全文获取类型
收费全文 | 658篇 |
免费 | 31篇 |
国内免费 | 3篇 |
专业分类
化学 | 497篇 |
晶体学 | 6篇 |
力学 | 6篇 |
数学 | 86篇 |
物理学 | 97篇 |
出版年
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 9篇 |
2020年 | 8篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2017年 | 7篇 |
2016年 | 18篇 |
2015年 | 19篇 |
2014年 | 20篇 |
2013年 | 50篇 |
2012年 | 58篇 |
2011年 | 50篇 |
2010年 | 22篇 |
2009年 | 24篇 |
2008年 | 39篇 |
2007年 | 48篇 |
2006年 | 46篇 |
2005年 | 20篇 |
2004年 | 26篇 |
2003年 | 26篇 |
2002年 | 22篇 |
2001年 | 8篇 |
2000年 | 9篇 |
1999年 | 5篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 8篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1987年 | 4篇 |
1986年 | 6篇 |
1985年 | 7篇 |
1984年 | 10篇 |
1982年 | 7篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 9篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1970年 | 3篇 |
1967年 | 3篇 |
1966年 | 2篇 |
1962年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有692条查询结果,搜索用时 15 毫秒
1.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
2.
Alfons Pascual 《Helvetica chimica acta》1989,72(3):556-569
Preparation of Substituted 2-Aminooxazole-4-carbonitriles During our synthetic programme to convert 4-isoxazolylthioureas 3 into the corresponding carbodiimides 5 , a side reaction leading to the hitherto unknown 2-aminooxazole-4-carbonitriles 6 was observed. By selecting appropriate reaction conditions, it was possible to improve the yields of the carbodiimides 5 as well as of the novel oxazole-carbonitriles 6 at will, thus allowing the synthesis of 6 to be conducted in very good yields. To overcome the difficulty of isolating unstable carbodiimides, the synthesis of 6 is best carried out in a one-pot procedure. A limited mechanistic study showed that the formation of 6 proceeds via 5 as the only intermediate. The stability of the N?C?N bonds against base attack (depending strongly on both sterical hindrance and electronic-density factors) forms the only limitation of this new synthetic pathway to oxazole-4-carbonitriles. 相似文献
3.
Pavla Fialová Inmaculada Robina Petr Sedmera Lucie Petrásková-Hušáková 《Tetrahedron letters》2005,46(50):8715-8718
Glycosyl azides are new efficient donors for glycosidases. Their high water solubility facilitates transglycosylations with comparable or better yields than common O-glycosides. The azido group totally changes the β-GalNAc-ase/β-GlcNAc-ase ratio in β-N-acetylhexosaminidases (from the usual 0.3-1.0 to <0.01), contrary to all known aglycons. 相似文献
4.
A. Cerdán Vidal A. R. Maurí Aucejo M. Llobat Estellés C. Pascual Martí J. Simeón Martí 《Fresenius' Journal of Analytical Chemistry》1994,350(12):706-711
The possibility of identification of substances which have similar spectral behaviour by means of Apparent Content Curves has been studied. This study is carried out with absorption, excitation and emission spectra of several amphetamines of widespread pharmaceutical use. Results obtained show that amphetamine, phenylpropanolamine, pseudoephedrine, phenylephrine, epinephrine, dopamine and methoxyamphetamine can be identified with a probability of >95%. 相似文献
5.
SbPO4, a phosphate with a layered structure, was tested as an electrode material for lithium cells spanning the 3.0-0.0 V range. Two main electrochemical processes were detected as extensive plateaus at ca. 1.6 and 0.7 V in galvanostatic measurements. The first process was found to be irreversible, thus excluding a potential intercalation-like mechanism for the reaction and being better interpreted as a decomposition reaction leading to the formation of elemental Sb. This precludes the use of this compound as a cathodic material for lithium cells. By contrast, the process at 0.7 V is reversible and can be ascribed to the formation of lithium-antimony alloys. The best electrochemical response was obtained by cycling the cell at a C/20 discharge rate over the voltage range 1.25-0.25 V. Under these conditions, the cell delivers an average capacity of 165 Ah/kg—a value greater than those reported for other phosphates—upon successive cycling. 相似文献
6.
Three new diterpenoids with a substituted α-cyclogeraniol skeleton have been isolated from the umbelliferae (Vahl) Lange, for which the names of magydar-2,13-dien-11,17-diol, , magydar-2,10 (20), 13-trien-17-ol, , and magydar-2,10(20), 13-trien-17-yl acetate, , are proposed. The structures of these substances have been deduced from spectroscopic and chemical data. 相似文献
7.
