全文获取类型
收费全文 | 1520篇 |
免费 | 27篇 |
国内免费 | 5篇 |
专业分类
化学 | 1180篇 |
晶体学 | 18篇 |
力学 | 12篇 |
数学 | 54篇 |
物理学 | 288篇 |
出版年
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 14篇 |
2018年 | 12篇 |
2017年 | 8篇 |
2016年 | 15篇 |
2015年 | 14篇 |
2014年 | 35篇 |
2013年 | 60篇 |
2012年 | 86篇 |
2011年 | 88篇 |
2010年 | 30篇 |
2009年 | 46篇 |
2008年 | 99篇 |
2007年 | 72篇 |
2006年 | 65篇 |
2005年 | 70篇 |
2004年 | 78篇 |
2003年 | 79篇 |
2002年 | 72篇 |
2001年 | 47篇 |
2000年 | 19篇 |
1999年 | 22篇 |
1998年 | 23篇 |
1997年 | 15篇 |
1996年 | 22篇 |
1995年 | 18篇 |
1994年 | 13篇 |
1993年 | 14篇 |
1992年 | 18篇 |
1991年 | 20篇 |
1990年 | 11篇 |
1989年 | 13篇 |
1988年 | 14篇 |
1987年 | 19篇 |
1986年 | 21篇 |
1985年 | 23篇 |
1984年 | 16篇 |
1983年 | 17篇 |
1982年 | 13篇 |
1981年 | 17篇 |
1980年 | 17篇 |
1979年 | 22篇 |
1978年 | 21篇 |
1977年 | 19篇 |
1976年 | 19篇 |
1975年 | 22篇 |
1974年 | 9篇 |
1973年 | 17篇 |
1971年 | 8篇 |
排序方式: 共有1552条查询结果,搜索用时 93 毫秒
21.
Watanabe M Sue K Adschiri T Inomata H Smith RL Arai K 《Chemical communications (Cambridge, England)》2001,(21):2270-2271
In supercritical water the rate of methanol oxidation was controlled by ionic behavior as follows: the oxidation rate of methanol decreased with increasing proton and hydroxide ion concentration, possibly due to stabilization of the reactant, while that of CO was suppressed by added protons and enhanced by added hydroxide ions. 相似文献
22.
Stability of porphyrin-calix[4]arene complexes analyzed by electrospray ionization mass spectrometry
Arai S Ishihara S Takeoka S Ohkawa H Shibue T Nishide H 《Rapid communications in mass spectrometry : RCM》2004,18(18):2065-2068
The stability of some porphyrin-calix[4]arene sodium-ion complexes were determined by a collision-activated decomposition (CAD) method utilizing electrospray ionization mass spectrometry (ESI-MS). Comparing the values of E(1/2), the collision energy at which the relative intensity of the complex ion is 0.5, we found that the porphyrin-calix[4]arene complex with the higher value of E(1/2) corresponded to that with the larger association constant (Kass), as measured by 1H-NMR in CDCl3. Both our ESI-MS and NMR studies proved that the number of hydrogen bonds and the rigidity of the calix[4]arene stabilized the complex. The ESI-MS technique could be successful in screening the binding affinity in host-guest systems with a small amount of sample. 相似文献
23.
Gronert S Fagin AE Okamoto K 《Journal of the American Society for Mass Spectrometry》2004,15(10):1509-1516
The collision-activated dissociations (CAD) of gas phase salt complexes composed of chiral ions were studied in a quadrupole ion trap mass spectrometer. Because both partners in the salt are chiral, diastereomeric complexes can be formed (e.g., RR, RS). Two general types of complexes were investigated. In the first, the complex was composed of deprotonated binaphthol and a chiral bis-tetraalkylammonium dication. CAD of these complexes leads to the transfer of a proton or an alkyl cation to the binaphtholate leading to a singly-charged tetraalkylammonium cation. During CAD, diastereomeric complexes give significantly different product distributions indicating reasonable stereoselectivity in the process. In the second system, the complexes involved a peptide dianion and a chiral tetraalkylammonium cation. These systems may be viewed as very simple models for the interactions of peptides/proteins with small chiral molecules. Again, stereoselectivity was evident during CAD, but the extent was dependent on the nature of the peptide and not observable in some cases. To better understand the structural features needed to achieve stereoselectivity in gas phase salt complexes, representative transition states were modeled computationally. The results suggest that it is critical for the asymmetry of the nucleophile (i.e., anion) to be well represented in the vicinity of its reactive center. 相似文献
24.
