全文获取类型
收费全文 | 2422篇 |
免费 | 75篇 |
国内免费 | 5篇 |
专业分类
化学 | 1579篇 |
晶体学 | 23篇 |
力学 | 67篇 |
数学 | 309篇 |
物理学 | 524篇 |
出版年
2023年 | 39篇 |
2022年 | 77篇 |
2021年 | 78篇 |
2020年 | 66篇 |
2019年 | 66篇 |
2018年 | 56篇 |
2017年 | 36篇 |
2016年 | 74篇 |
2015年 | 71篇 |
2014年 | 62篇 |
2013年 | 135篇 |
2012年 | 127篇 |
2011年 | 190篇 |
2010年 | 99篇 |
2009年 | 102篇 |
2008年 | 143篇 |
2007年 | 123篇 |
2006年 | 107篇 |
2005年 | 103篇 |
2004年 | 98篇 |
2003年 | 47篇 |
2002年 | 48篇 |
2001年 | 40篇 |
2000年 | 43篇 |
1999年 | 26篇 |
1998年 | 14篇 |
1997年 | 26篇 |
1996年 | 28篇 |
1995年 | 15篇 |
1994年 | 19篇 |
1993年 | 25篇 |
1992年 | 11篇 |
1991年 | 16篇 |
1990年 | 19篇 |
1989年 | 11篇 |
1988年 | 13篇 |
1987年 | 15篇 |
1986年 | 12篇 |
1985年 | 15篇 |
1984年 | 16篇 |
1983年 | 14篇 |
1982年 | 12篇 |
1981年 | 18篇 |
1980年 | 12篇 |
1979年 | 16篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1973年 | 12篇 |
1972年 | 7篇 |
排序方式: 共有2502条查询结果,搜索用时 15 毫秒
71.
Lemaître F Lucas D Groison K Richard P Mugnier Y Harvey PD 《Journal of the American Chemical Society》2003,125(18):5511-5522
The stoichiometric and catalytic activations of alkyl halides and acid chlorides by the unsatured Pd(3)(dppm)(3)(CO)(2+) cluster (Pd(3)(2+)) are investigated in detail. A series of alkyl halides (R-X; R = t-Bu, Et, Pr, Bu, allyl; X = Cl, Br, I) react slowly with Pd(3)(2+) to form the corresponding Pd(3)(X)(+) adduct and "R(+)". This activation can proceed much faster if it is electrochemically induced via the formation of the paramagnetic species Pd(3)(+). The latter is the first confidently identified paramagnetic Pd cluster. The kinetic constants extracted from the evolution of the UV-vis spectra for the thermal activation, as well as the amount of electricity to bring the activation to completion for the electrochemically induced reactions, correlate the relative C-X bond strength and the steric factors. The highly reactive "R(+)" species has been trapped using phenol to afford the corresponding ether. On the other hand, the acid chlorides react rapidly with Pd(3)(2+) where no induction is necessary. The analysis of the cyclic voltammograms (CV) establishes that a dissociative mechanism operates (RCOCl --> RCO(+) + Cl(-); R = t-Bu, Ph) prior to Cl(-) scavenging by the Pd(3)(2+) species. For the other acid chlorides (R = n-C(6)H(13), Me(2)CH, Et, Me, Pr), a second associative process (Pd(3)(2+) + RCOCl --> Pd(3)(2+.....)Cl(CO)(R)) is seen. Addition of Cu(NCMe)(4)(+) or Ag(+) leads to the abstraction of Cl(-) from Pd(3)(Cl)(+) to form Pd(3)(2+) and the insoluble MCl materials (M = Cu, Ag) allowing to regenerate the starting unsaturated cluster, where the precipitation of MX drives the reaction. By using a copper anode, the quasi-quantitative catalytic generation of the acylium ion ("RCO(+)") operates cleanly and rapidly. The trapping of "RCO(+)" with PF(6)(-) or BF(4)(-) leads to the corresponding acid fluorides and, with an alcohol (R'OH), to the corresponding ester catalytically, under mild conditions. Attempts were made to trap the key intermediates "Pd(3)(Cl)(+)...M(+)" (M(+) = Cu(+), Ag(+)), which was successfully performed for Pd(3)(ClAg)(2+), as characterized by (31)P NMR, IR, and FAB mass spectrometry. During the course of this investigation, the rare case of PF(6)(-) hydrolysis has been observed, where the product PF(2)O(2)(-) anion is observed in the complex Pd(3)(PF(2)O(2))(+), where the substrate is well-located inside the cavity formed by the dppm-Ph groups above the unsatured face of the Pd(3)(2+) center. This work shows that Pd(3)(2+) is a stronger Lewis acid in CH(2)Cl(2) and THF than AlCl(3), Ag(+), Cu(+), and Tl(+). 相似文献
72.
