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   649篇
  免费   21篇
  国内免费   2篇
化学   570篇
晶体学   3篇
力学   2篇
数学   30篇
物理学   67篇
  2023年   3篇
  2021年   4篇
  2020年   7篇
  2019年   9篇
  2018年   8篇
  2017年   4篇
  2016年   20篇
  2015年   20篇
  2014年   9篇
  2013年   25篇
  2012年   26篇
  2011年   53篇
  2010年   32篇
  2009年   24篇
  2008年   42篇
  2007年   49篇
  2006年   36篇
  2005年   45篇
  2004年   34篇
  2003年   26篇
  2002年   30篇
  2001年   16篇
  2000年   20篇
  1999年   2篇
  1998年   7篇
  1997年   7篇
  1996年   8篇
  1995年   7篇
  1994年   7篇
  1993年   4篇
  1992年   7篇
  1991年   2篇
  1990年   10篇
  1989年   5篇
  1988年   4篇
  1987年   3篇
  1986年   3篇
  1985年   7篇
  1984年   7篇
  1982年   3篇
  1981年   6篇
  1980年   5篇
  1979年   6篇
  1978年   4篇
  1974年   3篇
  1973年   3篇
  1972年   2篇
  1941年   1篇
  1929年   1篇
  1905年   2篇
排序方式: 共有672条查询结果,搜索用时 0 毫秒
61.
Hyperbranched poly(ether sulfone)s were prepared by the self‐polycondensation of the novel AB2 monomer, 4‐(3,5‐hydroxyphenoxy)‐4′‐fluorodiphenylsulfone. The high‐molecular‐weight polymers were isolated in good yields. The degree of branching (DB) of the resulting polymers was investigated by the preparation of dendritic and linear model compounds. The DB determined by gated decoupling 13C NMR measurements was in the range 0.17–0.41 and was dependent on the base used for the self‐polycondensation. It was found that cesium fluoride was an effective base to form the polymer having the DB of 0.41. The resulting hyperbranched poly(ether sulfone)s showed good solubility in organic solvents. The solubility and the glass transition temperature of the polymers were influenced by the terminal functional groups. The unique thermal crosslinking phenomenon was observed during the DSC measurements of the hydroxyl‐terminated hyperbranched poly(ether sulfone) under air condition. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   
62.
Aquation of [Cr(pic)3]0 and [Cr(pic)2(OH)]2 0 in aqueous HClO4 solutions leads to formation of the common product – [Cr(pic)2(H2O)2]+. The first, reversible stage, the ring opening via Cr—N bond breaking in [Cr(pic)3]0 is followed by the second, rate-determining step – one-end bonded pic ligand liberation. In the case of the [Cr(pic)2(OH)]2 0 complex, the first faster stage produces the singly bridged dimer, which undergoes cleavage into the parent monomers in the second, much slower step. The subsequent aquation of [Cr(pic)2(H2O)2]+ is extremely slow and leads to [Cr(pic)(H2O)4]2+ formation, which practically does not undergo further ligand substitution under the conditions applied. Kinetics of the first aquation stage for [Cr(pic)3]0 and of the second step for [Cr(pic)2(OH)]2 0 were studied spectrophotometrically in the 0.1–1.0 M HClO4 range at I = 1.0 M. The observed pseudo-first order rate constant for [Cr(pic)3]0 decreases with [H+] increase according to the rate law: k obs = k 1 + k –1 Q 1/[H+], where k 1 and k –1 are the rate constants of the forward and the reverse processes in the unprotonated substrate and Q 1 is the protonation constant of the pyridine nitrogen atom. In the case of the [Cr(pic)2(OH)]2 0 complex, the rate for the singly bridged dimer cleavage does not depend on [H+]. The activation parameters for the chelate-ring opening in [Cr(pic)3]0 and for the singly bridged dimer cleavage have been determined and discussed. Some kinetic data of the slow, second aquation stage for the [Cr(pic)3]0 complex and of the fast, first aquation stage for the doubly bridged dimer have been studied; for both reactions the rate increases linearly with the increase in [H+].  相似文献   
63.
