全文获取类型
收费全文 | 3127篇 |
免费 | 65篇 |
国内免费 | 294篇 |
专业分类
化学 | 1978篇 |
晶体学 | 4篇 |
力学 | 272篇 |
综合类 | 1篇 |
数学 | 762篇 |
物理学 | 469篇 |
出版年
2023年 | 140篇 |
2022年 | 39篇 |
2021年 | 70篇 |
2020年 | 75篇 |
2019年 | 91篇 |
2018年 | 88篇 |
2017年 | 80篇 |
2016年 | 58篇 |
2015年 | 61篇 |
2014年 | 134篇 |
2013年 | 300篇 |
2012年 | 106篇 |
2011年 | 189篇 |
2010年 | 135篇 |
2009年 | 203篇 |
2008年 | 192篇 |
2007年 | 221篇 |
2006年 | 195篇 |
2005年 | 155篇 |
2004年 | 144篇 |
2003年 | 78篇 |
2002年 | 65篇 |
2001年 | 44篇 |
2000年 | 51篇 |
1999年 | 46篇 |
1998年 | 79篇 |
1997年 | 41篇 |
1996年 | 41篇 |
1995年 | 31篇 |
1994年 | 44篇 |
1993年 | 59篇 |
1992年 | 33篇 |
1991年 | 28篇 |
1990年 | 24篇 |
1989年 | 19篇 |
1988年 | 14篇 |
1987年 | 21篇 |
1986年 | 9篇 |
1985年 | 7篇 |
1984年 | 11篇 |
1983年 | 11篇 |
1982年 | 12篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 2篇 |
1975年 | 2篇 |
1972年 | 2篇 |
1970年 | 4篇 |
1968年 | 2篇 |
排序方式: 共有3486条查询结果,搜索用时 31 毫秒
61.
Geometry optimizations at the UHF/6-31G* and UMP2/6-31G* levels of theory were performed to find the transition state in the interconversion between norbornadiene (N) and quadricyclane (Q) radical cations. Two transition structures, TS+·1 and TS+·2, were obtained which have C1 and C2 symmetry, respectively. Vibrational analysis at the UHF and UMP2 levels of theory and IRC calculation showed that TS+·1 is the true transition state connecting N+· and Q+·, while TS+·2 is a second order saddle point. 相似文献
62.
Friedrich W. Vierhapper 《Monatshefte für Chemie / Chemical Monthly》1980,111(2):551-554
Conformations of six title compounds were determined by13C-NMR spectroscopy. Equilibration of the 2-methyl-compounds gives as main products the derivatives of the amines least abundant in the product mixture of the catalytic hydrogenation.
Konformation und Base-katalysierte Äquilibrierungen von N-Nitroso-decahydrochinolinen und N-Nitroso-2-methyl-decakydrochinolinen (Kurze Mitt.)
Zusammenfassung Die Konformationen der sechs Titelverbindungen wurden mittels13C-NMR Spektroskopie bestimmt. Äquilibrierung der 2-Methyl-verbindungen ergab als Hauptprodukte die Derivate der bei katalytischer Hydrierung in geringster Menge entstandenen Amine.相似文献
63.
Heinz Günter Viehe Robert Mernyi Lucien Stella Zdenek Janousek 《Angewandte Chemie (International ed. in English)》1979,18(12):917-932
The 100 yers old Wurster's salts have long been recognized as compounds with redical cations. Their unusual stabilization derives partly form capto-dative (cd) substitution. This principle is now discussed as one factor of radical stabilization and it is applied to simple methine derivatives. cd-Substitution has synthetically useful applications: cd-substituents on a carbon atom allow its selective dehydrodimerization. Olefines with geminal and thus cross-conjugated cd-substituents are “radicophilic” and permit twofold carbon radical addition. cd-Substituted olefines are useful antioxidants, polymerization inhibitors and are promising agents in the control of biological radical reactions. Generally, many reactions of cd-substituted molecules appear to involve radicals. 相似文献
64.
65.
John A. McNaney Franz M. Zimmerman Howard K. Zimmerman 《Monatshefte für Chemie / Chemical Monthly》1984,115(8-9):1039-1045
The solubilities of potassium acetate and benzoate in aqueous 1,4-dioxane at a temperature of 85°C are reported together with a quasi-thermodynamic general treatment of the experimental results.This brief contribution is a second report upon the results of systematic solubility measurements, commenced with Ref.1, which have been performed by Dr.John A. McNaney during his abruptly truncated lifetime. 相似文献
66.
The kinetics of radical telomerization of VDF at 141 °C, initiated by ditertbutylperoxide, in the presence of three chain transfer agents (CTAs), HCCl3, CCl4 and CCl3Br, are presented. The values of the chain transfer constants were assessed as 35, 0.25 and 0.06 at 141 °C for CCl3Br, CCl4 and HCCl3, respectively. The values of the degree of polymerization (DPn) were obtained for each CTA and were compared for the same CTA concentration. Hence, CCl3Br behaved as an efficient CTA towards VDF and usually afforded the monoadduct selectively, but in certain conditions the VDF diadduct can also be produced. In contrast, HCCl3 was not so efficient since a polymeric structure was identified as the major product. 相似文献
67.
2-(2-Bromophenyl)ethyl groups have been used as building blocks in radical cyclisation reactions onto azoles to synthesise tri- and tetra-cyclic heterocycles. 2-(2-Bromophenyl)ethyl methanesulfonate was used to alkylate azoles (imidazoles, pyrroles, indoles and pyrazoles) for the synthesis of the radical precursors. Cyclisations of the intermediate aryl radicals yield new 6-membered rings attached to the azoles. The aryl radicals undergo intramolecular homolytic aromatic substitution onto the azole rings. Tributylgermanium hydride has been used with success to replace the toxic and troublesome tributyltin hydride. Initial studies show that the protocol can be used on solid phase resins. The molecular and crystal structures of methyl 5,6-dihydroimidazo[5,1-a]iso-quinoline-1-carboxylate and methyl 5,6-dihydroimidazo[2,1-a]isoquinoline-3-carboxylate were determined by X-ray crystallography. 相似文献
68.
Polyazoamide(PAA) was used as initiator to prepare block copolymer P(MMA-b-St) byfree radical polymerization. The fraction of block copolymer was about 50%. The structureof the block-copolymer was characterized by IR and the results of ~1H-NMR and GPCshowed that the content of the block and the molecular weight (M_w) of the prepolymerand block copolymer could be controlled by varying the mol ratio of styrene/PAA andMMA/prepolymer. DSC and TEM results revealed that the block copolymer has twoseparated glass transition temperatures and phase separation within the domain structure. 相似文献
69.
70.
Summary Tokaj wines (Szamorodni and Aszu wines) of Hungarian origin were investigated on the basis of free amino acids and biogenic
amines. The separation and determination of these compounds was performed by an amino acid analyser equipped with an ion-exchange
resin column. The total amount of free amino acids and biogenic amines was higher in Aszu wines than in Szamorodni wines.
The main amino acids were proline and arginine, while the major biogenic amines were tyramine and putrescine. The free amino
acid and biogenic amine content of Aszu wines depended on the vineyards the wines originated from.
Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001 相似文献