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   20456篇
  免费   550篇
  国内免费   113篇
化学   14494篇
晶体学   197篇
力学   391篇
综合类   1篇
数学   3045篇
物理学   2991篇
  2022年   168篇
  2021年   205篇
  2020年   297篇
  2019年   293篇
  2018年   188篇
  2017年   185篇
  2016年   416篇
  2015年   366篇
  2014年   460篇
  2013年   949篇
  2012年   1004篇
  2011年   1295篇
  2010年   634篇
  2009年   542篇
  2008年   1044篇
  2007年   1120篇
  2006年   1094篇
  2005年   1072篇
  2004年   896篇
  2003年   759篇
  2002年   747篇
  2001年   264篇
  2000年   275篇
  1999年   245篇
  1998年   229篇
  1997年   264篇
  1996年   294篇
  1995年   233篇
  1994年   219篇
  1993年   254篇
  1992年   211篇
  1991年   199篇
  1990年   177篇
  1989年   153篇
  1988年   151篇
  1987年   177篇
  1986年   142篇
  1985年   216篇
  1984年   255篇
  1983年   184篇
  1982年   232篇
  1981年   254篇
  1980年   184篇
  1979年   197篇
  1978年   229篇
  1977年   170篇
  1976年   170篇
  1975年   159篇
  1974年   168篇
  1973年   147篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
Fifty-seven values for the ortho-benzylic coupling constant 4JMe? C?C? H (henceforth denoted as 4JOB) were obtained for a variety of heteroaromatic systems. It was shown that a good correlation exists between 4JOB when the methyl group is not α to the heteroatom and the SCF-MO bond order. This method can therefore be used as an experimental means of determining bond orders in heteroaromatic systems. An examination of bond alternation in thirteen heteroaromatic systems has given a measure of relative “degree of aromaticity” for a larger number of systems than previously reported by any single method.  相似文献   
62.
It is proven that a microcanonical Gibbs measure on a classical discrete lattice system is a mixture of canonical Gibbs measures, provided the potential is approximately periodic, has finite range and possesses a commensurability property. No periodicity is imposed on the measure. When the potential is not approximately periodic or does not have the commensurability property, the inclusion does not hold.As a by-product, a new proof is given of the fact that for a large class of potentials, a canonical Gibbs measure is a mixture of grand canonical measures. Thus the equivalence of ensembles is obtained in the sense of identical correlation functions.  相似文献   
63.
64.
65.
66.
67.
The synthesis of 3,4,6 tri-O-benzyl-D-glucal (4) has been accomplished by direct benzylation of triacetylglucal (yield 55%) and by zinc reduction of 3,4,6-tri-O-henzyl-2-acetoxy-1-bromoglucose (yield 26%). The nmr spectra of tribenzyl- and triacetyl-D-glucal in the presence of lanthanide shift reagents were reported.  相似文献   
68.
Dihydrothiinone 9a undergoes photocycloaddition regioselectively to all three C?C bonds of penta‐1,2,4‐triene ( 10 ), the relative stabilities of the biradical intermediates determining the product distribution. In contrast, cyclohexenone 9b and dihydropyranone 9c afford more complex mixtures of bicyclo[4.2.0]octanones, which also turn out to be less stable on chromatographic workup, reflecting the higher strain due to the shorter bond lengths (C? O and C? C vs. C? S) in the six‐membered rings, respectively.  相似文献   
69.
Acid Catalysed Rearrangement of 1,5-Dimethyl-6-methyliden-tricyclo[3.2.1.02,7]oct-3-en-8endo-ols The tricyclic alcohols 2,3,4 and 6 (Scheme 1) are synthesized by the reaction of the tricyclic ketone 1 with sodiumborohydrid or metalloorganic reagents. Their configuration at C(8) is determined by NMR. in the presence of Eu(fod)3. The exo-attack of 1 by the nucleophil forming the endo-alcohol is favored, the π-electrons of C(3) = C(4) hindering the endo-attack. On treatment with sulfuric acid in dioxane/water at 25° the tertiary alcohols yield aryl-substituted ketones. 3 gives in 78.5% yield a mixture of the 3-(dimethylphenyl)-2-butanones 12 and 13 , in addition to 16.5% of (2,3,4-trimethylphenyl)-2-propanon ( 14 ) (Scheme 2). The alcohols 4 and 6 yield mixtures of the 2-(dimethylphenyl)-3-pentanones 19 and 20 (72%), and 2-(dimethylphenyl)-propiophenones 21 and 22 (68%), respectively (Scheme 2). In the case of the secondary alcohol 2 mainly products derived from hydration at the C(6), C(9) double bond are formed, namely the mixture of diols 23 and 24 (21%), and the mixture of the isomeric 2-(dimethylphenyl)propanals 25, 26 and 27 (3%) (Scheme 3). - The structures of 12–14, 19/20, 21/22, 23/24 and 25/26/27 were established by spectroscopic data. In the case of 12 and 13 the degradation of their mixture to the known 1-(dimethylphenyl)ethanols 17/18 confirmed the assignment. - The most probable mechanism for the rearrangement of 3 is shown in Schemes 4 and 5. The reaction proceeds from 3 through a, b and g to 12 and 13; 14 is formed via e, f and i . In the case of 4 and 6 only the reaction analogue to 3 → a → b → g ?12/13 takes place. The isomeric aldehyds 25–27 formed from 2 could have the structures s, t , and v . The former two could be generated in a similar way as 12/13 from 3 , the latter one as shown in Scheme 8.  相似文献   
70.
Stopped-flow was used to evaluate the methylation and reduction kinetics of the isolated alpha subunit of acetyl-Coenzyme A synthase from Moorella thermoacetica. This catalytically active subunit contains a novel Ni-X-Fe4S4 cluster and a putative unidentified n = 2 redox site called D. The D-site must be reduced for a methyl group to transfer from a corrinoid-iron-sulfur protein, a key step in the catalytic synthesis of acetyl-CoA. The Fe4S4 component of this cluster is also redox active, raising the possibility that it is the D-site or a portion thereof. Results presented demonstrate that the D-site reduces far faster than the Fe4S4 component, effectively eliminating this possibility. Rather, this component may alter catalytically important properties of the Ni center. The D-site is reduced through a pathway that probably does not involve the Fe4S4 component of this active-site cluster.  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