全文获取类型
收费全文 | 328篇 |
免费 | 7篇 |
专业分类
化学 | 269篇 |
晶体学 | 4篇 |
力学 | 8篇 |
数学 | 21篇 |
物理学 | 33篇 |
出版年
2023年 | 5篇 |
2022年 | 1篇 |
2021年 | 5篇 |
2020年 | 2篇 |
2019年 | 12篇 |
2018年 | 7篇 |
2017年 | 3篇 |
2016年 | 6篇 |
2015年 | 8篇 |
2014年 | 11篇 |
2013年 | 23篇 |
2012年 | 25篇 |
2011年 | 20篇 |
2010年 | 17篇 |
2009年 | 12篇 |
2008年 | 26篇 |
2007年 | 21篇 |
2006年 | 23篇 |
2005年 | 29篇 |
2004年 | 16篇 |
2003年 | 13篇 |
2002年 | 9篇 |
2001年 | 6篇 |
2000年 | 3篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1987年 | 2篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1981年 | 2篇 |
1979年 | 4篇 |
排序方式: 共有335条查询结果,搜索用时 15 毫秒
1.
2.
In order to determine the energetic driving forces for surface segregation in bimetallic clusters, we use a combined approach coupling numerical simulations within an N-body interatomic potential and a lattice-gas model. This approach, which has been used successfully to study both the superficial segregation in semi-infinite alloys and the intergranular segregation, allows us to determine the relative contributions of the three elementary driving forces for the different sites of the cluster surface (vertices, edges and facets) in both dilute limits for the Cu-Ag system. We show that the segregation hierarchy based on broken-bond arguments (preferential segregation to the vertex sites, less to edge sites, and least to facet sites) is not at all universal. In particular, unusual hierarchies are predicted when the sizes of the constituents are strongly different. Furthermore, we compare the segregation driving forces for cubo-octahedral and icosahedral clusters. They are similar for the vertex sites and edge sites, whereas they differ significantly for the sites of the triangular facets. The segregation of the species with the largest atomic radius (Ag) is indeed largely enhanced in the icosahedral structure due to dilations of the orthoradial distances. 相似文献
3.
Bruzón M. S. Gandarias M. L. Muriel C. Ramírez J. Saez S. Romero F. R. 《Theoretical and Mathematical Physics》2003,137(1):1367-1377
We use the classical and nonclassical methods to obtain symmetry reductions and exact solutions of the (2+1)-dimensional integrable Calogero–Bogoyavlenskii–Schiff equation. Although this (2+1)-dimensional equation arises in a nonlocal form, it can be written as a system of differential equations and, in potential form, as a fourth-order partial differential equation. The classical and nonclassical methods yield some exact solutions of the (2+1)-dimensional equation that involve several arbitrary functions and hence exhibit a rich variety of qualitative behavior. 相似文献
4.
tert-Butyl 2-hydroxyalkyl sulfides, prepared by reaction of epoxides with 2-methylpropane-2-thiol, are converted directly to 1,3-oxathiolanes upon treatment with pivalaldehyde and boron trifluoride diethyl etherate in the presence of thioanisole. 相似文献
5.
Erwin Gtschi Christian-Johannes Jenny Peter Reindl Fabienne Ricklin 《Helvetica chimica acta》1996,79(8):2219-2234
A total synthesis of cyclothialidine ( 1 ), a new DNA gyrase inhibitor isolated from Streptomyces filipinensis, is described. The synthetic concept was tested by preparing the lactone 13 (Scheme 2) which contains the characteristic bicyclic core entity of 1 . Key features of the synthesis of 1 are: preparation of 3,5-dihydroxy-2,6-dimethylbenzoic acid ( 23 ) from 3,5-dihydroxybenzoic acid ( 19 ) by two consecutive Mannich aminomethylation/hydrogenation sequences; benzylic N-bromosuccinimide bromination of an ester derivative 25 thereof and its subsequent coupling with Boc-Ser-Cys-OMe ( 11 ); cyclization of the ω-hydroxy acid 29 29 to the 12-membered lactone 30 using preferably Mitsunobu conditions; completion of the peptidic side chains of 1 using Boc strategy (Scheme 4). Optically pure cis-N-(tert-butoxycarbonyl)-3-hydroxy-L -proline ((–)- 14 ) was obtained by resolution of the racemate via an efficient reaction sequence containing a lipase-catalyzed enantiospecific acetate hydrolysis (Scheme 3). The structure of natural 1 was confirmed by comparison with the synthetic material. The synthetic route described provides also easy access to analogues of 1 , e.g., via the intermediate 30 . 相似文献
6.
