全文获取类型
收费全文 | 3230篇 |
免费 | 110篇 |
国内免费 | 15篇 |
专业分类
化学 | 2473篇 |
晶体学 | 52篇 |
力学 | 26篇 |
数学 | 138篇 |
物理学 | 666篇 |
出版年
2023年 | 13篇 |
2022年 | 25篇 |
2021年 | 26篇 |
2020年 | 37篇 |
2019年 | 36篇 |
2018年 | 33篇 |
2017年 | 26篇 |
2016年 | 58篇 |
2015年 | 64篇 |
2014年 | 75篇 |
2013年 | 160篇 |
2012年 | 179篇 |
2011年 | 197篇 |
2010年 | 138篇 |
2009年 | 131篇 |
2008年 | 187篇 |
2007年 | 205篇 |
2006年 | 205篇 |
2005年 | 203篇 |
2004年 | 168篇 |
2003年 | 172篇 |
2002年 | 149篇 |
2001年 | 40篇 |
2000年 | 40篇 |
1999年 | 50篇 |
1998年 | 27篇 |
1997年 | 40篇 |
1996年 | 50篇 |
1995年 | 16篇 |
1994年 | 25篇 |
1993年 | 24篇 |
1992年 | 37篇 |
1991年 | 27篇 |
1990年 | 17篇 |
1989年 | 18篇 |
1988年 | 16篇 |
1987年 | 13篇 |
1986年 | 24篇 |
1985年 | 56篇 |
1984年 | 52篇 |
1983年 | 16篇 |
1982年 | 47篇 |
1981年 | 41篇 |
1980年 | 37篇 |
1979年 | 31篇 |
1978年 | 27篇 |
1977年 | 17篇 |
1976年 | 17篇 |
1975年 | 11篇 |
1973年 | 15篇 |
排序方式: 共有3355条查询结果,搜索用时 15 毫秒
81.
Carlos Rodríguez-Abreu Massimo Lazzari Dharmesh Varade Masaya Kaneko Kenji Aramaki Manuel Arturo López Quintela 《Colloid and polymer science》2007,285(6):673-680
The structure and rheological properties of a poly(dimethylsiloxane)-graft-poly(oxyethylene) copolymer at high concentrations
in block-selective solvents were studied by small-angle X-ray scattering (SAXS) and rheometry. Analysis of SAXS data indicates
that quasispherical, reverse micellar aggregates (with no ordered packing) are present in concentrated solutions of the copolymer
in nonpolar solvents, and that upon addition of water, the size of such aggregates increases due to the solubilization inside
the micellar cores. The viscosity of concentrated polymer solutions increases exponentially as water is added, and finally,
viscoelastic, gel-like behavior is found in the vicinity of the phase separation limit. It was found that small silver nanoparticles
with an average diameter of ≈3 nm can be synthesized inside the copolymer aggregates without the need of a reducing agent;
namely, particles embedded in a viscoelastic matrix are obtained. The synthesis seems to follow first-order kinetics.
Electronic supplementary material Supplementary material is available in the online version of this article at and is accessible for authorized users. 相似文献
82.
(2R,5S)-2-Methyl-5-hexanolide and its antipode were synthesized in highly optically pure state (?98–99% e.e.) starting from ethyl (S)-lactate and the enantiomers of methyl β-hydroxyisobutyrate. The specific rotations of our samples were [α]D±91.0-93.5° (CHCl3), while the reported values of the samples prepared by resolution or asymmetric synthesis were ±64.5–65.6°. 相似文献
83.
Both the enantiomers of 2,3-dihydro-2-isopropyl-2,5-dimethylfuran were synthesized employing the Sharpless asymmetric epoxidation reaction. The (R)-(—)-enantiomer of this cyclic enol ether was also synthesized starting from (R)-(—)-linalool. 相似文献
84.
Takeshi Hanamoto Yuhko Iwamoto Kenji Yamada Ryoko Anno 《Journal of fluorine chemistry》2007,128(10):1126-1130
The 1,3-dipolar cycloaddition reaction of fluoro(trimethylsilyl)acetylene prepared in situ with an excess of diazomethane smoothly proceeded to give the corresponding 4-fluoro-5-trimethylsilyl-1H-pyrazole in 84% yield. The copper iodide-catalyzed N-arylation of the fluorinated pyrazole with a variety of aryl iodides afforded N-aryl-4-fluoropyrazoles as desilylation products in good to excellent yields. 相似文献
85.
86.
Stereoselective synthesis of cruciferous indole phytoalexin (R)-(+)-1-methoxyspirobrassinin and its unnatural (S)-(−)-enantiomer was achieved by spirocyclization of 1-methoxybrassinin in the presence of (+)- and (−)-menthol and subsequent oxidation of the obtained menthyl ethers. Methanolysis of menthyl ethers in the presence of TFA afforded (2R,3R)-(−)-1-methoxyspirobrassinol methyl ether as well its unnatural (2S,3S)-, (2R,3S)-, and (2S,3R)-isomers. 相似文献
87.
