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   27884篇
  免费   9275篇
  国内免费   1387篇
化学   35104篇
晶体学   3篇
力学   366篇
数学   1600篇
物理学   1473篇
  2022年   2篇
  2021年   132篇
  2020年   1206篇
  2019年   2561篇
  2018年   992篇
  2017年   627篇
  2016年   3152篇
  2015年   3336篇
  2014年   3212篇
  2013年   3776篇
  2012年   2641篇
  2011年   1805篇
  2010年   2569篇
  2009年   2565篇
  2008年   2062篇
  2007年   1445篇
  2006年   1158篇
  2005年   1358篇
  2004年   1176篇
  2003年   1005篇
  2002年   655篇
  2001年   637篇
  2000年   406篇
  1999年   16篇
  1998年   26篇
  1997年   20篇
  1993年   2篇
  1992年   1篇
  1991年   1篇
  1973年   1篇
  1962年   1篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Diastereo‐ and enantioselective cycloaddition of 3‐nitroindoles with vinyl aziridine was realized under Pd‐catalysis using commercially available Walphos as the ligand, affording pyrroloindolines in high yields with high diastereo‐ and enantioselectivities. The reaction can be scaled up to a gram scale and the reaction products are easily converted to amino pyrroloindoline and other pyrroloindoline derivatives.  相似文献   
2.
3.
A multi‐state and multi‐stimuli‐responsive oxazine molecular switch that combines an electro‐base property and sensitive base/acid‐responsive properties was designed and synthesized. The multi‐state structures of the molecular switch, with different colors, were predicted by comparing the optical properties with reference molecules and confirmed by using NMR spectroscopy. The color‐switching mechanism under stimulation with acids and bases was investigated by using DFT calculations. Three single states can be obtained and the switching is unidirectional under acid and base stimulation. The electrochromic phenomenon of the molecular switch, which combines its electro‐base and base‐sensitive properties, was demonstrated. An electrochromic device that exhibited good electrochromic properties with excellent reversibility (2000 cycles) and high coloration efficiency (804 cm2 C?1) was successfully constructed.  相似文献   
4.
5.
Piperazine‐functionalized nickel ferrite (NiFe2O4) nanoparticles were synthesized as recoverable heterogeneous base catalysts using a routine method. The synthesized materials were characterized using various spectroscopic techniques such as infrared, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray, thermogravimetry analysis, and vibrating sample magnetometry. Catalytic efficiency was investigated in the synthesis of 2‐amino‐4H‐chromene derivatives via a one‐pot three component reaction of aldehyde and malononitrile with β or α‐naphthol/5‐methyle resorcinol under solvent‐free conditions with good to high yields. This method is operationally simple and has several advantages such as good to high yield, short reaction times, solvent‐free conditions, and easy synthesis. Moreover, the catalyst was recovered easily using an external magnet and reused three times without distinctive loss in catalytic activity.  相似文献   
6.
An experimentally feasible strong coupling system between a spin ensemble and a superconducting qubit is studied. The coupling strength can be exponentially enhanced by applying the squeezing transformations to the system. By means of the two spin ensembles commonly coupled to a superconducting qubit, a set of universal nonadiabatic holonomic single‐qubit quantum gates can be realized in a decoherence‐free subspace. Furthermore, this proposal is robust with respect to decay of the system parameters, and it is experimentally feasible with currently available technology.  相似文献   
7.
Indeno[1,2‐b]fluorene‐based [2,2]cyclophanes with 4n/4n and 4n/[4n+2] π‐electron systems were prepared, and their structures were identified by X‐ray crystallography. With short π–π distances around 3.0 Å, [2.2](5,11)indeno[1,2‐b]fluorenophane and its precursor [2.2](5,11)indeno[1,2‐b]fluorene‐6,12‐dionophane exhibit remarkable transannular interactions, leading to their unusual electrochemical and photophysical properties. With the aid of femtosecond transient absorption spectroscopy, the transition from the monomeric excited state to the redshifted H‐type dimeric state was first observed, correlating to the calculated excitonic energy splitting and the steady‐state absorption spectra induced by charge‐transfer‐mediated superexchange interaction.  相似文献   
8.
9.
Black phosphorus (BP) has recently drawn attention in photocatalysis for its optical properties. However, limited by the rapid recombination of photogenerated carriers, the use of BP for photocatalytic water splitting still remains a huge challenge. Herein, we prepare a black/red phosphorus (BP/RP) hetero‐phase junction photocatalyst by a wet‐chemistry method to promote the interfacial charge separation and thus achieve Z‐scheme photocatalytic water splitting without using sacrificial agents. The Z‐scheme mechanism was confirmed by time‐resolved transient absorption spectroscopy. This work provides a novel insight into the interface design of hetero‐phase junction with atomic precision.  相似文献   
10.
The synthesis and applications of carboxy‐MIDA‐boronate, a novel C1 building block, are described. This molecule is accessible via a ruthenium tetraoxide‐mediated cleavage of commercially available ethynyl‐MIDA‐boronate. In the course of this study, carboxy‐MIDA‐boronate was found to possess ambident reactivity towards nucleophiles. Carboxylic acid derivatization produces a broad range of previously unknown carbamoyl‐, oxycarbo‐ and thiocarboboronates. Carboxy‐MIDA‐boronate and its derivatives undergo condensations to access borylated heterocycles with boron at positions that are difficult to access using alternate methods. The resulting heterocycles participate in the Suzuki–Miyaura cross‐coupling reaction, enabling entry into diverse bis(heteroaryl) motifs. The carbon monoxide‐releasing capacity of carboxy‐MIDA‐boronate was also examined and applied in palladium‐catalyzed carbonylation.  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