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   90988篇
  免费   4992篇
  国内免费   11874篇
化学   71018篇
晶体学   1157篇
力学   2426篇
综合类   843篇
数学   13155篇
物理学   19255篇
  2024年   115篇
  2023年   676篇
  2022年   1880篇
  2021年   1811篇
  2020年   2218篇
  2019年   2170篇
  2018年   1862篇
  2017年   2718篇
  2016年   2837篇
  2015年   2394篇
  2014年   3312篇
  2013年   6663篇
  2012年   6223篇
  2011年   4992篇
  2010年   4214篇
  2009年   5777篇
  2008年   5976篇
  2007年   6207篇
  2006年   5655篇
  2005年   4792篇
  2004年   4442篇
  2003年   3688篇
  2002年   4922篇
  2001年   2840篇
  2000年   2625篇
  1999年   2462篇
  1998年   2136篇
  1997年   1688篇
  1996年   1414篇
  1995年   1351篇
  1994年   1202篇
  1993年   996篇
  1992年   951篇
  1991年   637篇
  1990年   540篇
  1989年   518篇
  1988年   376篇
  1987年   300篇
  1986年   276篇
  1985年   227篇
  1984年   238篇
  1983年   137篇
  1982年   211篇
  1981年   174篇
  1980年   194篇
  1979年   182篇
  1978年   169篇
  1977年   122篇
  1976年   108篇
  1973年   67篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Indoles undergo smooth alkylation with propargylic alcohols in the presence of 10 mol % of scandium triflate under mild conditions to produce 3-propargylated indoles in excellent yields with high selectivity.  相似文献   
992.
1 INTRODUCTION Indole and its derivatives have attracted much at-tention due to their chemical properties as well asbiological activities[1, . They have been widely used 2]as the materials for producing pigment, perfume,plant growth regulators, etc. Recently, it has alsobeen found that some indole derivatives present anti-tumor and antiviral activities[3~5]. During our sear-ches for bioactive compounds, a series of indole deri-vatives were synthesized, among …  相似文献   
993.
The synthesis of dendrons with the end-capped 5-(N,N-dimethylamino)naphthyl-1-ethynyl unit connected to conjugated naphthylethynyl or p-phenylethynyl chains, as the branches of the 1,3,5-substituted benzene core, have been undertaken by heterocoupling reaction between 1,3,5-triiodobenzene and the convenient end-capped 5-(N,N-dimethylamino)naphthylacetylene or 5-(N,N-dimethylamino)naphthylethynylphenylacetylene in the presence of the palladium-copper catalyst system, in excellent yields. The influence of the alternating naphthylethynyl-phenylethynyl chains on the fluorescence emission radiation, in the dendron structures, has been analyzed.  相似文献   
994.
Enantiomerically enriched (E)- and (Z)-configured α-acetoxyallylsilanes have been prepared starting from a chiral acylsilane bearing an asymmetric unit at the silicon portion. Treatment of these compounds with organocuprates afforded the respective vinylogous substitution products in high yields and high stereoselectivities. The transformations proceed essentially by complete anti attack of the nucleophiles to the allylic acetates and predominantly via transition states leading to the (E)-configured vinylsilane products. By the proper choice of the double bond geometry in the starting material, the configuration of the newly formed stereogenic center can be controlled. The method represents a new and flexible entry into chiral vinylsilanes that can be used for subsequent transformations. As an example, the α,β-unsaturated γ-chiral, naturally occurring ketone (S)-(+)-bishomomanicone was synthesized with this method, which represents the first synthetic access to this compound.  相似文献   
995.
This investigation conducted reaction channels of weakly bound complexes CO2…HF, CO2…HF…NH3, CO2…HF…NH2CH3, CO2…HF…NH(CH3)2, and CO2…HF…N(CH3)3 systems, using the Gaussian 98 package at the B3LYP/6‐311++G(3df,2pd) level. The syn‐fluoroformic acid or syn‐fluoroformic acid plus NH3 or amine conformers are more stable than the related anti‐fluoroformic acid or anti‐fluoroformic acid plus NH3 or amine conformers. However, the above‐mentioned weakly bound complexes are more stable than both the related syn‐ and anti‐type fluoroformic acid or acid plus NH3 or amine conformers and their related decomposed into CO2 + HF or CO2 + NHR3F (R?H, CH3) combined molecular systems. Five reaction channels of the weakly bound complexes exist. Each channel includes weakly bound complexes and their related above‐mentioned systems. Moreover, each reaction channel contains two transition states. The transition state between the weakly bound complex and anti‐fluoroformic acid type structure (T13) is significantly higher than that of internal rotation (T23) between syn‐ and anti‐FCO2H (or FCO2H…NR3) structures. However, the above‐mentioned T13 can significantly decrease its energy by adding the third molecule NH3 or NR3 (R?H or CH3). The more CH3 that is substituted in NR3 of the reaction channel, the lower the activation energy of the transition state in the system is affected. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005  相似文献   
996.
Amidines can be prepared on a solid support by reducing polymer-bound amidoximes with SnCl2·2H2O. The method has proved to be straightforward and highly efficient. Amidoximes attached to the solid support are readily available by treating resin-bound nitriles with hydroxylamine.  相似文献   
997.
The crystal structure of the product of the condensation of (salicylideneamino)nitroguanidine with salicylaldehyde on a Ni2+ ion template, K[Ni(C15H10N5O4)] · DMF, has been studied. It was established that a planar Ni complex, consisting of isolated [NiL] anions and solvated [K+ · DMF] cations, is formed. The negative charge of the anion is localized mainly on the O atoms of the nitro group. The nitroguanidine fragment of the ligand occurs in the tautomeric form, which was not reported previously.Deceased in 1995Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2273–2277, September, 1996.  相似文献   
998.
Ar原子电离能谱和Ar3p电子动量谱研究   总被引:1,自引:0,他引:1  
电子动量谱学(ElectronMomentumSPectroscoP则是近.二十年来发展起来的一种新兴的探测原子、分子和固体结构的手段,它不仅能够获得轨道结合能的信息,而且能够能壳分辨地得到轨道电子的动量分布(即动量表象中的波函数模方);同时它还是研究电子关联的最有效的实验手段.其  相似文献   
999.
1000.
The molecular structure of 1,3,5-tris (trimethylstannyl) benzene has been determined by gas-phase electron diffraction. The C — C bond length is in good agreement with that in benzene. In agreement with the somewhat electron-releasing character of the substituents, the endocyclic bond angles at the substituents are somewhat smaller than 120°. The mean value of Sn — C bond lengths is greater than that in tetraphenyltin and tetramethyltin. The SnMe3 groups appear freely rotating around the Caryl — Sn bonds. The following bond lengths (r g) and bond angles were determined: (Sn — C)mean 2.150 ± 0.007 Å, C — C 1.399 ± 0.005 Å, (C — H)mean 1.105 ± 0.006 Å, < C — C(Sn) — C 117.7 ± 1.7º, < Caryl — Sn — Cmethyl 106.7 ± 0.7º < Sn — C — H 111.5 ± 0.9º.  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