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   5308篇
  免费   1318篇
  国内免费   743篇
化学   6130篇
晶体学   13篇
力学   108篇
综合类   15篇
数学   178篇
物理学   925篇
  2024年   2篇
  2023年   59篇
  2022年   123篇
  2021年   157篇
  2020年   300篇
  2019年   139篇
  2018年   203篇
  2017年   150篇
  2016年   325篇
  2015年   411篇
  2014年   396篇
  2013年   502篇
  2012年   456篇
  2011年   414篇
  2010年   373篇
  2009年   384篇
  2008年   456篇
  2007年   401篇
  2006年   357篇
  2005年   318篇
  2004年   289篇
  2003年   345篇
  2002年   103篇
  2001年   104篇
  2000年   98篇
  1999年   65篇
  1998年   52篇
  1997年   89篇
  1996年   80篇
  1995年   63篇
  1994年   32篇
  1993年   28篇
  1992年   26篇
  1991年   13篇
  1990年   18篇
  1989年   10篇
  1988年   7篇
  1987年   6篇
  1986年   3篇
  1985年   4篇
  1983年   3篇
  1982年   1篇
  1981年   1篇
  1980年   2篇
  1979年   1篇
排序方式: 共有7369条查询结果,搜索用时 46 毫秒
991.
992.
CuII‐macrocycle functionalized hexametaphosphate‐capped silica mesoporous nanoparticles have been prepared and used for the selective and sensitive detection of hydrogen sulfide in aqueous environments. The possibility of using different metal complexes combined with different capping anions and choice of different dyes or other sensing molecules as indicators makes this new protocol highly appealing for the preparation of new sensing systems for sulfide detection in different environments.  相似文献   
993.
Diels–Alder reactions have become established as one of the most effective ways to prepare stereochemically complex six-membered rings. Different catalysis concepts have been reported, including dienophile activation by Lewis acids or H-bond donors and diene activation by bases. Herein we report a new concept, in which an acidic prodiene is acidified by a Lewis acid to facilitate deprotonation by an imidazolium–aryloxide entity within a polyfunctional catalyst. A metal dienolate is thus formed, while an imidazolium–ArOH moiety probably forms hydrogen bonds with the dienophile. The catalyst type, readily prepared in few steps in high overall yield, was applied to 3-hydroxy-2-pyrone and 3-hydroxy-2-pyridone as well as cyclopentenone prodienes. Maleimide, maleic anhydride, and nitroolefin dienophiles were employed. Kinetic, spectroscopic, and control experiments support a cooperative mode of action. High enantioselectivity was observed even with unprecedented TONs of up to 3680.  相似文献   
994.
Herein, we report that highly chemoselective and enantioselective reduction of 2-vinyl-substituted pyridines has been achieved for the first time. The reaction, which uses chiral spiro-bicyclic bisboranes as catalysts and HBpin and an acidic amide as reducing reagents, proceeds through a cascade process involving 1,4-hydroboration followed by transfer hydrogenation of a dihydropyridine intermediate. The retained double bond in the reduction products permits their conversion to natural products and other useful heterocyclic compounds by simple transformations.  相似文献   
995.
Recent advances in computational design have enabled the development of primitive enzymes for a range of mechanistically distinct reactions. Here we show that the rudimentary active sites of these catalysts can give rise to useful chemical promiscuity. Specifically, RA95.5‐8, designed and evolved as a retro‐aldolase, also promotes asymmetric Michael additions of carbanions to unsaturated ketones with high rates and selectivities. The reactions proceed by amine catalysis, as indicated by mutagenesis and X‐ray data. The inherent flexibility and tunability of this catalyst should make it a versatile platform for further optimization and/or mechanistic diversification by directed evolution.  相似文献   
996.
We report 8‐step syntheses of (?)‐minovincine and (?)‐aspidofractinine using easily available and inexpensive reagents and catalyst. A key element of the strategy was the utilization of a sequence of cascade reactions to rapidly construct the penta‐ and hexacyclic frameworks. These cascade transformations included organocatalytic Michael‐aldol condensation, a multistep anionic Michael‐SN2 cascade reaction, and Mannich reaction interrupted Fischer indolization. To streamline the synthetic routes, we also investigated the deliberate use of steric effect to secure various chemo‐ and regioselective transformations.  相似文献   
997.
998.
Numerous protocols have been developed for the functionalization of aromatic substances. Among them, the strategy by which aromatic substrates are activated in situ to generate dearomatized intermediates is highly efficient but challenging, especially in the field of asymmetric catalysis. In this Concept article, the application of some well-established chiral Lewis base catalysis, including primary/secondary amines and N-heterocyclic carbenes, that can covalently form catalyst-tethered dearomatized ortho/para-quinodimethane species with diverse heteroaryl and aryl carbonyl substrates is summarized in a number of asymmetric cycloaddition and addition reactions with diverse reagents generally having electrophilic properties. As a result, a variety of enantioenriched aromatic products with higher molecular complexity are constructed effectively through a rearomatization process.  相似文献   
999.
Recent advances in catalytic asymmetric carbon–carbon bond‐forming reactions of non‐heteroaromatic amide substrates are highlighted. Among carbonyl compounds, amides have received limited attention in catalytic asymmetric transformations mainly owing to their lower reactivity. Amides are reluctant to form enolates for nucleophilic addition, and α,β‐unsaturated amides exhibit diminished electrophilicity at the β‐carbon. Recent advances in asymmetric catalysis rendered these amides amenable to enantioselective reactions with perfect atom economy, producing synthetically useful chiral building blocks. This Minireview summarizes recent developments in the field.  相似文献   
1000.
ABSTRACT

We study the effect of the external electric field Fext on the low-temperature electron mobility μ in an asymmetrically doped AlxGa1-xAs based V-shaped double quantum well (VDQW) structure. We show that nonlinearity of µ occurs under double subband occupancy on account of intersubband effects. The field Fext alters the VDQW potential leading to transfer of subband wave functions between the wells, which affects the scattering potentials and hence μ. In the VDQW structure, due to the alloy channel layer, the alloy disorder (Al-) scattering happens to be significant along with the ionised impurity (Imp-) scattering. The non-linear behaviour of μ is because of μImp, while the overall magnitude of μ is mostly due to μAl. The increase of difference in the doping concentrations of the outer barriers increases the nonlinearity of μ. The oscillatory character of μ is amended by varying the width of the well and barrier and also the height of the VDQW. Our results can be used to study VDQW based nanoscale field effect transistor structures.  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