全文获取类型
收费全文 | 367篇 |
免费 | 13篇 |
专业分类
化学 | 182篇 |
力学 | 23篇 |
数学 | 36篇 |
物理学 | 139篇 |
出版年
2022年 | 4篇 |
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 6篇 |
2018年 | 3篇 |
2016年 | 8篇 |
2015年 | 8篇 |
2014年 | 12篇 |
2013年 | 17篇 |
2012年 | 16篇 |
2011年 | 14篇 |
2010年 | 9篇 |
2009年 | 8篇 |
2008年 | 10篇 |
2007年 | 9篇 |
2006年 | 20篇 |
2005年 | 11篇 |
2004年 | 12篇 |
2003年 | 7篇 |
2002年 | 20篇 |
2001年 | 9篇 |
2000年 | 9篇 |
1999年 | 12篇 |
1998年 | 6篇 |
1997年 | 7篇 |
1996年 | 3篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 7篇 |
1982年 | 8篇 |
1981年 | 8篇 |
1980年 | 2篇 |
1978年 | 4篇 |
1977年 | 7篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 6篇 |
1971年 | 3篇 |
1933年 | 5篇 |
1930年 | 2篇 |
1929年 | 2篇 |
1886年 | 2篇 |
1883年 | 2篇 |
排序方式: 共有380条查询结果,搜索用时 15 毫秒
11.
12.
Summary The complex [RuII(hedta)(4NH2pym)]−, hedta3− = N-hydroxyethylethylenediaminetriacetate, 4NH2pym = 4-aminopyrimidine, exists at pH 7 as five different coordination isomers, which are most readily distinguished by their
electrochemical waves in comparison with the 2-aminopyridine (2NH2py) complex. The 2NH2py complex exhibits N(1) (pyridine bound), exo-NH2 (amine bound) and N(1), NH2-chelated species. The 4NH2pym complex forms N(1), exo-amine and N(3), NH2-chelated isomers analogues to the 2NH2py species, but also engages in η2 (olefin bound) coordination of the dearomatized 4NH2pym ring in C(5)–C(6), and another η2 type of complex involving electron density between N(1) and N(3) of the ring (η3 form). N(1), η2 and η3 isomers have also been detected for unsubstituted pyrimidine (pym), 4-methylprimidine (4CH3pym) and 2-aminopyrimidine (2NH2pym). Electrochemical waves (V versus NHE) for the five isomers are assigned as follows: (RuII/III) exo-NH2 (0.06 V), N(1) (0.29 V), η2 (0.49 V); (RuII/III) η3 (0.76 V); N(3), NH2-chelated (1.09 V). 相似文献
13.
Summary The following [(NH3)5RhLH]Cl3 salts were preparedvia the [(NH3)5Rh(O3SCF3)](O3SCF3)2 synthetic route; LH=1-methylimidazole (1CH3imH), 2-methylimidazole (2CH3imH), 4-methylimidazole (4CH3imH), 5-methylimidazole(5CH3imH), and pyrazole (pyzH). pKa's at 25.0°C were determined for [(NH3)5RhLH]3+ complexes as follows: 2CH3imH, 10.4±0.1; 5CH3imH/4CH3imH isomer mixture, 10.3±0.1; pyzH, 6.54±0.05. The influence on the pKa's of imidazoles is dominated by withdrawal of the rhodium(III) centre and may be compensated by the presence of ring methylation by only 0.5log units for cobalt(III) and rhodium(III) derivatives, compared to 1.3 units for the -withdrawing ruthenium(III) centre. In the case of the -acceptor pyrazole ring, [(NH3)5Rh]3+ is observed to serve as a slight -donor and raises the pKa above the cobalt(III) analogue. The1H n.m.r. spectra of [(NH3)5RhLH]3+ complexes of the substituted imidazoles and pyrazole exhibit a deshielding order. C–2H>C–5H>C–4H for imidazoles and C–3H>C–5H>C–4H for pyrazole, as do their cobalt(III) analogues. The magnitude of values (=free L-complex) are virtually the same as in the cobalt(III) systems which shows that TIP influences are unimportant compared to ring rehybridization in estabilishing chemical shifts for both the cobalt(III) and rhodium(III) complexes. The imidazolato and pyrazolato complexes exhibit resonances upfield of the respective substituted imidazole or pyrazole complex in keeping with more negative charge on the rings; the influence is largest at C–2H of imidazolates and C–3H of pyrazolate. 相似文献
14.