Tomohisa Nagamatsu Yoshiji Hantani Minoru Yamada Kenji Sasaki Hiromi Ohtomo Taiji Nakayama Takashi Hirota 《Journal of heterocyclic chemistry》1993,30(1):193-202
As a series of polyheterocyclic compounds for exploitation as anti-platelet agents, tricyclic heterocyclic compounds, 4-substituted 6,7-dihydro-5H-pyrimido[5,4-d][1]benzazepines 3–6, 9, 12–14 , and 16–26 , having nitrogen, oxygen, or sulfur containing functional groups at the 4-position, were prepared. In addition, tetra-cyclic heterocyclic compounds, 3-methyl-1,2,5,6-tetrahydro-4H-imidazo[1′,2′:1,6]pyrimido[5,4-d][1]benzaze-pinium chloride ( 7 ), 1,2,5,6-tetrahydro-4H-imidazo[1′,2′:1,6]pyrimido[5,4-d][1]benzazepines 10a-e , 2,3,6,7-tetrahydro-1H 5H-pyrimido[1′,2′:1,6]pyrimido[5,4-d][1]benzazepine ( 11 ), and 1,2,5,6-tetrahydro-4H-thiazolo-[3′,2′:1,6]pyrimido[5,4-d][1]benzazepinium chloride ( 15 ) via ring closure of 4-(hydroxyalkylamino)- 6, 9a-e , and 3c , and 4-(2-hydroxyethylthio)-6,7-dihydro-5H-pyrimido[5,4-d][1]benzazepine ( 14 ) with phosphoryl chloride or thionyl chloride, respectively, were also prepared. Their inhibitory activities against collagen-induced aggregation of rabbit blood platelets in vitro were investigated. Among them, compound 5 having a morpholino group at the 4-position on the tricyclic nucleus, which enhanced the activity more than 14-fold as compared with aspirin, was found to have the most satisfactory in inhibitory activity. 相似文献
88.
J. Koarashi K. Akiyama T. Asano T. Yokota 《Journal of Radioanalytical and Nuclear Chemistry》2005,262(3):771-774
The effects of incorporating tritiated water into a 14C-sampling system in sample preparation and 14C activity measurement by liquid scintillation counting were investigated. Experiments derived the limit of water content in the prepared sample, and also demonstrated that 14C activity can be determined without any interference from 3H contamination for a clear-sample solution. The results enabled us to estimate the permissible relative humidity of air required for accomplishing sample preparation and 14C activity measurement. These showed that for sampling of air with less than the permissible relative humidity, total 14C activity in airborne effluent can be evaluated accurately without dehumidification of air.The authors would like to thank T. Kozawa, K. Isaka and Y. Adachi of Inspection Development Company Ltd., Y. Hiyama of Zuihou Sangyou Company Ltd., and T. Mizutani, H. Watanabe, M. Takeishi and K. Shinohara of Japan Nuclear Cycle Development Institute for their valuable assistance. 相似文献
89.
Hisao Yokota Yozo Otsuka Tsutomu Kagiya Kenichi Fukui 《Journal of polymer science. Part A, Polymer chemistry》1967,5(11):2825-2834
A kinetic study of the γ-ray polymerization of formaldehyde in toluene solution in the presence of carbon dioxide was carried out at temperatures of + 13 to ?17°C. Two modes of the polymerization, spontaneous and γ-ray polymerization, occur in this system. The γ-ray polymerization, experimentally separated from the spontaneous polymerization, was investigated. The rate of γ-ray polymerization increased slightly with the square root of carbon dioxide concentration. The rate of polymerization was also found to be proportional to the dose rate and the square of monomer concentration. The molecular weight of polymer formed was independent of the reaction condition. The apparent activation energy was estimated to be 10.3 kcal./mole. The kinetics of the γ-ray polymerization in the presence of carbon dioxide are explained quantitatively by a cationic mechanism, and the role of carbon dioxide is as an action of retardation for neutralization of the cationic initiating species, which was produced by γ-radiation, by means of a reverse reaction with an electron. Physical and mechanical properties of the polymer obtained by γ-ray polymerization were also investigated. 相似文献
90.
Polypeptides with two histidines and an iron porphyrin (1H40-7H46) were synthesized with a variety of positions of a histidine. In 4H43, histidine (H43) was in the hydrophobic region of an α-helix. The other polypeptides were of slightly or substantially distorted conformation. In the pH 7.2 buffer solution, two histidines of the polypeptide coordinated the iron porphyrin regardless of their positions. Some polypeptides (1H40, 3H42, and 5H44) showed an enhanced catalytic activity in the peroxidase reaction using cumene hydroperoxide compared to that of 4H43, whereas some polypeptides (2H41 and 6H45) were ineffective catalysts. The distortion of the peptide conformation by the addition of MeOH was also effective for the peroxidase reaction. 相似文献