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   7394篇
  免费   260篇
  国内免费   50篇
化学   4817篇
晶体学   54篇
力学   192篇
数学   1333篇
物理学   1308篇
  2023年   53篇
  2022年   114篇
  2021年   201篇
  2020年   169篇
  2019年   176篇
  2018年   166篇
  2017年   122篇
  2016年   281篇
  2015年   204篇
  2014年   247篇
  2013年   416篇
  2012年   431篇
  2011年   517篇
  2010年   341篇
  2009年   287篇
  2008年   448篇
  2007年   360篇
  2006年   353篇
  2005年   329篇
  2004年   318篇
  2003年   226篇
  2002年   228篇
  2001年   99篇
  2000年   88篇
  1999年   88篇
  1998年   75篇
  1997年   63篇
  1996年   103篇
  1995年   56篇
  1994年   57篇
  1993年   55篇
  1992年   63篇
  1991年   55篇
  1990年   23篇
  1989年   24篇
  1988年   27篇
  1987年   31篇
  1986年   30篇
  1985年   34篇
  1984年   40篇
  1983年   21篇
  1982年   38篇
  1981年   45篇
  1980年   20篇
  1979年   30篇
  1978年   38篇
  1977年   21篇
  1976年   33篇
  1972年   21篇
  1885年   16篇
排序方式: 共有7704条查询结果,搜索用时 15 毫秒
91.
The crystalline host–guest type complex [(18-crown-6NH4)2][SiF6]4H2Ohas been obtained as the result of the interaction of SiF42NH3 with 18-crown-6 (18C6) in an aqueous medium. Crystal data: monoclinic, space groupC 2 c, a=26.541(2), b=8.363(2), c=20.469(2) Å, = 122.43(1)°and Z=4. The final R-value is 0.070 for 3253 reflections with I 2(I).The crystals consist of the complex [NH418C6]+ cations, [SiF6]2-anions and water molecules. The ammonium cation is hydrogen bonded by three of its H-atoms to the crown ether oxygen atoms with N(1) O separations2.923(5)–2.940(5) Å and by the fourth H-atom to the fluorine atom of thehexafluorosilicate anion, the N(1)F(4) distance being 2.797(6) Å.The conformation of the macrocycle and the hydrogen-bond geometry in thecomplex cation closely resemble those in related adducts between 18-crown-6and ammonium salts. All crystal components are connected via a system of hydrogen bonds into a ribbon along the b axis in the unit cell.  相似文献   
92.
Two series of 5-[[4-[4-(dialkylamino)butyl]-l-cyclohexyl]acetyl], and 5-[(dialkylamino)acyl]-10,11-dihydro-5H- dibenzo[b,e][1,4]diazepin-11-ones were synthesized as potential m2-selective ligands 1,2. Their affinity and selectivity for the muscarinic cholinergic receptor m-AChR subtypes were determined. Replacing a nitrogen with CH in the piperidine ring of 5-[[4-[4-(dialkylamino)butyl]-l-piperidinyl]acetyl]-10,11-dihydro-5H-dibenzo-[b,e][1,4]diazepin-11-ones 3 significantly altered the affinity and selectivity to the muscarinic receptor subtypes.  相似文献   
93.
Nb6.74Ta5.26S4 has been prepared by high temperature techniques. The crystal structure has been determined from single crystal X-ray diffraction data (R/Rw = 0.0588/0.0655). The compound crystallizes in the orthorhombic space group Pnma with unit cell dimensions a = 959.11 (26) pm, b = 336.37 (10) pm, and c = 3282.51 (74) pm. The orthorhombic cell contains four formula units. Its structure is similar to that of Nb-rich sulfides, rather than to that of Ta-rich sulfides. The metal coordinations are capped distorted cubic prisms and pentagonal prisms while the coordinations of sulfur are capped trigonal prisms.  相似文献   
94.
