全文获取类型
收费全文 | 1483篇 |
免费 | 18篇 |
国内免费 | 6篇 |
专业分类
化学 | 874篇 |
晶体学 | 9篇 |
力学 | 59篇 |
数学 | 396篇 |
物理学 | 169篇 |
出版年
2019年 | 15篇 |
2017年 | 9篇 |
2016年 | 25篇 |
2015年 | 16篇 |
2014年 | 26篇 |
2013年 | 88篇 |
2012年 | 46篇 |
2011年 | 47篇 |
2010年 | 38篇 |
2009年 | 27篇 |
2008年 | 64篇 |
2007年 | 64篇 |
2006年 | 48篇 |
2005年 | 68篇 |
2004年 | 45篇 |
2003年 | 43篇 |
2002年 | 35篇 |
2001年 | 39篇 |
2000年 | 33篇 |
1999年 | 13篇 |
1998年 | 17篇 |
1997年 | 16篇 |
1996年 | 22篇 |
1995年 | 18篇 |
1994年 | 20篇 |
1993年 | 17篇 |
1992年 | 17篇 |
1991年 | 16篇 |
1990年 | 19篇 |
1989年 | 23篇 |
1988年 | 26篇 |
1987年 | 26篇 |
1986年 | 14篇 |
1985年 | 29篇 |
1984年 | 21篇 |
1983年 | 26篇 |
1982年 | 32篇 |
1981年 | 25篇 |
1980年 | 27篇 |
1979年 | 29篇 |
1978年 | 18篇 |
1977年 | 27篇 |
1976年 | 13篇 |
1975年 | 20篇 |
1974年 | 27篇 |
1973年 | 22篇 |
1972年 | 13篇 |
1971年 | 13篇 |
1969年 | 12篇 |
1965年 | 9篇 |
排序方式: 共有1507条查询结果,搜索用时 31 毫秒
21.
Anthony OKeefe Andreas J. Illies James R. Gilbert Michael T. Bowers 《Chemical physics》1983,82(3):471-478
High-resolution translational-energy spectroscopy (up to 0.1 eV) has been carried out on 8 V beams of NO? and NO2?. Several features in the spectrum of NO4 are assigned to the transitions within the triplet manifold of this ion. The observed transitions originate in several excited electronic states, indicating long lifetimes (> 10 μs) for the states involved. Two electronic transitions in NO2' have been observed at low energies which are attributed to excitations to the first two excited states of this ion. 相似文献
22.
Hydroboration of β-acetylenic alcohols followed by NaOH/H2O2 oxidation leads to hemiacetals of γ-aldols which are easily dehydrated to 2,3-dihydrofuran compounds. The reaction gives good yields with hindered alcohols and its stereochemistry may be controlled during the organometallic synthesis of the starting alcohol. 相似文献
23.
24.
M. J. Whitcombe A. Gilbert G. R. Mitchell 《Journal of polymer science. Part A, Polymer chemistry》1992,30(8):1681-1691
The syntheses of three methacrylate monomers with cinnamate ester side-chains and of a further monomer with a corresponding cinnamide side-chain are described. Two of the monomers, with isomeric structures, were thermotropic liquid crystals. Although the clearing points were very similar the crystal melting points differed by 8°C. One compound also exhibited a monotropic smectic phase, behavior not shown by its isomer. The other two monomers were not liquid crystalline. The monomers were polymerized by free radical polymerization, both as homopolymers and as copolymers with methyl methacrylate. In the case of one of the mesogenic ester monomers, copolymers with a cyanophenyl benzoate monomer were also prepared. Three of the four monomers formed thermotropic liquid crystalline homopolymers and the copolymers with the benzoate monomer were also liquid crystalline. The monomers were considered as photoactive components of polymeric liquid crystals. As a preliminary investigation of their photochemistry, copolymers with methyl methacrylate were prepared and irradiated in solution with a broad-band source. Under these conditions two of the materials show a facile photo-Fries rearrangement of the aryl cinnamate ester group. © 1992 John Wiley & Sons, Inc. 相似文献
25.
The mass spectra of twenty-six commercially available medicinal phenothiazines have been determined at high resolution. In each compound, the side chain attached to the 10-position of the phenothiazine ring contains nitrogen and fission of the C? C bond α to this nitrogen gives in most cases the base peak. Some of the compounds are also substituted at the 2-position and this substituent generally remains intact, though some substituents such as acetyl, propionyl, methoxyl and methylthio can undergo fragmentation. Fragmentations fall into three groups; those which give ions representing a part of the side chain; those which give ions representing the intact phenothiazine ring with part of the side chain attached; those which give ions representing a partially fragmented ring system. 相似文献
26.
