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   27388篇
  免费   3790篇
  国内免费   4538篇
化学   21900篇
晶体学   425篇
力学   1219篇
综合类   374篇
数学   3134篇
物理学   8664篇
  2024年   44篇
  2023年   251篇
  2022年   671篇
  2021年   688篇
  2020年   734篇
  2019年   893篇
  2018年   724篇
  2017年   729篇
  2016年   1108篇
  2015年   1269篇
  2014年   1507篇
  2013年   2028篇
  2012年   2345篇
  2011年   2380篇
  2010年   1801篇
  2009年   1792篇
  2008年   2136篇
  2007年   1934篇
  2006年   1735篇
  2005年   1533篇
  2004年   1392篇
  2003年   1177篇
  2002年   1330篇
  2001年   1080篇
  2000年   829篇
  1999年   605篇
  1998年   424篇
  1997年   405篇
  1996年   330篇
  1995年   281篇
  1994年   264篇
  1993年   227篇
  1992年   206篇
  1991年   160篇
  1990年   153篇
  1989年   115篇
  1988年   83篇
  1987年   68篇
  1986年   59篇
  1985年   50篇
  1984年   32篇
  1983年   25篇
  1982年   16篇
  1981年   17篇
  1980年   12篇
  1978年   12篇
  1977年   10篇
  1976年   9篇
  1973年   7篇
  1936年   9篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
Pure copolymer nanoparticles from 8-aminoquinoline (AQ) and 2-ethylaniline (EA) were easily synthesized by a chemically oxidative polymerization in three different aqueous media. The potential and temperature of polymerization solution were used to successfully follow the polymerization progress. The molecular and morphological structures of the resulting AQ/EA copolymer particles were systematically characterized by IR, UV/Vis, NMR, gel permeation chromatography, laser particle-size analysis, atomic force and transmission electron microscopy. The oxidation potential of the monomers as well as the polymerization yield, structure, and properties of the particles were found to significantly depend on AQ/EA ratio, polymerization temperature and medium. It is surprisingly found that AQ homopolymerization and AQ/EA (50:50) copolymerization at 5 degrees C in HCl simply afford nano-ellipsoids with the major/minor axis diameters of 24/14 nm and 80/67 nm, respectively. A simple method of synthesizing semiconducting pure nanoparticles by introducing the AQ units with positively charged quaternary ammonium groups but in the absence of adscititious stabilizer or sulfonic substituent on the monomers is established first. Both the molecular weight and bulk electroconductivity of the copolymers exhibit a maximum at AQ content of 10 mol %. The solubility and film formability of the copolymers are good in highly polar solvents and reach the optimal at the AQ content of 20 and 10 mol %, respectively.  相似文献   
42.
用火焰原子吸收法检测了深圳市1408例13岁以下儿童发中钙,铁,镁的元素含量,并探讨了元素含量与年龄,性别的关系,结果显示,性别差异有显著意义,钙,镁含量随年龄增长有相似变化。  相似文献   
43.
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   
44.
Capillary supercritical fluid chromatographic (SFC) method has been developed for the determination of panaxadiol and panaxatriol in ginseng and its preparations. 0.1 g ginseng or an appropriate amount of its preparations was hydrolysed by 15% H2SO4 in an ethanol:water (1:1 v/v) solution for 4 h followed by 15% NaOH for 0.5 h. The mixture was extracted by cyclohexane. The cyclohexane extracts were purified by a partition column and concentrated by an adsorption column and then analysed by SFC. Methyltestosterone was used as the internal standard.  相似文献   
45.
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   
46.
本文提出了富烯碳原子簇的石墨层间闭合形成机理,由该机理推出的许多结果与实验事实符合很好。我们认为碳原子簇自由基的快速淬灭及其淬灭速度是富烯碳原子簇形成及其丰度的决定因素。由此得出富烯碳原子簇在给定实验条件下产生的必然性,并预言不同大小的富烯碳原子簇可以通过优化实验条件选择性地合成。  相似文献   
47.
The Ru-catalyzed intramolecular [5+2] cycloaddition of cyclopropylenynes is investigated with respect to the regio- and diastereoselectivity as well as the functional group compatibility of the reaction. Evidence for the mechanism as occurring through a ruthenacyclopentene intermediate is elucidated from 1) the study of the diastereoselectivity of the cycloaddition; 2) the effect of variation of substituents on the regioselectivity of cyclopropyl bond cleavage in 1,2-trans- and 1,2-cis-disubstituted cyclopropanes and 3) examples that clearly do not involve ruthenacyclohexene as intermediates as products still incorporate the cyclopropyl moiety. The scope and limitations of the Ru-catalyzed cycloaddition are discussed and compared with the Rh-catalyzed reaction. The potential power of this methodology towards natural product total synthesis is demonstrated by the formation of several polycyclic systems with the chosen reaction conditions and readily available cyclopropylenyne substrates.  相似文献   
48.
49.
The addition of carboxylic acids to terminal alkynes is efficiently catalyzed by the early transition-metal complex Re(CO)5Br in toluene or n-heptane at 110 degrees C in an air atmosphere, affording the anti-Markovnikov adducts in good yields with high selectivity. In most cases, the reactions afford unusual Z-adduct predominantly. When n-heptane was used as solvent, Re(CO)5Br can be partly recovered from the reaction mixture.  相似文献   
50.
Polyoxime-urethanes have been synthesized from dioximes and diisocyanates, and their structures have been ascertained by elemental analysis and infrared spectroscopy. They can be represented by the general formula: These polymer films were photolyzed by using a high-pressure 100-W mercury lamp, and the rate of decomposition of the N? O bond was determined by use of ultraviolet and infrared spectra, or comparing the photochemical behavior with that of corresponding model compounds. Upon irradiating these polymers in the presence or absence of sensitizers or a hydrogen donor, there were obtained photolyzed polymers of low molecular weight, of which the molecular weights were estimated by observing the viscosity changes. To deduce the mechanism of photodegradation of polyoxime-urethane, photolysis of benzophenone oxime-phenyl urethane was investigated as a model compound.  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