMR and 2D NMR methods and single crystal Xray structural characterization reveal an almost flat structure with two heterocyclic rings inverted. Specifically, in 14 two selenophene rings (one on each biselenophene unit) are inverted while in 15 two furan rings (one on each bifuran unit) are inverted when the meso substituent are mesityl groups. On changing the mesityl substituent to m-xylyl group as in 19, the location of ring inversion shifts to pyrrole rings (one on each bipyrrole unit) indicating the dependence of structure on the meso substituents. UV/Vis studies, both in freebase and protonated forms reveal typical porphyrinic character and the aromatic nature of the octaphyrins. The Deltadelta values evaluated by (1)H NMR spectroscopy also support their aromatic nature. The protonated forms of octaphyrins bind TFA anion in a 1:2 ratio. The TFA anions are located one above and below the plane of the octaphyrin macrocycle and they are held by weak electrostatic NH-O interactions similar to that observed for protonated rubyrins. However, in the present case, there is an additional non-electrostatic CH-O interaction involving beta-CH of the inverted heterocyclic ring and the carbonyl oxygen of the TFA. Furthermore, inter molecular interactions between the Cbond;H of the meso-mesityl group and the fluorine of CF(3) group of bound TFA leads to the formation of one-dimensional supramolecular arrays with interplanar distance of 13 A between two octaphyrins.  相似文献   
39.
A new type of bismaleimide resin (EPBMI), containing epoxy unit and phosphorus in the main chain, was synthesized. The structure of the new resin was confirmed by infrared spectroscopy (IR), 1H NMR and 13C NMR spectroscopies. In addition, the compositions of the new synthesized bismaleimide with two reactants, 4,4′-diaminodiphenylsulfone (DDS) and 4,4′-diaminodiphenylether (DDE), was used to compare its reactivity and thermal properties with conventional bismaleimide (EBMI). Reactivity was measured by differential scanning calorimetry. Thermogravimetric analysis revealed that the polymers, obtained through the reactions between bismaleimides and diamine agents, also demonstrated excellent thermal properties and high char yield.  相似文献   
40.
The Bu(3)Sn radical-induced reaction of o-iodobenzylvinylsilanes and o-iodoallylsilanes leads to cyclic products in yields of 40-60%. These regioselective cyclizations occur with high preference for a 5-exo and a 7-endo mode with a 6-exo mode being absent. An example for ring closure via a 7-exo mode is described.  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