全文获取类型
收费全文 | 4704篇 |
免费 | 984篇 |
国内免费 | 699篇 |
专业分类
化学 | 5713篇 |
晶体学 | 11篇 |
力学 | 86篇 |
综合类 | 11篇 |
数学 | 167篇 |
物理学 | 399篇 |
出版年
2024年 | 4篇 |
2023年 | 55篇 |
2022年 | 98篇 |
2021年 | 131篇 |
2020年 | 268篇 |
2019年 | 123篇 |
2018年 | 184篇 |
2017年 | 131篇 |
2016年 | 271篇 |
2015年 | 352篇 |
2014年 | 335篇 |
2013年 | 437篇 |
2012年 | 382篇 |
2011年 | 358篇 |
2010年 | 335篇 |
2009年 | 342篇 |
2008年 | 405篇 |
2007年 | 331篇 |
2006年 | 315篇 |
2005年 | 287篇 |
2004年 | 259篇 |
2003年 | 319篇 |
2002年 | 87篇 |
2001年 | 86篇 |
2000年 | 82篇 |
1999年 | 53篇 |
1998年 | 39篇 |
1997年 | 73篇 |
1996年 | 69篇 |
1995年 | 59篇 |
1994年 | 22篇 |
1993年 | 25篇 |
1992年 | 24篇 |
1991年 | 8篇 |
1990年 | 11篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
排序方式: 共有6387条查询结果,搜索用时 15 毫秒
151.
Hai‐Dong Xia Zhong‐Liang Li Qiang‐Shuai Gu Xiao‐Yang Dong Jia‐Heng Fang Xuan‐Yi Du Li‐Lei Wang Xin‐Yuan Liu 《Angewandte Chemie (International ed. in English)》2020,59(39):16926-16932
We describe a photoinduced copper‐catalyzed asymmetric radical decarboxylative alkynylation of bench‐stable N‐hydroxyphthalimide(NHP)‐type esters of racemic alkyl carboxylic acids with terminal alkynes, which provides a flexible platform for the construction of chiral C(sp3)?C(sp) bonds. Critical to the success of this process are not only the use of the copper catalyst as a dual photo‐ and cross‐coupling catalyst but also tuning of the NHP‐type esters to inhibit the facile homodimerization of the alkyl radical and terminal alkyne, respectively. Owing to the use of stable and easily available NHP‐type esters, the reaction features a broader substrate scope compared with reactions using the alkyl halide counterparts, covering (hetero)benzyl‐, allyl‐, and aminocarbonyl‐substituted carboxylic acid derivatives, and (hetero)aryl and alkyl as well as silyl alkynes, thus providing a vital complementary approach to the previously reported method. 相似文献
152.
Jonathan C. Golec Eve M. Carter John W. Ward William G. Whittingham Luis Simn Robert S. Paton Darren J. Dixon 《Angewandte Chemie (International ed. in English)》2020,59(40):17417-17422
A bifunctional iminophosphorane (BIMP)‐catalysed enantioselective synthesis of α,β‐unsaturated cyclohexenones through a facially selective 1,3‐prototropic shift of β,γ‐unsaturated prochiral isomers, under mild reaction conditions and in short reaction times, on a range of structurally diverse substrates, is reported. α,β‐Unsaturated cyclohexenone products primed for downstream derivatisation were obtained in high yields (up to 99 %) and consistently high enantioselectivity (up to 99 % ee). Computational studies into the reaction mechanism and origins of enantioselectivity, including multivariate linear regression of TS energy, were carried out and the obtained data were found to be in good agreement with experimental findings. 相似文献
153.
Supramolecular capsules can be used to change the activity and selectivity of a catalyst through the influence of the second coordination sphere, reminiscent of how enzymes control the selectivity of their processes. In enzymes, this approach is used to also control the enantioselectivity of reactions in which the active catalytic site is often not chiral but the second coordination sphere is. We are interested in the possibility to generate a chiral second coordination sphere around an otherwise achiral transition metal complex for asymmetric catalysis. In this paper we show that the ligand template approach can be used to generate a chiral second coordination sphere around a rhodium complex, which is used in asymmetric hydroformylation. 相似文献
154.
155.
156.
157.
以焦谷氨酸为原料,通过两种路线,分别合成了5-位反式苯基取代脯氨酸和5-位顺式苯基取代脯氨酸,总收率分别为43.9%和51.0%。其结构经1H NMR,13C NMR和MS表征。 相似文献
158.
In this work, we designed and studied a feasible dual-layer binary metagrating, which can realize controllable asymmetric transmission and beam splitting with nearly perfect performance. Owing to ingenious geometry configuration, only one meta-atom is required to design for the metagrating system. By simply controlling air gap between dual-layer metagratings, high-efficiency beam splitting can be well switched from asymmetric transmission to symmetric transmission. The working principle lies on gap-induced diffraction channel transition for incident waves from opposite directions. The asymmetric/symmetric transmission can work in a certain frequency band and a wide incident range. Compared with previous methods using acoustic metasurfaces, our approach has the advantages of simple design and tunable property and shows promise for applications in wavefront manipulation, noise control and one-way propagation. 相似文献
159.
Yang-Je Cheng Cai-Wei Li Cing-Ling Kuo Tzenge-Lien Shih Jih-Jung Chen 《Molecules (Basel, Switzerland)》2022,27(8)
In this paper, the syntheses of twelve asymmetric curcumin analogs using Pabon’s method are reported. Generally, the previously reported yields of asymmetric curcuminoids, such as 9a (53%), 9c (38%), and 9k (38%), have been moderate or low. Herein, we propose that the low yields were due to the presence of water and n-BuNH2 in the reaction media. To prove this formulated hypothesis, we have demonstrated that the yields can be improved by adding molecular sieves (MS) (4 Å) to the reaction mixture, thus reducing the interference of water. Therefore, improved yields (41–76%) were obtained, except for 9b (36.7%), 9g (34%), and 9l (39.5%). Furthermore, compounds 9b, 9d, 9e, 9f, 9g, 9h, 9i, 9j, and 9l are reported herein for the first time. The structures of these synthetic compounds were determined by spectroscopic and mass spectrometry analyses. The free radical scavenging ability of these synthetic asymmetric curcuminoids was evaluated and compared to that of the positive control butylated hydroxytoluene (BHT). Among the synthesized asymmetric curcuminoids, compounds 9a (IC50 = 37.57 ± 0.89 μM) and 9e (IC50 = 37.17 ± 1.76 μM) possessed effective 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging abilities, and compounds 9h (IC50 = 11.36 ± 0.65 μM) and 9i (IC50 = 10.91 ± 0.77 μM) displayed potent 2,2’-azinobis-(3-ethylbenzthiazoline-6-sulphonate) (ABTS) radical scavenging abilities comparable to that of curcumin (IC50 = 10.14 ± 1.04 μM). Furthermore, all the synthetic asymmetric curcuminoids were more active than BHT. 相似文献
160.