全文获取类型
收费全文 | 1207篇 |
免费 | 55篇 |
国内免费 | 4篇 |
专业分类
化学 | 838篇 |
晶体学 | 7篇 |
力学 | 13篇 |
数学 | 33篇 |
物理学 | 375篇 |
出版年
2022年 | 6篇 |
2021年 | 10篇 |
2020年 | 16篇 |
2019年 | 24篇 |
2018年 | 22篇 |
2017年 | 11篇 |
2016年 | 31篇 |
2015年 | 20篇 |
2014年 | 15篇 |
2013年 | 48篇 |
2012年 | 69篇 |
2011年 | 73篇 |
2010年 | 35篇 |
2009年 | 35篇 |
2008年 | 57篇 |
2007年 | 56篇 |
2006年 | 68篇 |
2005年 | 82篇 |
2004年 | 54篇 |
2003年 | 43篇 |
2002年 | 30篇 |
2001年 | 27篇 |
2000年 | 27篇 |
1999年 | 31篇 |
1998年 | 15篇 |
1997年 | 21篇 |
1996年 | 18篇 |
1995年 | 7篇 |
1994年 | 17篇 |
1993年 | 12篇 |
1992年 | 20篇 |
1991年 | 13篇 |
1990年 | 9篇 |
1989年 | 16篇 |
1988年 | 12篇 |
1987年 | 10篇 |
1986年 | 9篇 |
1985年 | 12篇 |
1984年 | 23篇 |
1983年 | 9篇 |
1982年 | 14篇 |
1981年 | 10篇 |
1980年 | 17篇 |
1979年 | 13篇 |
1978年 | 16篇 |
1977年 | 16篇 |
1976年 | 12篇 |
1975年 | 11篇 |
1974年 | 7篇 |
1973年 | 6篇 |
排序方式: 共有1266条查询结果,搜索用时 15 毫秒
141.
We report on the in situ observation of temperature-driven drastic morphology evolution and surface pre-melting of the Bi(0 0 1) nanofilm deposited on the Si(1 1 1)-7 × 7 surface by use of spot-profile-analyzing low-energy electron diffraction (SPA-LEED). Surface step density of the single-crystalline, epitaxial Bi(0 0 1) film decreases above 350 K in a critical manner. On annealed Bi(0 0 1) films, we have detected surface pre-melting with a transition temperature of 350 K, which yields reversible diffraction intensity drop in addition to the harmonic Debye-Waller behavior. The observed surface flattening of the as-deposited film is driven by the increased amount of mobile adatoms created through the surface pre-melting. 相似文献
142.
A new phenol glycoside named berchemolide was isolated together with (+)-catechin and (-)-epicatechin (as acetates), from the stems of Berchemia racemosa Sieb. et Zucc. (Rhamnaceae). The structure of berchemolide, having a dimeric dilactone structure with a 22-membered ring, was determined on the basis of spectral and chemical investigations. The conformation of berchemolide was calculated by MNDO (modified neglect of diatomic overlap). 相似文献
143.
144.
Teruo Kurihara Yutaka Watanabe Kouichi Takayama Akihiro Ohta 《Journal of heterocyclic chemistry》1991,28(6):1557-1560
Naturally occurring pyrazines fit well the theory that conformity to the TCS rule gives a stable molecular system. Thus, many pyrazines so far synthesized and those in nature which are energetically very stable molecules can be synthetically quite accessible. The TCS rule applies very well to the construction route of pyrazine rings. 相似文献
145.
Toshihiko Sakurai Maki Horikawa Makoto Takafuji Atsushi Kubo Hirotaka Ihara 《Applied Surface Science》2006,253(2):869-873
An l-glutamic acid-derived lipid with a terminal thiol has been synthesized and its corresponding self-assembled structure on Au(1 1 1) surfaces described. The surface morphology of the lipid self-assembled monolayer (SAM) exhibits nano-order patterning, where the height of the monolayer (approximately 1.5 nm) could be interpreted as due to the monolayer structure estimated from molecular models. The molecular orientation in the monolayer is almost perpendicular to the Au(1 1 1) surface depending on the three-point hydrogen-bonding sites in the molecule. 相似文献
146.
