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   1439篇
  免费   74篇
  国内免费   274篇
化学   1248篇
晶体学   8篇
力学   72篇
综合类   1篇
数学   179篇
物理学   279篇
  2023年   9篇
  2022年   19篇
  2021年   29篇
  2020年   24篇
  2019年   19篇
  2018年   34篇
  2017年   25篇
  2016年   29篇
  2015年   30篇
  2014年   46篇
  2013年   134篇
  2012年   114篇
  2011年   122篇
  2010年   71篇
  2009年   97篇
  2008年   81篇
  2007年   80篇
  2006年   55篇
  2005年   76篇
  2004年   145篇
  2003年   120篇
  2002年   90篇
  2001年   29篇
  2000年   26篇
  1999年   27篇
  1998年   26篇
  1997年   24篇
  1996年   21篇
  1995年   11篇
  1994年   7篇
  1993年   16篇
  1992年   10篇
  1990年   7篇
  1989年   9篇
  1987年   6篇
  1986年   6篇
  1984年   9篇
  1983年   5篇
  1982年   5篇
  1980年   8篇
  1979年   8篇
  1978年   8篇
  1976年   4篇
  1975年   4篇
  1974年   4篇
  1973年   4篇
  1972年   6篇
  1967年   4篇
  1958年   4篇
  1929年   4篇
排序方式: 共有1787条查询结果,搜索用时 31 毫秒
951.
The X-ray crystal structures of trigonal silver(I) cyclodextrin complexes of introverted bidentate sulfur (1) and phosphorus (2) ligands give a clear indication on how a cyclodextrin-included ligand may bind in a ditopic fashion both the encapsulated metal ion and the cyclodextrin inner wall. In the solid state, the silver-coordinated water molecule of complex [Ag(H2O)(1)]BF4 induces a major distortion of the macrocyclic structure, along with dramatic conformational changes in the two opposite glucose units with which it is hydrogen bonded. In complex [AgBr(2)], the included bulky bromide anion, which lacks hydrogen bonding capability, does not affect the overall circular shape of the cyclodextrin receptor. A 1H-19F HOESY experiment conducted on the silver(I) complex of 1 in CDCl3 showed that in this solvent, the water molecule is displaced by the BF4 counterion at the metal coordination site, the cavity being here no longer distorted.  相似文献   
952.
A series of systematically varied ’rigid-rod’ octahedral ruthenium-acetylide complexes, bearing conjugated bis(acylamino)triazine (DAT) substituents capable of ADAD-DADA pairing, of general formula trans-[(dppe)2Ru(Cl)(CC-C6H4-DAT(R)2)] (R = Et, i-Pr, t-Bu, n-C5H11) have been synthesized and thoroughly characterized in solution by 1H NMR and in the solid state. trans-[Ru(-CC-C6H4-DAT(R)2)2(dppe)2] (R = n-C5H11) has also been designed to form discrete oligomeric chains in solution.  相似文献   
953.
This work is aimed to show that various problems from different fields can be modeled more efficiently using multiplicative calculus, in place of Newtonian calculus. Since multiplicative calculus is still in its infancy, some effort is put to explain its basic principles such as exponential arithmetic, multiplicative calculus, and multiplicative differential equations. Examples from finance, actuarial science, economics, and social sciences are presented with solutions using multiplicative calculus concepts. Based on the encouraging results obtained it is recommended that further research into this field be vested to exploit the applicability of multiplicative calculus in different fields as well as the development of multiplicative calculus concepts.  相似文献   
954.
A two-state oscillator in a viscous liquid is composed of a micron-scale particle whose intrinsic dynamics is defined by linear potentials that undergo configuration-coupled transitions and is externally driven by a piecewise constant periodic force of varying amplitude and frequency. This elementary example of "active matter" has the minimal elements that allow us to study synchronization in the presence of thermal fluctuations. Experiments reveal the presence of synchronized states (and Arnol'd tongues), which we explain using analytical and numerical calculations. The system maintains synchronization by adjusting the phase between the bead and the clock. We discuss the relevance of this model to synchronization in real-world systems, including the role of thermal noise.  相似文献   
955.
