全文获取类型
收费全文 | 556篇 |
免费 | 7篇 |
国内免费 | 4篇 |
专业分类
化学 | 339篇 |
力学 | 27篇 |
数学 | 47篇 |
物理学 | 154篇 |
出版年
2021年 | 4篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2016年 | 6篇 |
2015年 | 6篇 |
2014年 | 16篇 |
2013年 | 20篇 |
2012年 | 23篇 |
2011年 | 21篇 |
2010年 | 14篇 |
2009年 | 9篇 |
2008年 | 23篇 |
2007年 | 25篇 |
2006年 | 33篇 |
2005年 | 21篇 |
2004年 | 23篇 |
2003年 | 19篇 |
2002年 | 15篇 |
2001年 | 9篇 |
2000年 | 16篇 |
1999年 | 5篇 |
1998年 | 12篇 |
1997年 | 7篇 |
1996年 | 15篇 |
1995年 | 5篇 |
1994年 | 10篇 |
1993年 | 7篇 |
1992年 | 9篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1987年 | 4篇 |
1985年 | 13篇 |
1984年 | 5篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 9篇 |
1980年 | 13篇 |
1979年 | 9篇 |
1978年 | 17篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1975年 | 8篇 |
1973年 | 7篇 |
1970年 | 4篇 |
1969年 | 4篇 |
1968年 | 4篇 |
1967年 | 4篇 |
1966年 | 4篇 |
1870年 | 4篇 |
排序方式: 共有567条查询结果,搜索用时 78 毫秒
1.
Patrick Mather Nino Grizzuti Glenn Heffner Mathias Ricker Willie E. Rochefort Markus Seitz Hans-Werner Schmidt Dale S. Pearson 《Liquid crystals》1994,17(6):811-826
In this paper, we report on the synthesis and detailed characterization of a new semiflexible nematic liquid crystalline polyester which could serve as a 'model' polyester for a variety of physical and physico-chemical investigations. The polymer is a nematic liquid over a wide temperature range-from the glass transition temperature at ∼95°C to the isotropic transition at ∼240°C. We expect this polyester to be particularly useful for studying the effect of flow on the orientation of liquid crystalline polymers, as well as the production and removal of disclinations. 相似文献
2.
3.
4.
[reaction: see text] A practical synthesis of the potent class I alpha-mannosidase inhibitor kifunensine (1) beginning from the inexpensive and readily available starting material L-ascorbic acid (15) is described. The protected amino-alcohol ((2R,3R,4R,5R)-5-amino-2,3:4,6-diisopropylidenedioxyhexanol, 11) served as a key intermediate from which several N-1 substituted kifunensine analogues (including N-methyl, N-cyclohexyl, and N-bis(hydroxymethyl)methyl) and 2-desoxakifunensine analogues (including N-H and N-methyl) were prepared and screened for inhibition of human endoplasmic reticulum alpha-mannosidase I (ER Man I) and mouse Golgi alpha-mannosidase IA (Golgi Man IA). In addition, several pseudodisaccharide kifunensine analogues in which a mannose residue was tethered to N-1 of kifunensine via a two-, three-, or four-carbon linker and an affinity-bound kifunensine analogue were also prepared and evaluated for biological activity. While the synthesized N-1 kifunesine analogues were found to be less potent inhibitors of Class I alpha-mannosidases than kifuensine itself, the bis(hydroxymethyl)methylkifunensine analogue 6 was shown to selectively inhibit ER Man I over Golgi Man IA. 相似文献
5.
