全文获取类型
收费全文 | 787篇 |
免费 | 9篇 |
国内免费 | 4篇 |
专业分类
化学 | 481篇 |
晶体学 | 1篇 |
力学 | 35篇 |
数学 | 136篇 |
物理学 | 147篇 |
出版年
2021年 | 10篇 |
2020年 | 9篇 |
2017年 | 7篇 |
2016年 | 12篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 19篇 |
2011年 | 28篇 |
2010年 | 17篇 |
2009年 | 18篇 |
2008年 | 31篇 |
2007年 | 22篇 |
2006年 | 15篇 |
2005年 | 18篇 |
2004年 | 14篇 |
2003年 | 14篇 |
2002年 | 21篇 |
2001年 | 17篇 |
2000年 | 10篇 |
1999年 | 11篇 |
1998年 | 9篇 |
1997年 | 13篇 |
1996年 | 16篇 |
1995年 | 12篇 |
1994年 | 14篇 |
1993年 | 8篇 |
1992年 | 14篇 |
1988年 | 13篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 15篇 |
1981年 | 9篇 |
1980年 | 10篇 |
1979年 | 11篇 |
1978年 | 7篇 |
1977年 | 17篇 |
1976年 | 11篇 |
1975年 | 7篇 |
1974年 | 11篇 |
1973年 | 12篇 |
1970年 | 7篇 |
1967年 | 8篇 |
1936年 | 7篇 |
1933年 | 6篇 |
1930年 | 6篇 |
1909年 | 7篇 |
1884年 | 7篇 |
排序方式: 共有800条查询结果,搜索用时 15 毫秒
31.
Oxidative Addition of Haloheteroarenes to Palladium(0): Concerted versus SNAr‐Type Mechanism
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Bert U. W. Maes Dr. Stefan Verbeeck Dr. Tom Verhelst Audrey Ekomié Niklas von Wolff Dr. Guillaume Lefèvre Dr. Emily A. Mitchell Prof. Anny Jutand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7858-7865
The kinetics of the oxidative additions of haloheteroarenes HetX (X=I, Br, Cl) to [Pd0(PPh3)2] (generated from [Pd0(PPh3)4]) have been investigated in THF and DMF and the rate constants have been determined. In contrast to the generally accepted concerted mechanism, Hammett plots obtained for substituted 2‐halopyridines and solvent effects reveal a reaction mechanism dependent on the halide X of HetX: an unprecedented SNAr‐type mechanism for X=Br or Cl and a classical concerted mechanism for X=I. These results are supported by DFT studies. 相似文献
32.
33.
Patrick Homenya Markus Messerschmidt Muhammad Nawaz Tahir Victor Martinez Yajun Cheng Jochen S. Gutmann Michael Klein Stefan Jung Morris Wolff Reza Saadat Driss Nariaki Roman Bo?a G?star Klingelh?fer Wolfgang Tremel Franz Renz 《Hyperfine Interactions》2012,205(1-3):63-67
The nonanuclear coordination compound [MoIV{(CN)FeIII(3-methyl-saldptn)}8]Cl4 exhibits multiple spin transitions (3-methyl-saldptn = N,N′-bis(3′′-methyl-2′′-hydroxy-benzyliden)-1,7-diamino-4-azaheptane). This spin crossover cluster is bound via a self-assembled monolayer onto a two dimensional array gold surface. M?ssbauer spectroscopy indicates that the thermally and optically induced spin crossover of the compound is maintained. Thereby, the foundation for its potential practical application (e.g. in the field of information storage) was laid. 相似文献
34.
Ibtissam Elaaraj Safae ER. Raouan Asmae Nakkabi Bouchra Es-sounni Ibnsouda Koraichi Noureddine El moualij Mohammed Fahim 《印度化学会志》2022,99(5):100404
New metal complexes of (Zn(II), Co(II), Ni(II) and Cu(II)) based on the ligand 2-(thiophen-2-yl)-1-(thiophen-2-ylmethyl)-1H-benzo[d]imidazole] were synthesized, whose structures were determined with the different spectroscopic techniques 1H NMR,13C NMR, FT-IR, UV–Visible and by mass spectrometry. The thermal analysis was performed by TG-DTA. The antioxidant activity of the ligand and its complexes was evaluated by DPPH (2,2-diphenyl-1-picrylhydrazyl) method, in comparison with the synthetic antioxidant, ascorbic acid. The results obtained showed that the antioxidant activity of the ligand and its complexes is moderate and that the copper complex has a high activity that exceeds that of ascorbic acid. Antimicrobial activity of the ligand and its metal complexes was studied against two Gram-positive bacteria: Bacillus subtilis ILP1428B, Staphylococcus aureus CIP543154 and two Gram-negative bacteria: Pseudomonas aeruginosa ATCC27653, Escherichia coli CIP5412 (American Type Culture Collection)the activity data show that the metal complexes are more potent than the free ligand. 相似文献
35.