The anisotropic shape transformation of gold nanorods (GNRs) with H2O2 was observed in the presence of “cethyl trimethylammonium bromide” (CTAB). The adequate oxidative dissolution of GNR is provided by the following autocatalytic scheme with H2O2: Au0 → Au+, Au0 + Aun+ → 2Au3+, n = 1 and 3. The shape transformation of the GNRs was investigated by UV-vis spectroscopy and transmission electron microscopy (TEM). As-synthesised GNRs exhibit transverse plasmon band (TPB) at 523 nm and longitudinal plasmon band (LPB) at 731 nm. Upon H2O2 oxidation, the LPB showed a systematic hypsochromic (blue) shift, while TPB stays at ca. 523 nm. In addition, a new emerging peak observed at ca. 390 nm due to Au(III)-CTAB complex formation during the oxidation. TEM analysis of as-synthesised GNRs with H2O2 confirmed the shape transformation to spherical particles with 10 nm size in 2 h, whereas centrifuged nanorod solution showed no changes in the aspect ratio under the same condition. Au3+ ions produced from oxidation, complex with excess free CTAB and approach the nanorods preferentially at the end, leading to spatially directed oxidation. This work provides some information to the crystal stability and the growth mechanism of GNRs, as both growth and shortening reactions occur preferentially at the edge of single-crystalline GNRs, all directed by Br ions.  相似文献   
956.
New pyrimidine nucleoside derivatives with nitric oxide(NO) donor were systematically synthesized.The antivirus activities of these nucleoside analogues against vesicular stomatitis virus(VSV) in Wish cell were evaluated.It was demonstrated that most of compounds had stronger antiviral acitivity than acyclovir,while their toxicities were similar or lower to acyclovir.  相似文献   
957.
(3S,4R)-Bengamide E(2) was synthesized starting from D-glucono-δ-lactone(3) and the key deoxygenation step from 13 to 15 was achieved by the application of NaBH3CN and ZnI2.Compared with natural bengamide E(1),the synthetic compound(35,4R)-bengamide E(2) was inactive against the cell growth of HUVEC and cancer cells.These data represent the significance of the stereochemistry at C-3 and C-4 of bengamides for structural recognition and binding with the target(s).  相似文献   
958.
Two new phenethanol glycosides,named ligurobustoside P(1),ligurobustoside Q(2) have been isolated from the leaves of Ligustrum robustum,together with the known compound angoroside A(3) which was firstly isolated from this species.The structures of the two new phenethanol glycosides(1-2) were elucidated by a combination of high-resolution electron ionization mass spectrometry(HR-ESI-MS),1H NMR,13C NMR,HMQC,and HMBC spectra for the first time.  相似文献   
959.
We report on the electrochemical behaviour and electropolymerization of self‐assembled monolayers (SAMs) of methylene blue (MB) on gold electrodes. The SAMs of MB on gold electrodes were prepared by immersing the substrates into a solution of 1.0 mM MB in absolute ethanol for different times at room temperature. Cyclic voltammetry experiments exhibited that reductive desorption of MB monolayer takes place at three different potentials on polycrystalline gold electrodes, while reductive desorption of MB monolayer consists of only one peak on single crystal Au(111) substrates. Calculated charge densities for different immersion times indicated that optimal immersion time for self‐assembly of MB is 96 h. Electropolymerization of SAMs of MB on gold electrode was achieved by applying 0.95 V for 1 s in 0.1 M borate buffer solution (pH: 9.0). It was observed that poly(MB) monolayers are highly stable in acidic media. ATR‐FTIR and UV‐vis spectra exhibited differences between monomer and polymer monolayers, which are attributed to surface‐confined electropolymerization. STM image of poly(MB) monolayer on Au(111) substrate revealed a surface that is covered by well‐ordered, collateral nanowires with an average size of 3 nm.  相似文献   
960.
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