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   55422篇
  免费   11502篇
  国内免费   4003篇
化学   54044篇
晶体学   618篇
力学   1820篇
综合类   207篇
数学   4008篇
物理学   10230篇
  2024年   87篇
  2023年   447篇
  2022年   825篇
  2021年   979篇
  2020年   2034篇
  2019年   3337篇
  2018年   1703篇
  2017年   1382篇
  2016年   4234篇
  2015年   4461篇
  2014年   4579篇
  2013年   5511篇
  2012年   4758篇
  2011年   4119篇
  2010年   4118篇
  2009年   4088篇
  2008年   3544篇
  2007年   2916篇
  2006年   2388篇
  2005年   2394篇
  2004年   2071篇
  2003年   1800篇
  2002年   2491篇
  2001年   1824篇
  2000年   1681篇
  1999年   712篇
  1998年   347篇
  1997年   277篇
  1996年   299篇
  1995年   208篇
  1994年   234篇
  1993年   164篇
  1992年   144篇
  1991年   132篇
  1990年   129篇
  1989年   105篇
  1988年   70篇
  1987年   60篇
  1986年   61篇
  1985年   49篇
  1984年   31篇
  1983年   20篇
  1982年   15篇
  1981年   14篇
  1980年   9篇
  1979年   12篇
  1977年   6篇
  1976年   10篇
  1975年   7篇
  1957年   6篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
An efficient approach has been developed for the synthesis of an isofervenulin analogue 1 employing a one‐pot condensation‐substitution reaction of a chlorocarboethoxytriazine (electrophile) with a urea (nucleophile). The resulting cyclization reaction resulted in the synthesis of a pyrimido‐heterocycle in good yield in either acidic or basic media. The former was assisted by utilizing trimethylsilyl chloride.  相似文献   
102.
Crystal Structure of the Zinc Amide Zn[N(SiMe3)2]2 X‐ray quality crystals of Zn[N(SiMe3)2]2 (monoclinic, P21/c) are obtained by sublimation of the zinc amide Zn[N(SiMe3)2]2 at —30 °C in vacuo (300 torr). According to the result of the X‐ray structural analysis, Zn[N(SiMe3)2]2 contains an almost linear N‐Zn‐N unit with two short N‐Zn bonds.  相似文献   
103.
5‐Methylene‐2‐oxazolidinone (1) and 5‐methylene‐1,3‐thiazolidine‐2‐thione (4) react with various isocyanates to give the corresponding urethanes 3 and 5 in high yields in the presence of palladium(0) or palladium(II) catalyst under mild reaction conditions. A mechanism is proposed. Copyright © 2003 John Wiley & Sons, Ltd.  相似文献   
104.
林惠文  朱文祥 《中国化学》2003,21(8):1054-1058
The structure of the title adduct comprises a phenanthroline derivative 2-phenyl-imidazo[4,5-f]1,10-phenanthroline and a methanol.The composition of the crystalline adduct was characterized as C19H12N4.CH3OH.It belongs to orthorhombic system,space group Pna21 with a=1.3693(4)nm,b=2.2988(7)nm,c=0.51338(15)nm,V=1.6160(8)nm^3.Z=4,and final R1=0.0423.wR2=0.1012 .Crystal structure shows that all the 19 carbon atoms and 4 nitrogen atoms are coplanar.The bond length data indicated that a very extensive conjugation system was formed.This conjugation makes the compound being a potentially excellent energy transformer used for luminescent materials.  相似文献   
105.
考虑到量子相干效应和界面散射效应 ,利用 L ambert理论模型 ,计算正常金属 /绝缘层 /超导 /绝缘层 /正常金属双垒隧道结中的准粒子输运系数和隧道谱。研究表明 :( 1)所有的准粒子输运系数和电导谱在超导能隙之上都随能量作周期性振荡 ,其振荡周期依赖于超导层的厚度 ;( 2 )在超导能隙之上 Andreev反射系数随能量呈现周期性消失现象 ;( 3)在绝缘层势垒强度取很大的隧道极限下 ,超导层中会形成一系列的准粒子束缚态 ,其位置由量子化条件决定 ;( 4)界面散射效应不仅能压低各子能隙电导峰 ,还能使子能隙电导峰劈裂为两个峰。  相似文献   
106.
107.
A new method based on anion exchange resin separation and graphite furnace atomic absorption spectrometry (GFAAS) detection is proposed for the determination of inorganic tin species. The result showed that Sn(IV) was quantitatively retained on the resin when [HCl] = 9.0 mol · L−1, but Sn(II) could not be adsorbed on the resin under the same condition. Thus, a separation of Sn(II) and Sn(IV) has been realized. When the concentration of NaOH solution was between 2.0–7.0 mol · L−1, Sn(IV) that adsorbed on the resin could be eluated from the resin completely. Meanwhile, under the atmosphere and the nitrogen states, the translation between Sn(II) and Sn(IV) was investigated. Under the optimal conditions, the detection limit of Sn(IV) is 0.40 μg · L−1 with RSD of 2.3% (n = 5, c = 2.0 μg · L−1). The proposed method was applied to the speciation analysis of tin in different water samples and the recovery of total Sn was in the range of 98.7–101.7%. In order to verify the accuracy of the method, a certified reference water sample was analyzed and the results obtained were in good agreement with the certified value.  相似文献   
108.
109.
Mesoporous polymer microspheres with gold (Au) nanoparticles inside their pores were prepared considering their surface functionality and porosity. The Au/polymer composite microspheres prepared were characterized by transmission electron microscope (TEM), X‐ray diffraction (XRD), and Brunauer–Emmett–Teller (BET) techniques. The results showed that the adsorption of Au nanoparticles could be increased by imparting the pore structure and surface‐functional groups into the supporting polymer microspheres (in this study, poly (ethylene glycol dimethacrylate‐co‐acrylonitrile) and poly (EGDMA‐co‐AN) system). Above all, from this study, it was established that the porosity of the polymer microspheres is the most important factor that determines the distribution and adsorption amount of face‐centered cubic (fcc) Au nanoparticles in the final products. Our study showed that the continuous adsorption of Au nanoparticles with the aid of the large surface area and surface interaction sites formed more favorably the Au/polymer composite microspheres. The BET measurements of Au/poly(EGDMA‐co‐AN) composite microspheres reveals that the adsorption of Au nanoparticles into the pores kept the pore structure intact and made it more porous. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5627–5635, 2004  相似文献   
110.
Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe2Cl2(PMP)] and [SnMe2Br2(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (1H, 13C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.  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