Adams LA Aggarwal VK Bonnert RV Bressel B Cox RJ Shepherd J de Vicente J Walter M Whittingham WG Winn CL 《The Journal of organic chemistry》2003,68(24):9433-9440
A simple and high-yielding method for the preparation of cyclopropane amino acids is described. The novel method involves the one-pot cyclopropanation of readily available dehydroamino acids using aryl and unsaturated diazo compounds generated in situ from the corresponding tosylhydrazone salts. It was found that thermal 1,3-dipolar cycloaddition followed by nitrogen extrusion gave the cyclopropane amino acid derivatives with good E selectivity, while reactions in the presence of meso-tetraphenylporphyrin iron chloride gave predominantly the corresponding Z isomers. The synthetic utility of this process was demonstrated in the synthesis of (+/-)-(Z)-2,3-methanophenylalanine [(+/-)-(Z)-1], the anti-Parkinson (+/-)-(E)-2,3-methano-m-tyrosine [(+/-)-(E)-2], and the natural product (+/-)-coronamic acid [(+/-)-3]. 相似文献
15.
16.
17.
18.
Andreas Dorian Emily J. Landgreen Hayley R. Petras Prof. James J. Shepherd Prof. Florence J. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(42):10839-10843
The facile production of ArCF2X and ArCX3 from ArCF3 using catalytic iron(III)halides is reported, which constitutes the first iron-catalyzed halogen exchange for non-aromatic C−F bonds. Theoretical calculations suggest direct activation of C−F bonds by iron coordination. ArCX3 and ArCF2X products of the reaction are synthetically valuable due to their diversification potential. In particular, chloro- and bromodifluoromethyl arenes (ArCF2Cl, ArCF2Br respectively) provide access to a myriad of difluoromethyl arene derivatives (ArCF2R). To optimize for mono-halogen exchange, a statistical method called Design of Experiments was used. Optimized parameters were successfully applied to electron rich and electron deficient aromatic substrates, and to the late stage diversification of flufenoxuron, a commercial insecticide. These methods are highly practical, being run at convenient temperatures and using inexpensive common reagents. 相似文献
19.
Cornelius von Morze Douglas A.C. Kelley Timothy M. Shepherd Suchandrima Banerjee Duan Xu Christopher P. Hess 《Magnetic resonance imaging》2010
Ventral and rostral regions of the brain are of emerging importance for the MRI characterization of early dementia, traumatic brain injury and epilepsy. Unfortunately, standard single-shot echo planar diffusion-weighted imaging of these regions at high fields is contaminated by severe imaging artifacts in the vicinity of air–tissue interfaces. To mitigate these artifacts and improve visualization of the temporal and frontal lobes at 7 T, we applied a reduced field-of-view strategy, enabled by outer volume suppression (OVS) with novel quadratic phase radiofrequency (RF) pulses, combined with partial Fourier and parallel imaging methods. The new acquisition greatly reduced the level of artifacts in six human subjects (including four patients with early symptoms of dementia). 相似文献
20.
Dr. Tran Quang Hung Dr. Ferial Terki Dr. Souleymane Kamara Mourad Dehbaoui Prof. Salam Charar Brajalal Sinha Prof. CheolGi Kim Dr. Philippe Gandit Il'ya A. Gural'skiy Dr. Gabor Molnar Dr. Lionel Salmon Dr. Helena J. Shepherd Dr. Azzedine Bousseksou 《Angewandte Chemie (International ed. in English)》2013,52(4):1058-1058