36.
Dr. Marina Büchert Torben Steenbock Christian Lukaschek Marie C. Wolff Prof. Dr. Carmen Herrmann Prof. Dr. Jürgen Heck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(44):14351-14361
Parallel alignment of dipolar electron‐donor–π‐bridge‐electron‐acceptor entities can strongly enhance their nonlinear optical properties. This favorable arrangement can be in principle achieved by linking these units covalently or through metal coordination. Four dipolar single‐strand chromophores decorated with a 5‐electron‐donor–5′‐electron‐acceptor‐modified 2,2′‐bipyridine functionality were synthesized. For two of these chromophores triple‐stranded dendritic structures were successfully formed. All of the compounds were characterized with respect to their linear and nonlinear optical properties. For the aldehyde derivatives an enhancement of the first hyperpolarizability of 4.5 rather than 3 was obtained when going from single to triple strands. Theoretical calculations with density functional theory suggest that interstrand transitions contribute to the optical properties of the dendritic structures. 相似文献
37.
ukasz Balewski Franciszek Sczewski Patrick J. Bednarski Lisa Wolff Anna Nadworska Maria Gdaniec Anita Kornicka 《Molecules (Basel, Switzerland)》2020,25(24)
The appropriate 1-arylhydrazinecarbonitriles 1a–c are subjected to the reaction with 2-chloro-4,5-dihydro-1H-imidazole (2), yielding 7-(4,5-dihydro-1H-imidazol-2-yl)-2-aryl-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-imines 3a–c, which are subsequently converted into the corresponding amides 4a–e, 8a–c, sulfonamides 5a–n, 9, ureas 6a–I, and thioureas 7a–d. The structures of the newly prepared derivatives 3a–c, 4a–e, 5a–n, 6a–i, 7a–d, 8a–c, and 9 are confirmed by IR, NMR spectroscopic data, as well as single-crystal X-ray analyses of 5e and 8c. The in vitro cytotoxic potency of these compounds is determined on a panel of human cancer cell lines, and the relationships between structure and antitumor activity are discussed. The most active 4-chloro-N-(2-(4-chlorophenyl)-7-(4,5-dihydro-1H-imidazol-2-yl)-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-ylidene)benzamide (4e) and N-(7-(4,5-dihydro-1H-imidazol-2-yl)-2-(p-tolyl)-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-ylidene)-[1,1′-biphenyl]-4-sulfonamide (5l) inhibits the growth of the cervical cancer SISO and bladder cancer RT-112 cell lines with IC50 values in the range of 2.38–3.77 μM. Moreover, N-(7-(4,5-dihydro-1H-imidazol-2-yl)-2-phenyl-6,7-dihydro-2H-imidazo[2,1-c][1,2,4]triazol-3(5H)-ylidene)-4-phenoxybenzenesulfonamide (5m) has the best selectivity towards the SISO cell line and induces apoptosis in this cell line. 相似文献
38.
The dependence of the rotation of the mesogenic unit around its long axis (β-relaxation) on the actual mesophase in liqid crystalline polymethacrylates and polyacrylates was studied by dielectric spectroscopy in the frequency range from 10−2 Hz to 106 Hz and in a temperature range from 170 K to 430 K. As mesogenic units derivatives of (p-alkoxy-phenyl)-benzoate were used where different mesophases were achieved by small variation of the mesogenic structure, the spacer length and the tail group of the mesogenic unit. For all samples the temperature dependence of the relaxation rate of the β-relaxation can be described by an Arrhenius equation where both the pre-exponential factor and the activation energy increase significantly with the order of the mesophase. To characterize the structure X-ray measurements were also carried out. The mean lateral mesogenic distance was correlated directly with relaxational quantities. 相似文献
39.
40.