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   136460篇
  免费   25321篇
  国内免费   17043篇
化学   84161篇
晶体学   1381篇
力学   6090篇
综合类   21篇
数学   21677篇
物理学   65494篇
  2023年   1088篇
  2022年   1031篇
  2021年   1189篇
  2020年   1703篇
  2019年   2213篇
  2018年   2634篇
  2017年   3140篇
  2016年   4340篇
  2015年   4146篇
  2014年   3989篇
  2013年   8039篇
  2012年   8001篇
  2011年   9332篇
  2010年   11503篇
  2009年   11306篇
  2008年   6474篇
  2007年   5797篇
  2006年   5211篇
  2005年   5476篇
  2004年   6023篇
  2003年   4859篇
  2002年   4507篇
  2001年   4370篇
  2000年   3493篇
  1999年   3370篇
  1998年   2792篇
  1997年   2539篇
  1996年   3079篇
  1995年   3282篇
  1994年   3466篇
  1993年   3466篇
  1992年   3053篇
  1991年   2621篇
  1990年   2316篇
  1989年   2337篇
  1988年   2316篇
  1987年   1575篇
  1986年   1614篇
  1985年   1462篇
  1984年   1561篇
  1983年   813篇
  1982年   1348篇
  1981年   1200篇
  1980年   1190篇
  1979年   899篇
  1978年   904篇
  1977年   1018篇
  1976年   1404篇
  1973年   780篇
  1972年   723篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen.  相似文献   
52.
A combination of pentafluorophenylboronic acid and oxalic acid catalyses the dehydrative substitution of benzylic alcohols with a second alcohol to form new C−O bonds. This method has been applied to the intermolecular substitution of benzylic alcohols to form symmetrical ethers, intramolecular cyclisations of diols to form aryl-substituted tetrahydrofuran and tetrahydropyran derivatives, and intermolecular crossed-etherification reactions between two different alcohols. Mechanistic control experiments have identified a potential catalytic intermediate formed between the aryl boronic acid and oxalic acid.  相似文献   
53.
54.
Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface.  相似文献   
55.
56.
Nonlinear Dynamics - The main purpose of this paper is to study both the underdamped and the overdamped dynamics of the nonlinear Helmholtz oscillator with a fractional-order damping. For that...  相似文献   
57.
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.  相似文献   
58.
59.
Analytical and Bioanalytical Chemistry - Formaldehyde is often applied in the industrial production of different products, such as textiles, insulation materials, or cosmetics, due to its...  相似文献   
60.
Summary Carbon deposits on the surface ofRu/Fe2O3 catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to reduce the amount of carbon deposit. .   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