Konda-Yamada Y Asano K Satou T Monma S Sakayanagi M Satou N Takeda K Harigaya Y 《Chemical & pharmaceutical bulletin》2005,53(5):529-536
Oxopropyl E-(pyrrolidine-2-ylidene)glycinamide (5c) and allyl E-(pyrrolidine-2-ylidene)glycinate (5d) were effectively synthesized from 2,3,5-tri-O-benzyl-4-O-tert-butyldimethylsilyl(TBDMS)-D-arabinal (7) using intramolecular 1,3-dipolar cyclic reaction of azide and olefin as a key reaction. These results proved this cyclic reaction should be applicable for the synthesis of various (pyrrolidine-2-ylidene)glycinate and glycinamide. In addition, the development of a synthetic route for the precursor of an unsaturated cyclic dehydro amino acid involved in azinomycins (carzinophilin) using relating glycinate, methyl E-(pyrrolidine-2-ylidene)glycinate (5a) was described. 相似文献
25.
N. A. Keiko L. G. Stepanova I. D. Kalikhman M. G. Voronkov 《Chemistry of Heterocyclic Compounds》1976,12(10):1094-1097
The conditions of heteropolar and radical thiylation of 2-formyl-2,5-diethoxy-2,3-dihydro--pyrans were studied. Oxidation of the carbonyl group occurs along with the Cannizzaro reaction in the reaction of 2-formyl-2,5-diethoxy-2,3-dihydro--pyran with silver oxide in alkaline media. Oxidation of 2-formyl-2,5-dibutylthio-2,3-dihydro--pyran with silver oxide leads to stable 2,5-dibutylthio-2,3-dihydro--pyran-2-carboxylic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1319–1322, October, 1976. 相似文献
26.
Goto S Masuda K Miura M Kanazawa K Sasaki M Masui M Shiramizu M Terada H Chuman H 《Chemical & pharmaceutical bulletin》2002,50(4):445-449
We measured the affinity of more than 20 sugars with concanavalin A (ConA) by an optical biosensor (surface plasmon resonance sensor) using asialofetuin (ASF) as an immobilized binding partner of ConA. We determined kinetic parameters of the effects of sugars on the dissociation of ConA from ASF quantitatively, and the structural requirements of the functional groups of sugars for binding with ConA. We found that the affinity of ConA for sugars is dependent on its conformation induced by interaction with the binding partner. In addition, the results showed that optical biosensor system is well mimics the interaction of ConA with sugars in biomembrane. 相似文献
27.
Sadao Arai Masanori Ishikura Kiyoshi Sato Takamichi Yamagishi 《Journal of heterocyclic chemistry》1995,32(3):1081-1083
The 16c-azonia[6]helicene salts, in which a carbon atom at the inner helix skeleton of [6]helicene is replaced by a quaternary nitrogen atom, have been synthesized by photo-induced intramolecular quater-nization of 2-[2-(1-chloronaphthyl)vinyl]benzo[h]quinolines in acetonitrile. 相似文献
28.
Yusei Maruyama Keiko Takamiya-Ichikawa 《International journal of quantum chemistry》1980,18(2):587-593
Fluorescence spectra and their temperature dependence of amorphous anthracene films doped with naphthacene were observed. An amorphous film was prepared by vacuum evaporation technique on a quartz plate cooled down to 30–40°K. The obtained results were discussed in relation to the structural change in the amorphous film. 相似文献
29.
Itoh T Nagata K Yokoya M Miyazaki M Kameoka K Nakamura S Ohsawa A 《Chemical & pharmaceutical bulletin》2003,51(8):951-955
Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline (16) in a highly enantioselective manner. 相似文献
30.
M. F. Shostakovskii A. S. Atavin E. P. Vyalykh B. A. Trofimov N. A. Vodhol'skaya V. V. Keiko 《Russian Chemical Bulletin》1966,15(7):1239-1240
Conclusions Cyclic alkoxysilanes — 1,3-dioxa-2-silacyclanes — and their oligomers are decomposed by organomagnesium compounds with the formation of the corresponding silanols (disiloxanes) and tetraalkylsilanols.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1283–1285, July, 1966. 相似文献