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   30323篇
  免费   3675篇
  国内免费   3173篇
化学   21945篇
晶体学   371篇
力学   1458篇
综合类   234篇
数学   3697篇
物理学   9466篇
  2024年   77篇
  2023年   465篇
  2022年   848篇
  2021年   934篇
  2020年   945篇
  2019年   966篇
  2018年   822篇
  2017年   783篇
  2016年   1191篇
  2015年   1202篇
  2014年   1440篇
  2013年   2034篇
  2012年   2369篇
  2011年   2611篇
  2010年   1809篇
  2009年   1772篇
  2008年   2007篇
  2007年   1832篇
  2006年   1635篇
  2005年   1461篇
  2004年   1174篇
  2003年   937篇
  2002年   916篇
  2001年   746篇
  2000年   635篇
  1999年   590篇
  1998年   511篇
  1997年   452篇
  1996年   489篇
  1995年   398篇
  1994年   375篇
  1993年   350篇
  1992年   330篇
  1991年   282篇
  1990年   235篇
  1989年   198篇
  1988年   171篇
  1987年   137篇
  1986年   145篇
  1985年   156篇
  1984年   102篇
  1983年   64篇
  1982年   72篇
  1981年   57篇
  1980年   53篇
  1979年   60篇
  1978年   40篇
  1976年   39篇
  1974年   42篇
  1973年   46篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
31.
Novel chiral bisbinaphthyl compounds have been synthesized for the enantioselective fluorescent recognition of mandelic acid. By introducing dendritic branches to the chiral receptor unit, the fluorescence signals of the receptors are significantly amplified because of the light-harvesting effect of the dendritic structure. This has greatly increased the sensitivity of the sensors in the fluorescent recognition. Study of the three generation sensors demonstrates that the generation zero sensor is the best choice for the recognition of mandelic acid because of its greatly increased fluorescence signal over the core and its high enantioselectivity. This sensor is potentially useful for the high throughput screening of chiral catalysts for the asymmetric synthesis of alpha-hydroxycarboxylic acids.  相似文献   
32.
建立了一种人工神经网络-X射线荧光光谱法测定钢中酸溶铝的方法,用X射线荧光光谱法测定低合金钢中总铝值,应用所建立的ANN-BP网络模型,输入总铝含量直接预测出酸溶铝含量。同时使用改进的BP算法,避免了神经网络学习中可能产生的麻痹现象。该方法用于钢中酸溶铝的测定,结果满意。  相似文献   
33.
The rate constant for the reaction of phenyl radical with hydrogen bromide has been measured with the cavity-ring-down method at six temperatures between 297 and 523 K. The Arrhenius expression for the H abstraction reaction can be effectively given by: . The values of these parameters are similar to those for the H + HBr reaction, but are in sharp contrast to those for alkyl radical reactions. The gross difference between the alkyl radical reactions and the phenyl and H-atom reactions could be rationalized in terms of the inductive effects of these radicals as measured by Taft's σ* (polar) constants. © 1993 John Wiley & Sons, Inc.  相似文献   
34.
New anti-HIV prodrugs, conjugates of AZT and d4T with boranophosphates, were prepared by the H-phosphonate method. Their structures were determined by negative ion electrospray ionization mass spectrometry (ESI-MS) in conjunction with tandem mass spectrometry (MS/MS). The fragmentation pathways were investigated, and most of the fragment ions contained the boranophosphate or phosphinate group.  相似文献   
35.
1:1 and 2:1 palladium(II) complexes of egta4– (egta4– = glycine, N,N-(1,2-ethanediylbis)(oxy-2,1-ethanediyl)bis[N-carboxymethyl]) were prepared by 1:1 and 2:1 addition of K2PdCl4 to K4egta, and examined by 1H-, 13C- and 15N-n.m.r. methods. The 1:1 complex, [Pd(egta)]2– in solution, utilizes a square-planar coordination comprised of two nitrogen and two glycinato carboxylate donors of egta4–, leaving two glycinato carboxylates pendant. The complex has a cis-(R,S) stereochemistry which places both pendant carboxylates below the PdN2O2 square plane and the tether backbone of egta4– in the up, up sense above the same plane. The cis-(R,S) assignment was assisted by computer simulations of the 13C-n.m.r. spectrum for four possible isomers. Only cis-(R,S) and trans-(R,R) calculated 13C-spectra were compatible with the observed 13C-n.m.r. pattern. The HH NOESY spectrum of [Pd(egta)]2– detects long range coupling of the backbone –OCH2CH2O– linkage with both coordinated and pendant glycinato CH2 moieties. The cis-(R,S) isomer's tortional movements allow such contacts whereas a trans-(R,R) isomer does not. The 2:1 complex, [Pd2(egta)(H2O)2] in solution has an extended-chain structure with each palladium(II) center coordinated in the mer-iminodiacetate-like coordination with two bound glycinato-functionalities.  相似文献   
36.
The UV light irradiation of isoniazid (I) in methanol four products, isonicotinic acid (II), isonicotinamide (III), N, N′-bis(isonicotinic acid)hydrazide (IV) and isonicotinaldehyde isonicotinyl hydrazone (V), in ethanol three products, (III), (IV) and acetaldehyde isonicotinyl hydrazone (VI) were isolated and identified. Also, the photoreaction mechanism of isoniazid in methanol and ethanol were discussed.  相似文献   
37.
Hua J  Lin W 《Organic letters》2004,6(6):861-864
[structure: see text] A family of chiral metallacyclophanes has been readily assembled based on robust Pt-acetylide linkage and characterized by a variety of spectroscopic techniques and X-ray crystallography. The steric congestion around the chiral dihydroxy groups in rigid metallacyclophane 4 prevents their reactions with Ti(O(i)()Pr)(4) to form active catalysts for enantioselective diethylzinc additions to aromatic aldehydes. In contrast, chiral dihydroxy groups in more flexible unclosed metallacyclophane 5 are effective ligands for enantioselective catalytic diethylzinc additions to aromatic aldehydes.  相似文献   
38.
39.
Let be a bounded smooth domain in , and a function with compact support in . Moser's inequality states that there is a constant , depending only on the dimension , such that

where is the Lebesgue measure of , and the surface area of the unit ball in . We prove in this paper that there are extremal functions for this inequality. In other words, we show that the

is attained. Earlier results include Carleson-Chang (1986, is a ball in any dimension) and Flucher (1992, is any domain in 2-dimensions).

  相似文献   

40.
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