J.-T.De Pascual E. Caballero C. Caballero M. Medarde A.F. Barrero M. Grande 《Tetrahedron》1982,38(12):1837-1842
Trixagol 1 and fourteen derivatives with the skeleton of γ-cyclogeranil geraniol were isolated from Bellardia trixago, the structures were determined by spectroscopic methods and confirmed by partial synthesis. Furthermore. 3,4-dihydro-γ-ionone, α-ambrinol, β-sitosterol and three flavonoids 5-O-demethyl tangeretin, 5-hydroxy auranetin and 3′-methoxy calycopterin were also isolated. 相似文献
8.
J. I. Latorre P. Pascual S. Narison 《Zeitschrift fur Physik C Particles and Fields》1987,34(3):347-360
We clarify the discrepancies of previous results for the masses and decay amplitudes of hermaphrodite mesons obtained from QCD sum rules. We study the case of the strange quark within a light quark expansion formalism. We find tht the hermaphrodite masses are much higher than the ones of their ordinary meson partners. Our values of the set of masses and continuum thresholds are compared with some other sum rule results. We analyze the hadronic couplings of the isovector 1?+ exotic hermaprodite \(\tilde \rho \) using a three-point function sum rule evaluated at the symmetric euclidean point. We find that the \(\tilde \rho \) can be very broad and prefers to decay into ρπ andK * K. Its most characteristic decays are the ones into πγ, ηπ and μ′π. The former and the latter are of the order of (3~8) MeV. 相似文献
9.
Avilés M. A. Ginés J. M. del Rio J. C. Pascual J. Pérez-Rodríguez J. L. Sánchez-Soto P. J. 《Journal of Thermal Analysis and Calorimetry》2002,67(1):177-188
This paper examines the polymerization of acrylonitrile to poly(acrylonitrile)(PAN), and its cyclization, in bulk form and using N,N-dimethylformamide (DMF) as solvent in which both monomer and polymer are soluble. Thermal analysis of the resultant products after polymerization has been performed by DSC and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). Scanning electron microscopy has been used to study the morphology of the resultant products and after thermal treatments. The DSC thermal curve of PAN-DMF sample is quite different from the PAN bulk sample, showing a single sharp exothermic peak associated with nitrile group polymerization (cyclization) of PAN at lower temperature (240°C) than that of bulk PAN sample (314°C). Cyclization of PAN was confirmed by IR spectroscopy. It was found that the amide molecules are difficult to eliminate completely in the product obtained after the polymerization reaction, even after prolonged heating at 110°C, and remain occluded. The formation of a complex by dipolar bonding is also possible and it is discussed. It is concluded that the amount of heat evolved as well as the temperature interval over which it is released are influenced by the chemical processing of PAN when using DMF as solvent of both monomer and polymer. Pyrolysis of these PAN samples revealed the release of occluded molecules of DMF, and several compounds containing nitrogen produced from the thermal degradation processes. All these results are interesting to know the chemical processing of carbon fibres and activated carbon fibres from PAN modified precursors.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
10.
VISIBLE CHEMILUMINESCENCE ASSOCIATED WITH THE REACTION BETWEEN METHEMOGLOBIN OR OXYHEMOGLOBIN WITH HYDROGEN PEROXIDE 总被引:1,自引:0,他引:1
Eduardo A. Lissi Jorge Escobar Carlos Pascual Maria del Castillo Tais H. Schmitt Paolo Di Mascio 《Photochemistry and photobiology》1994,60(5):405-411
Abstract Visible chemiluminescence is emitted in the irreversible deactivation of hemoglobin or methemoglobin with excess H2 O2 . The emission takes place in two phases. The most intense one lasts a few seconds and is followed by a second phase of lower intensity that remains for longer periods. This second phase presents chaotic or sustained oscillations. Free radicals are implicated in the luminescent process since the emission can be reduced by free radical scavengers such as 6-hydroxy-2,5,7,8,-tetramethylchroman-2-carboxylic acid (Trolox) or ascorbic acid. These additives lead to a delay in reaching the maximum intensity, which can be related to their consumption, implying substantial recycling of the hemoprotein. Chemiluminescence is also observed in the oxidation of hemin by H2 O2 , suggesting a role for the heme group in the processes leading to the excited state production. The lower intensity observed in the presence of hemin can be related to the contribution of the globin chains. 相似文献