Ballesteros I. Ballesteros M. CabaÑas A. Carrasco J. MartÍn C. Negro M. J. Saez F. Saez R. 《Applied biochemistry and biotechnology》1991,(1):307-315
A total of 27 yeast strains belonging to the groupsCandida, Saccharomyces, andKluyveromyces were screened for their ability to grow and ferment glucose at temperatures ranging 32-45°C.
K. marxianus andK. fragilis were found to be the best ethanol producing organisms at the higher temperature tested and, so, were selected for subsequent
simultaneous saccharification and fermentation (SSF) studies. 相似文献
7.
8.
A new kinetic method for determination of selenium is based on its inhibitory effect on the Pd(II)-catalysed reaction between Pyronine G and hypophosphite. Under the optimum experimental conditions (6 x 10(-5)M Pyronine G, 0.4M hypophosphite, 0.4 mug/ml Pd(II), pH 2.8, temperature 22.0 +/- 0.2 degrees ), Se can be determined in the concentration range 0.033-0.50 mug/ml. The method suffers from numerous interferences and is thus limited in application. It has been applied to the determination of selenium in spring waters and pharmaceutical preparations. 相似文献
9.
A kinetic method for the determination of Te based on its inhibitory effect on the PdII-catalysed reaction between pyronine G and H2PO2- is described. The influence of experimental variables on the rate of the process and the potential interfering effect of a large number of ions has been studied. Under the selected experimental conditions: 6 x 10(-5) M pyronine G; 0.6 M H2PO2-; pH 2.6, adjusted with Britton-Robinson buffer; 0.80 microgram ml-1 of PdII; and a temperature of 22 +/- 0.2 degrees C, Te was determined in the concentration range 0.08-0.85 microgram ml-1. The method was applied to the determination of Te in waters and lead concentrates. 相似文献
10.
Pierre L. Huyskens Fabienne van den Broeck Thrse Zeegers-Huyskens 《Journal of Molecular Structure》1997,416(1-3):91-104
CHCl3 solutions containing a few percent polyethylene oxide PEO (MW = 200 000) or the low-molecular model dioxane are stirred at 50°C during more than 100 h in the presence of small amounts of KCl. The specific conductance, the viscosity and the density of the solutions are measured at 25°C as a function of time. Both PEO and dioxane act as ligands improving the solubility of KCl. The relaxation times are of the order of several hours. After 40 h or more the viscosity of the solutions increases in a spectacular way. However, the most striking observation is that the specific conductance of the polymeric solutions at 25°C is systematically 5% higher than the value measured with the same sample at 45°C, just as for metals. The effect of the dilution of the primary stirred solutions either in the pure solvent or in the initial polymer solution is investigated. These results are discussed in terms of a three-step mechanism in the polymer systems: (1) Loading of the coils to polymeric cations with a full elementary charge, as a consequence of charge transfer interactions of the crown-ether type with numerous K+ ions penetrating into the coils; (2) Electron tunnelling conduction of the Hamill—Ceulemans type from one positive coil to the neighbouring one; (3) Alteration of the structure of the coils and of their hydrodynamic radius by the motions of K+ in the coils. These ‘brachiation’ motions by a hopping mechanism result from an increased mobility of the complexed K+ ions, which is also the origin of the Zundel effect. They do not directly contribute to the conductance but are responsible for the delayed increase of the viscosity. 相似文献