64.
The oxidation of alcohols using catalytic amounts of metal complexes is highly attractive from the viewpoint of green chemistry principles. However, examples of metal complex-catalyzed oxidations of alcohols with O2 using water as the solvent are still rare, and precious metals, high-pressure O2 or air, and a stoichiometric amount of base are often required. In this study, it was found that an oxovanadium-4,4′-t-Bubpy (4,4′-di-tert-butyl-2,2′-bipyridyl) complex exhibited high catalytic activity in the oxidation of benzhydrols under an atmosphere of O2 in water as the sole solvent. Interestingly, this catalytic oxidation method could be applied to the gram-scale aerobic oxidation of alcohols in water under the atmosphere.  相似文献   
65.
The reaction of enol acetates with alcohols in the presence of a catalytic amount of a rhenium complex, such as ReBr(CO)5, produced the corresponding ketones and aldehydes in moderate to good yields. It was suggested that the preparation of an ether, an intermolecular dehydrated product, was the first step of the reaction.  相似文献   
66.
A newly synthesized one‐dimensional (1D) hydrogen‐bonded (H‐bonded) rhodium(II)–η5‐semiquinone complex, [Cp*Rh(η5p‐HSQ‐Me4)]PF6 ([ 1 ]PF6; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl; HSQ=semiquinone) exhibits a paraelectric–antiferroelectric second‐order phase transition at 237.1 K. Neutron and X‐ray crystal structure analyses reveal that the H‐bonded proton is disordered over two sites in the room‐temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6? ion. The relative permittivity εb′ along the H‐bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of 13C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low‐temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10?4–10?6 s in the temperature range of 240–270 K. DFT calculations predict that the protonation/deprotonation of [ 1 ]+ leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π‐bonded rhodium fragment, producing the stable η6‐hydroquinone complex, [Cp*Rh3+6p‐H2Q‐Me4)]2+ ([ 2 ]2+), and η4‐benzoquinone complex, [Cp*Rh+4p‐BQ‐Me4)] ([ 3 ]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [ 2 ]2+ and [ 3 ], which would be generated in the H‐bonded chain.  相似文献   
67.
A rhodium-catalyzed silylation reaction of carbon-cyano bonds using disilane has been developed. Under these catalytic conditions, carbon-cyano bonds in aryl, alkenyl, allyl, and benzyl cyanides bearing a variety of functional groups can be silylated. The observation of an enamine side product in the silylation of benzyl cyanides and related stoichiometric studies indicate that the carbon-cyano bond cleavage proceeds through the deinsertion of silyl isocyanide from eta(2)-iminoacyl complex B. Knowledge gained from these studies has led to the development of a new intramolecular biaryl coupling reaction in which aryl cyanides and aryl chlorides are cross-coupled.  相似文献   
68.
69.
70.
An efficient solution‐phase synthesis of rac‐15‐deoxy‐Δ12,14‐PGJ2 (15dPGJ2) derivatives that contain variable α and ω chains based on a polymer‐assisted strategy and their neurite‐outgrowth‐promoting activity are described. The strategy for the synthesis of PGJ2 derivatives involves the use of a vinyl iodide bearing cyclopentenone as a key intermediate, which undergoes Suzuki–Miyaura coupling and subsequent Lewis acid catalyzed aldol condensation for incorporation of the ω and α chains, respectively. For easy access to the PGJ2 derivatives, a polymer‐supported catalyst and scavengers were adapted for use in these four diverse steps, in which workup and purification can be performed by simple filtration of the solid‐supported reagents. By using this methodology, we succeeded in the synthesis of 16 PGJ2 derivatives with four alkyl boranes and four aldehydes. The neurite‐outgrowth‐promoting activity of the 16 synthetic compounds in PC12 cells revealed that the side‐chains play a major role in modulating their biological activity. The carboxylic acid on the α chain improved the biological activity, although it was not absolutely required. Furthermore, a PGJ2 derivative with a phenyl moiety on the ω chain was found to exhibit an activity comparable to that of natural 15dPGJ2.  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