Gilbert E. Janauer 《Mikrochimica acta》1968,56(6):1111-1123
Summary Distribution ratios between Dowex 50 W-X 8 resin and DMSO-H2O-HCl systems have been determined for Mg, Ca, Sr, Ba, Ga, In, Sn(II) and Pb(II) as a function of both DMSO content and HCl-molarity. At high DMSO concentrations and high HCl concentrations theD values for all metal ions were not much different from those in corresponding aqueous systems. However, at lower and intermediate HCl concentrations (0.10 to 0.60M) D values differed greatly from those in aqueous systems, especially in the range from 20 to 50 mole% DMSO. Maxima in the logD vs. mole% DMSO plots at constant HCl concentrations were obtained for all cations except Sn(II) and Pb(II). Separation procedures for various pairs and combinations of cations seem feasible in DMSO-media [e. g., Ga/In and Sn(II)/Pb(II)] and the DMSO-water system is suggested as a very promising novel solvent medium for ion exchange separations.
Zusammenfassung Für Mg, Ca, Sr, Ba, Ga, In, Sn(II) und Pb(II) wurden die Verteilungsverhältnisse zwischen Dowex 50 W-X 8 und Dimethylsulfoxid—Wasser—Salzsäure in Abhängigkeit vom DMSO-Gehalt und der Salzsäuremolarität bestimmt. Bei hohen DMSO-Konzentrationen und hohen HCl-Konzentrationen unterscheiden sich die Verteilungskoeffizienten (D) aller Metallionen nicht sehr von denen in entsprechenden wäßrigen Systemen. Aber bei niederen und mäßigen HCl-Konzentrationen (0,10-bis 0,60-m) istD sehr verschieden gegenüber wäßrigen Systemen, besonders bei Anwesenheit von 20 bis 50 Mol-% DMSO. Trägt man logD gegen Mol-% DMSO bei konstanter HCl-Konzentration auf, so erhält man für alle Metalle außer Sn(II) und Pb(II) Maxima. Trennungsverfahren für verschiedene Ionenpaare und -gemische scheinen in DMSO-hältigem Plasma durchführbar zu sein, z. B. Ga/In und Sn(II)/Pb(II). Wäßrige DMSO-Systeme sind neue, vielversprechende Lösungsmittel für Trennungen mit Hilfe von Ionenaustauschern.相似文献
27.
Gilbert Dana Feiga Weisbuch Brigitte Lo Cicero Jean-Michel Drancourt Jacqueline Mercier 《Tetrahedron》1985,41(7):1241-1249
We show that the four studied 4-hydrindenones (with or without a methyl substituant at C3 or C7a) give by hydrogenation on Raney nickel or on Pd/C, in various solvants, the cis 4-hydrindanones, by a kinetically controlled process. During the hydrogenation, the double bond can migrate only in the positions conjugated to the carbonyl group.In contrast, when the carbonyle is protected as a dioxolanne, the double bond is free to migrate around the five membered ring. In spite of this mobility the optical purity of the saturated dioxolannes formed is high. In the case of the (+)3-methyl Δ3(3a) 4-hydrindenone, the enantiomeric hydrindanones obtained by direct hydrogenation or with isomerization of the double bond are not the same. Therefore, the optical purity of the product is low, but its value allows an estimation of the relative importance of the two reaction pathways. 相似文献
28.
The present paper deals with the experimental and theoretical determination of energies of conjugation of organic molecules.A computation process has been applied, first to simple molecules comprising an hydrocarbon (styrene), an oxygen function (benzaldehyde) and a nitrogen function (aniline). The results are compared with those obtained from the literature.The application of this computation process to naphthoic acids permits the determination of energies of conjugation and isomerization of these molecules. 相似文献
29.
Electron deficient 1,2-diacylcyclopropenes represent synthetic equivalent for both acylcarbenes and vinylcarbenes; in their cycloreaction with ynamines aminofuranes and/or aminocyclopentadienes are formed. 相似文献
30.
Nathalie Laronze Jean-François Moisan Catherine Roch-Marchal Feng-Xian Liu Gilbert Hervé 《Journal of Cluster Science》2002,13(3):355-368
Transition metal salts of heteropolyacids have been prepared taking into account the strong acidic and cation exchanging properties of the solid heteropolyacids. The exchange between protons and the transition metal cation is carried out by stirring a suspension of the hydrated heteropolyacid in a solution of the metal acetylacetonate complex in toluene. The exchange occurs on the surface of the solid particles and diffusion of protons and metal cations into the hydrated lattice leads to the substitution of all the protons. The method can be utilized in order to prepare supported vanadyl and copper molybdophosphates from supported heteropolyacids and they have been studied in the catalysis of the oxidative dehydrogenation of isobutyric acid. The effect of vanadyl counter-ions on the catalytic behavior is the same as observed with bulk catalysts but, on the contrary, copper supported molybdophosphate shows an acid catalytic activity not observed with bulk catalysts. 相似文献