Jos R. Ascenso Maria de Deus Carvalho Alberto R. Dias Carlos C. Romo Maria J. Calhorda Luis F. Veiros 《Journal of organometallic chemistry》1994,470(1-2):147-152
The metallocene thioether derivatives [Cp2M(MeSCH2CH2SMe)][PF6]2 (1, M = MO; 2, M = W), [Cp2Mo(SCH2CH2SMe)][PF6] (3) and [Cp2M(SCH2CH2S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol−1), 2 (51.2 ± 4.6 kJ mol−1) and 3 (30.0 ± 3.1 kJ mol−1). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour. 相似文献
73.
Goulart MO Machado Reys JR Emery FS Pinto AV de Souza Filho JD 《Magnetic resonance in chemistry : MRC》2004,42(7):663-665
Peroxidation of the phenazine of beta-lapachone using m-ClC6H4CO3H-CH2Cl2 furnished a macrolactone with a rigid 10-membered ring, and the corresponding N-oxide, along with a dihydrobenzophenazine-5-one. All of the new compounds were fully characterized by spectroscopic methods, with the unambiguous assignment of the hydrogens and carbon NMR signals for the N-oxide, with the aid of 2-D NMR, mainly COSY, HMQC, HSQC and HMBC. For the other two compounds some signals could not be assigned owing to their own intrinsic features. 相似文献
74.
Reactions of ligands 2-vinylpyridine 1, 4-vinylpyridine 2, 2-allylpyridine 3, 1-allylpyrazole 4, acrylonitrile 5 and allylcyanide 6 with the metallocene derivatives [Mo(η5-C5H5)2H3][PF6] 7, [Mo(η5-C5H5)2HI] 8, [W(η5-C5H5)2H3] [PF6] 9, [Mo(η5-C5H5)2H2] 10, [M(η5-C5H5)2Br2], M = Mo 11, M = W 12 are described. Reaction of 7 with 1, 8 with 1, 3 with 8 and 4 with 8 gave mixtures of metallocyle isomers resulting from coordination of the nitrogen atom to molybdenum followed by internal hydrometallation; reaction of 11 with 1 gave an olefinic π complex; reaction of either 9 or 11 with 1 gave intractable oils; reactions of 8 with 2, 11 with 5, 12 with 5, 11 with 6 and 12 with 6 yielded monosubstituted products in which the ligand is N-coordinated. 相似文献
75.
76.
77.
Competitive location problems can be characterized by the fact that the decisions made by others will affect our own payoffs. In this paper, we address a discrete competitive location game in which two decision-makers have to decide simultaneously where to locate their services without knowing the decisions of one another. This problem arises in a franchising environment in which the decision-makers are the franchisees and the franchiser defines the potential sites for locating services and the rules of the game. At most one service can be located at each site, and one of the franchisees has preferential rights over the other. This means that if both franchisees are interested in opening the service in the same site, only the one that has preferential rights will open it. We consider that both franchisees have budget constraints, but the franchisee without preferential rights is allowed to show interest in more sites than the ones she can afford. We are interested in studying the influence of the existence of preferential rights and overbidding on the outcomes for both franchisees and franchiser. A model is presented and an algorithmic approach is developed for the calculation of Nash equilibria. Several computational experiments are defined and their results are analysed, showing that preferential rights give its holder a relative advantage over the other competitor. The possibility of overbidding seems to be advantageous for the franchiser, as well as the inclusion of some level of asymmetry between the two decision-makers. 相似文献
78.
79.
We review the process of star formation, detailing the theories underlying the stability of molecular clouds and their collapse to protostars, and discussing the empirical evidence and models which inform them. We give emphasis to the role that the magnetic field plays in influencing the stability of molecular clouds and hence the star formation rate. The end result of star formation is a mass function which appears constant within our Galaxy. A relative abundance of low mass stars is observed over high mass stars and most of the stars that do form are found to exist as members of a binary system. The origin of binarity is reviewed as is the discovery, formation and observations of some of the lowest mass stars known, the brown dwarfs. 相似文献