Shuichi Ban Yoshiki Takano Naoki Ohkubo Hisanobu Hoya Yumiko Takahashi Kouichi Takase Kazuko Sekizawa 《Hyperfine Interactions》2005,165(1-4):95-99
The transition metal phosphorus trichalcogenides MnPS3 and the FePS3 are CdCl2 type layered compounds, where the transition metal ions form a hexagonal lattice. While these compounds order anti-ferromagnetically at low temperature, the magnetic structures are different. We have reported that these mixtures Mn0.5Fe0.5PS3 is a spin glass with a glass transition temperature T g=33.7 K. Then, in this work, we report that the results of the temperature variation of the 57Fe Mössbauer spectra of FePS3 and Mn0.5Fe0.5PS3, in detail. In the anti-ferromagnetic state of FePS3, the hyperfine magnetic field H int increases with decreasing temperature and the Isomer shift I. S. increases slightly with decreasing temperature. However in Mn0.5Fe0.5PS3, the two broadened peaks are observed and the two peaks became a single peak with decreasing temperature at about 50.0 K, which is higher than T g=33.7 K. In the spin glass Mn0.5Fe0.5PS3, the Mössbauer spectra suggest that the magnetic interactions exist far above T g. 相似文献
147.
The mechanism of the gold nanocluster‐catalyzed aerobic homocoupling of arylboronic acids has been elucidated by means of DFT calculations with Au20? as a model cluster for the Au:[poly(N‐vinylpyrrolidin‐2‐one)] catalyst. We found that oxygen affects the adsorption of phenylboronic acid and, by lowering the energy barrier, a water molecule enhances dissociation of the C?B bond, which is probably the rate‐determining step. The key role of oxygen is in activating the surface of the gold cluster by generating Lewis acidic sites for adsorption and activation of the phenylboronic acid, leading to the formation of biphenyl through a superoxo‐like species. Moreover, the oxygen adsorbed on the Au nanocluster can act as an oxidant for phenylboronic acid, giving phenol as a byproduct. As shown by NBO analysis, the basic aqueous reaction medium facilitates the reductive elimination process by weakening the Au?C bond, thereby enhancing the formation of biphenyl. The coupling of phenyl and reductive elimination of biphenyl occur at the top or facet site with low‐energy‐barrier through spillover of phenyl group on Au NC. The present findings are useful for the interpretation or design of other coupling reactions with Au NC. 相似文献
148.
Gold/Palladium Alloy for Carbon–Halogen Bond Activation: An Unprecedented Halide Dependence
下载免费PDF全文
![点击此处可从《化学:亚洲杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Raghu Nath Dhital Dr. Karan Bobuatong Prof. Dr. Masahiro Ehara Prof. Dr. Hidehiro Sakurai 《化学:亚洲杂志》2015,10(12):2669-2676
New catalytic activity of gold/palladium alloy nanoclusters (NCs) for carbon–halogen bond activation is demonstrated. In the case of an aryl chloride, the inclusion of gold in a bimetallic catalyst is indispensable to achieve the coupling reactions. Gold has the unique effect of stabilizing palladium, such that Pd2+ leached from clusters by means of spillover of chloride during oxidative addition. The thus‐formed spillover intermediate further reacts heterogeneously in both Ullmann and Suzuki‐type coupling reactions through a new type of mechanism. In the case of an aryl bromide, Ullmann coupling occurs through the spillover of bromide, similar to that of aryl chloride. However, a significant fraction of palladium also leached, which diminished the Ullmann coupling activity of the aryl bromide and, as a result, the order of reactivity was ArCl>ArBr. With regard to the activation of the C?Br bond towards a Suzuki‐type reaction, the inclusion of a higher gold content in gold/palladium clusters stabilized palladium to prevent the leaching of Pd2+ from the clusters by means of spillover of bromide. The spillover intermediate reacts heterogeneously with PhB(OH)2, palladium‐rich gold/palladium, or pure palladium clusters; the oxidative addition of ArBr favors the extraction of palladium from the clusters, yielding Pd2+ intermediates. The extracted intermediates react homogenously (Pd2+/Pd0 catalysis) with PhB(OH)2, which results in the higher selectivity of the cross‐coupling product. An initial step to observe such unprecedented halide dependency, together with the dynamic behavior of palladium on the surface of gold is the oxidative addition of Ar?X. A detailed insight into the first oxidative addition process was also examined by quantum chemical calculations. 相似文献
149.
150.
Sakai N Lista M Kel O Sakurai S Emery D Mareda J Vauthey E Matile S 《Journal of the American Chemical Society》2011,133(39):15224-15227
Facile access to complex systems is crucial to generate the functional materials of the future. Herein, we report self-organizing surface-initiated polymerization (SOSIP) as a user-friendly method to create ordered as well as oriented functional systems on transparent oxide surfaces. In SOSIP, self-organization of monomers and ring-opening disulfide exchange polymerization are combined to ensure the controlled growth of the polymer from the surface. This approach provides rapid access to thick films with smooth, reactivatable surfaces and long-range order with few defects and high precision, including panchromatic photosystems with oriented four-component redox gradients. The activity of SOSIP architectures is clearly better than that of disordered controls. 相似文献