Dehydroluciferyl-coenzyme A (L-CoA) was chemically synthesized and characterized by MS, UV-vis spectrometry and RP-HPLC. The identity of the chemically synthesized compound with the one that was produced by firefly luciferase was confirmed. Moreover, the reversibility of the enzymatic conversion of dehydroluciferin ? dehydroluciferyl-adenylate ? L-CoA was also confirmed. The chemical synthesis of L-CoA, described here, may help the clarification of the activator effect of CoA on luciferase bioluminescent assays, in which the enzyme catalyzed formation of L-CoA and the consequent destruction of L-AMP is one of the possible explanations for that effect.  相似文献   
95.
The CD spectra of L-2-methylpyrrolidine, L-prolinol, and their N-methylated derivatives have been determined. As in the 2-substituted piperidines, N-methylation results in an inversion of the sign of the Cotton effects (CE). However, the sign of the long-wavelength CE does not follow the simple helicity rule found for 2-substituted piperidines, since the pyrrolidine ring is itself chiral and makes its own contributions to the observed CE's. The rotational contribution due to pyrrolidine ring chirality appears to be opposite in sign to and larger in magnitude than that due to the 2-substituent in both the secondary and the tertiary amines.  相似文献   
96.
Summary Poly(methyloctylsiloxane) (PMOS), sorbed into the pores of HPLC silica particles by solvent evaporation, can function as a useful stationary phase for reversed-phase chromatography. The present work addresses the question of how the PMOS is distributed in the pores. Measurements of the surface area (BET, N2) of a series of partially loaded samples (0–40% PMOS, m/m) using a typical batch of HPLC silica (10 μm irregular particles with 6 nm pores) show that the specific surface area of the samples decreases linearly with the specific loading (mass of PMOS per gram of silica). This result is not consistent with a “film” model in which the PMOS is deposited uniformly on the pore walls, but is consistent with a model in which long segmented “plugs” of PMOS are deposited within the pore system. Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996  相似文献   
97.
98.
The novel iridal 10 has been isolated from rhizome extracts of Iris foetidissima. Its structure was established by spectroscopic methods and oxidative degradation. Final proof of the spirobicyclic nature of the compound – a new feature in the triterpenoid field – was afforded by the correlations observed in the 2D-HMBC- (1H-detected multiple-bond heteronuclear multiple-quantum coherence) spectrum. The possible biogenesis of this unusual compound is discussed.  相似文献   
99.
Transmembrane proteins (TMPs), particularly ion channels and receptors, play key roles in transport and signal transduction. Many of these proteins are pharmacologically important and therefore targets for drug discovery. TMPs can be reconstituted in planar-supported lipid bilayers (PSLBs), which has led to development of TMP-based biosensors and biochips. However, PSLBs composed of natural lipids lack the high stability desired for many technological applications. One strategy is to use synthetic lipid monomers that can be polymerized to form robust bilayers. A key question is how lipid polymerization affects TMP structure and activity. In this study, we have examined the effects of UV polymerization of bis-Sorbylphosphatidylcholine (bis-SorbPC) on the photoactivation of reconstituted bovine rhodopsin (Rho), a model G-protein-coupled receptor. Plasmon-waveguide resonance spectroscopy (PWR) was used to compare the degree of Rho incorporation and activation in fluid and poly(lipid) PSLBs. The results show that reconstitution of Rho into a supported lipid bilayer composed only of bis-SorbPC, followed by photoinduced lipid cross-linking, does not measurably diminish protein function.  相似文献   
100.
The reaction of oxides of internal trans- and cis-perfluoroolefins with (1S, 4S)- or racemic camphor thiosemicarbazone leads to the formation of trans- and cis-isomers of (1S, 4S)- or racemic camphor 5′-fluoro-4′-hydroxy-4′,5′-di(perfluoroalkyl)-1′,3′-thiazolinyl-2′-hydrazones, respectively. Unsymmetrical dodecafluoro-2,3-epoxyhexane yields a mixture of regioisomeric hydrazones. The molecular structure of the trans-isomer of (1S, 4S)-camphor 5′-fluoro-4′-hydroxy-4′,5′-bis(trifluoromethyl)-1′,3′-thiazolinyl-2′-hydrazone has been established by X-ray crystallography. The quite rare example of cocrystallization of two diastereomers of the latter in homochiral crystal (sp. group P21) has been revealed.  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