The 13C and proton NMR spectra of six porphyrins bearing the substituent orientation characteristic of the natural “Type-IX” arrangement are reported and assigned. Significant concentration effects in the spectra of the free base porphyrins, together with the broadening of the Cα (and occasionally Cβ) carbon resonances due to NH tautomerism caused a significant loss of data in these spectra. However, the spectra of the corresponding zinc(II) porphyrins (with addition of excess pyrrolidine) show that both these extraneous effects are completely removed to give well-resolved spectra with accurately reproducible chemical shifts. These spectra are assigned and an analysis of the chemical shifts allows the deduction of substituent chemical shift (SCS) parameters for the peripheral substituents at the beta and meso carbons. There is no global effect of these beta substituents, the beta carbon SCS being confined to the immediate pyrrole ring, and the meso carbon SCS to the two adjacent pyrrole rings. The SCS parameters are analyzed and it is shown how they can be used to predict the peripheral and meso carbon chemical shifts of any porphyrin bearing the substituents discussed. 相似文献
6.
7.
8.
William H. Pearson Joseph E. Celebuski Yam-Foo Poon Brian R. Dixon Jeffrey H. Glans 《Tetrahedron letters》1986,27(52):6301-6304
Cyclization of heterosubstituted ω-azidodienes 11 provides fused bicyclic 3-pyrrolines 12 in one operation. These pyrrolines are potentially useful intermediates for natural products synthesis, as illustrated by further functionalization. 相似文献
9.
The intramolecular capture of benzocyclobutyl, benzocyclopentyl, and benzocyclohexyl carbocations 7 by azides produces spirocyclic aminodiazonium ions 8, which undergo 1,2-C-to-N rearrangement with loss of dinitrogen to produce benzo-fused iminium ions resulting from either aryl (9) or alkyl (10) migration to the electron-deficient nitrogen atom. Reduction of the iminium ions affords regioisomeric benzo-fused 1-azabicyclo[m.n.0]alkanes, e.g., benzopyrrolizidines, benzoindolizidines, benzoquinolizidines, or perhydrobenzo[f]pyrrolo[1,2-a]azepines in two regioisomeric versions, anilines (e.g., 11-14) and benzylic amines (e.g., 15-18), the result of aryl and alkyl migrations, respectively. Generally, aryl migration is preferred, despite modeling that shows that the lowest energy aminodiazonium ions are those where the departing dinitrogen is preferentially antiperiplanar to the migrating alkyl group rather than the aryl group. The utility of this methodology was illustrated by a formal synthesis of the alkaloid gephyrotoxin 4. A dependence on the efficiency and regioselectivity of the Schmidt reaction upon subtle changes in the structure of the cation precursor was observed, necessitating the exploration of a variety of substrates. Fortunately, these materials were easily made. Ultimately, the azido-alkene 81 bearing a 2-bromoethyl side-chain was useful for the Schmidt reaction, producing the known benzo-fused indolizidine 49, which had been transformed by Ito et al. into gephyrotoxin 4. The synthesis of 49 required nine steps (five purifications) from commercially available 4-methoxy-1-indanone 60 and proceeded in 22% overall yield. 相似文献
10.
Abstract— One of the four major photoproducts formed by UV irradiation of TpT in aqueous solution has a number of unusual properties. This compound, which we arbitrarily call TpT4 , is produced irreversibly from TpT with single-hit kinetics and seems to represent a novel pathway for TpT photolysis different from the conventional cyclobutane ring dimer formation. This communication describes the preparative isolation of TpT4 by ion-exchange chromatography on DEAE-cellulose and its UV, fluorescence and IR spectra. TpT4 has an absorption maximum at 325 mμ, fluoresces at 405 mμ when excited at 325 mμ, and has an IR spectrum consistent with the assumption that one of the thymine rings has been converted to a pyrimidin-2-one structure. In addition, TpT4 appears to have both pyrimidine rings linked together and does not contain a peroxide group as previously supposed. Spectrophotometric titration shows that TpT4 has a pKâ of 10.75 and is unstable to prolonged treatment at extreme pH. A model structure consistent with the present data is given. This model contains the glycosidic and phosphodiester bonds intact with a 5-methylpyrimidine-2-one ring and a thymine ring joined in ether linkage at the C4 positions, with an OH at the C4 position in the thymine ring. 相似文献