全文获取类型
收费全文 | 1973篇 |
免费 | 176篇 |
国内免费 | 6篇 |
专业分类
化学 | 1594篇 |
晶体学 | 23篇 |
力学 | 23篇 |
数学 | 107篇 |
物理学 | 408篇 |
出版年
2023年 | 22篇 |
2022年 | 22篇 |
2021年 | 42篇 |
2020年 | 64篇 |
2019年 | 75篇 |
2018年 | 48篇 |
2017年 | 31篇 |
2016年 | 104篇 |
2015年 | 96篇 |
2014年 | 94篇 |
2013年 | 115篇 |
2012年 | 192篇 |
2011年 | 219篇 |
2010年 | 85篇 |
2009年 | 80篇 |
2008年 | 152篇 |
2007年 | 117篇 |
2006年 | 107篇 |
2005年 | 99篇 |
2004年 | 82篇 |
2003年 | 51篇 |
2002年 | 44篇 |
2001年 | 24篇 |
2000年 | 22篇 |
1999年 | 9篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 7篇 |
1995年 | 10篇 |
1994年 | 8篇 |
1993年 | 11篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 8篇 |
1989年 | 10篇 |
1988年 | 7篇 |
1987年 | 9篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 13篇 |
1983年 | 6篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1976年 | 2篇 |
1975年 | 3篇 |
1973年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有2155条查询结果,搜索用时 15 毫秒
41.
New conformationally restricted analogues of tumor promoter (−)-indolactam-V (1), indolinelactam-Vs (8, 11) and their hexyl derivatives at position 1 or 7 (9, 10, 12, 13), were synthesized from 1. (3R)-Indolinelactam-V (8) adopted a conformation similar to the twist form of 1 with a cis amide, while the conformation of (3S)-indolinelactam-V (11) was close to that of the sofa form of 1 with a trans amide. 7-Hexyl derivatives of 8 and 11 (10, 13) showed binding affinities for C1 domains of protein kinase C (PKC) isozymes compared to 1, but exhibited little selectivity among these PKC isozymes. However, introduction of the hexyl group at position 1 of 8 and 11 significantly enhanced their binding selectivity for novel PKC isozymes. The best selectivity for novel PKC isozymes was observed in (3S)-1-hexylindolinelactam-V (12) with a sofa-like conformation. These results suggest that a sofa-restricted analogue of 1 with a hydrophobic chain at an appropriate position would be a promising lead for designing agents with a high selectivity for novel PKC isozymes. 相似文献
42.
An effective method was developed to use an enzyme in ionic liquids; the asymmetric reduction of ketones by Geotrichum candidum in ionic liquids proceeded smoothly with excellent enantioselectivity when the cell was immobilized on water-absorbing polymer containing water, while the reaction without the polymer did not proceed. 相似文献
43.
Tatsuhiko Kashimura Tomoya Ikezaki Yusuke Ohta Satoshi Yabushita 《Journal of computational chemistry》2019,40(2):482-499
One of the most spectacular yet unsolved problems for the ICN -band photodissociation is the non-statistical spin-rotation F1 = N + 1/2 and F2 = N − 1/2 populations for each rotation level N of the CN fragment. The F1/F2 population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (2P3/2) and I (2P1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F1 and F2 levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N . We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F1 and F2 level populations observed by Zare's group and Hall's group, respectively. © 2018 Wiley Periodicals, Inc. 相似文献
44.
Using modern NMR techniques, including DQF-COSY, NOESY, HETCOR and HMBC, the full assignments of all 1H and 13C chemical shifts were made for stigmastane-3,6-dione and stigmast-4-ene-3,6-dione, isolated from the roots of Piper nigrum (Piperaceae). Their stereochemistry was resolved by a combination of 2D NOESY data and analysis of coupling constants. The two compounds were isolated from the genus Piper for the first time. 相似文献
45.
46.
Koichiro Koyama Yusuke Hirasawa Tomohiro Hoshino Norimichi Nakahata 《Tetrahedron》2005,61(15):3681-3690
Seven new Lycopodium alkaloids, lannotinidines A-G (1-7), have been isolated from the club moss Lycopodium annotinum and L. annotinum var. acrifolium. Stereochemistry of 1-7 was elucidated by combination of NOESY correlations and chemical transformation. Lannotinidines B-E (2-5) elevated NGF mRNA expression. 相似文献
47.
Ohno H Ando K Hamaguchi H Takeoka Y Tanaka T 《Journal of the American Chemical Society》2002,124(51):15255-15266
The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by B3LYP density functional calculations together with the 6-31+G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner. 相似文献
48.
Ikuo Ashikawa Mariko Kito Kimiyuki Satoh Hiroyuki Koike Yorinao Inoue Kayoko Saiki Kiyoshi Tsukida Yasushi Koyama 《Photochemistry and photobiology》1987,46(2):269-275
All- trans β-carotene-5,6-epoxide has been found in the thylakoid membranes of spinach and of the cyanobacterium Synechococcus vulcanus Copeland. The epoxide was extracted from the thylakoid membranes with acetone, and was isolated by high-performance liquid chromatography (HPLC). The structure of the epoxide was identified by means of mass, Raman, and electronic absorption spectroscopy. Changes in the amount of the epoxide, as a result of epoxidation and (apparent) de-epoxidation reactions in the membranes, were traced by analysis of extracts on HPLC. In isolated thylakoid membranes, only the epoxidation reaction took place. The reaction was caused by irradiation or by the addition of ferricyanide, suggesting that electron transport reactions in the membranes are involved in the epoxidation. In intact spinach leaves, however, both epoxidation and de-epoxidation took place; the extent of epoxidation correlated with the intensity of light incident on the leaves. The epoxidation and de-epoxidation of all- trans β-carotene are contrasted with those of xanthophylls (in the violaxanthin cycle). 相似文献
49.
An on-line purification method for catecholamines was studied using a flow system equipped with an alumina microcolumn. The procedure involves catecholamine adsorption, column washing and catecholamine elution steps. The system is designed not to decompose catecholamines under alkaline conditions in the adsorption step. Flow-rates and times for different solutions delivered in each step (alkaline buffer for adsorption, water for washing and an acidic solution for elution), column length and sample volume to be loaded were systematically investigated by liquid chromatography. Under optimum conditions, norepinephrine, epinephrine, dopamine and 3,4- dihydroxybenzylamine (internal standard) can be purified with recoveries of ? 90% within 11 min with manual operation. This method was efficiently applied to urine samples and the results indicate the possibility that catecholamines in biological samples are automatically purified. 相似文献
50.
N. Momoshima Y. Takashima M. Koike Y. Imaizumi T. Harada 《Journal of Radioanalytical and Nuclear Chemistry》1994,177(2):219-228
A determination procedure has been developed for210Bi and210Po in environmental samples and was applied for pine needles. Bismuth-210 and210Po separated from the parent nuclide210Pb as BiOCl precipitate were extracted simultaneously by TOPO/toluene containing PPO and POPOP. The separation of210Bi and210Po from210Pb was almost satisfactory. The activity of210Bi+210Po in the TOPO/toluene was measured periodically by liquid scintillation counting for about 20 days after separation. The time course of the decreasing pattern of the activity was determined by the initial activity ratio210Po/210Bi. The decreasing pattern of the activity was compared with theoretical patterns, and best estimates for210Po and210Bi were obtained by non-linear least-squares fitting. The activities of210Bi and210Po were determined for one-year and two-year old pine needles fro the same pine tree, and weathering half-time and deposition rate of these nuclides was discussed. 相似文献