全文获取类型
收费全文 | 22651篇 |
免费 | 2010篇 |
国内免费 | 4905篇 |
专业分类
化学 | 26064篇 |
晶体学 | 136篇 |
力学 | 276篇 |
综合类 | 115篇 |
数学 | 426篇 |
物理学 | 2549篇 |
出版年
2024年 | 63篇 |
2023年 | 358篇 |
2022年 | 686篇 |
2021年 | 799篇 |
2020年 | 1183篇 |
2019年 | 992篇 |
2018年 | 1021篇 |
2017年 | 931篇 |
2016年 | 1012篇 |
2015年 | 951篇 |
2014年 | 1431篇 |
2013年 | 2227篇 |
2012年 | 1242篇 |
2011年 | 1549篇 |
2010年 | 1171篇 |
2009年 | 1283篇 |
2008年 | 1368篇 |
2007年 | 1496篇 |
2006年 | 1385篇 |
2005年 | 1294篇 |
2004年 | 1271篇 |
2003年 | 971篇 |
2002年 | 581篇 |
2001年 | 478篇 |
2000年 | 496篇 |
1999年 | 418篇 |
1998年 | 374篇 |
1997年 | 332篇 |
1996年 | 302篇 |
1995年 | 295篇 |
1994年 | 248篇 |
1993年 | 192篇 |
1992年 | 189篇 |
1991年 | 140篇 |
1990年 | 110篇 |
1989年 | 102篇 |
1988年 | 82篇 |
1987年 | 53篇 |
1986年 | 48篇 |
1985年 | 53篇 |
1984年 | 48篇 |
1983年 | 26篇 |
1982年 | 36篇 |
1981年 | 35篇 |
1980年 | 26篇 |
1979年 | 24篇 |
1978年 | 27篇 |
1977年 | 29篇 |
1976年 | 36篇 |
1974年 | 38篇 |
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
91.
A bicyclo[2.2.2]octane C/D ring system,with a lactonic ring at C-8 and C-9,of the atisine-type C20-diterpenoid alkaloids,was successfully synthesized,using an oxidative dearomatization/intramolecular Diels-Alder reaction. 相似文献
92.
An effective and environmentally benign benzylic oxidation for transition of alkylarenes into the corresponding carbonyl compounds was reported.Alkylarenes were mixed and stirred with potassium bromide,m-chloroperbenzoic acid and a catalytic amount of iodobenzene in water at 60 8C for several hours,a series of the corresponding carbonyl compounds was obtained in moderate to good yields.In the reaction,iodobenzene was first oxidized by m-chloroperbenzoic acid into the hypervalent iodine intermediate which then reacted with potassium bromide to form the key radical initiator for the benzylic oxidation. 相似文献
93.
An expeditious synthesis of 2-aryl-benzimidazoles by the condensation of o-phenylenediamine with various araldehydes is described. This greener protocol is catalyzed by Amberlite IR-120, and proceeds efficiently in the absence of any organic solvent under microwave irradiation within 3–5 min. 相似文献
94.
95.
96.
《Journal of Coordination Chemistry》2012,65(1-4):77-89
Abstract A steric effect in the carbon-skeleton rearrangement catalyzed by heptamethyl cobyrinate perchlorate, [Cob(II)7C1ester]C104, was investigated under electrochemical conditions. The controlled-potential electrolyses of alkyl halides having two carboxylic ester groups of different bulkiness on the same carbon atom, such as 2,2-bis(ethoxycarbonyl)-l-bromopropane, l-bromo-2-tert-butoxycarbonyl-2-ethoxy-carbonylpropane, l-bromo-2-cyclohexyloxycarbonyl-2-ethoxycarbonylpropane, and l-bromo-2-ethoxy-carbonyl-2-phenoxycarbonylpropane, were carried out in N,N-dimethylformamide, as catalyzed by [Cob(II)7C1ester]CIO4, to give the corresponding ester-migrated products in the dark at—1.5 V vs SCE in the presence of acetic acid and at—2.0 V vs SCE without acetic acid. As regards a correlation between bulkiness of an ester group and a migration aptitude, a smaller ester group tends to migrate to the adjacent carbon atom more readily than a larger one. The origin of such a steric effect is discussed with attention to the rate-determining step. 相似文献
97.
《Journal of Coordination Chemistry》2012,65(8):1396-1404
The synthesis and characterization of 1-phenyl-3-alkyl-substituted carbene precursors that were prepared from 1-phenyl substituted benzimidazole and various alkyl halides are reported. The new benzimidazolium salts (1a–e) were characterized by 1H NMR, 13C NMR, FT-IR spectroscopic methods and elemental analyses. New in situ generated palladium-benzimidazolium complexes were tested for catalytic activity in the Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions. 相似文献
98.
Hong‐Juan Deng Yu‐Jing Fang Gao‐Wei Chen Miao‐Chang Liu Hua‐Yue Wu Jiu‐Xi Chen 《应用有机金属化学》2012,26(4):164-167
An efficient and convenient copper‐catalyzed Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with amines in aqueous media has been developed, providing a wide range of N‐substituted pyrroles in good yields. It is noteworthy that the Clauson–Kass reaction of 2,5‐dimethoxytetrahydrofuran with p‐phenylenediamine or m‐phenylenediamine proceeds smoothly to afford the corresponding monopyrroles and bispyrroles with high selectivity in impressive yields. A plausible mechanism for the formation of N‐substituted pyrroles has been proposed. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
99.
100.
Raoul Kopelman 《Journal of statistical physics》1986,42(1-2):185-200
Heterogeneous kinetics are shown to differ drastically from homogeneous kinetics. For the elementary reaction A + A products we show that the diffusion-limited reaction rate is proportional tot
– h[A]2 or to [A]x, whereh=1- d
s/2, X=1+2/d
s
=(h-2)(h-1), andd
s
is the effective spectral dimension. We note that ford = d
s
=1, h =1/2 andX = 3, for percolating clustersd
s = 4/3,h = 1/3 andX = 5/2, while for dust ds <1, 1 >h > 1/2 and >X > 3. Scaling arguments, supercomputer simulations and experiments give a consistent picture. The interplay of energetic and geometric heterogeneity results in fractal-like kinetics and is relevant to excitation fusion experiments in porous membranes, films, and polymeric glasses. However, in isotopic mixed crystals, the geometric fractal nature (percolation clusters) dominates. 相似文献