全文获取类型
收费全文 | 189篇 |
免费 | 3篇 |
专业分类
化学 | 100篇 |
力学 | 1篇 |
数学 | 67篇 |
物理学 | 24篇 |
出版年
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 5篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2016年 | 4篇 |
2015年 | 2篇 |
2014年 | 6篇 |
2013年 | 6篇 |
2012年 | 11篇 |
2011年 | 11篇 |
2010年 | 2篇 |
2009年 | 2篇 |
2008年 | 14篇 |
2007年 | 8篇 |
2006年 | 10篇 |
2005年 | 8篇 |
2004年 | 9篇 |
2003年 | 7篇 |
2002年 | 6篇 |
2001年 | 6篇 |
2000年 | 6篇 |
1999年 | 6篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 2篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 5篇 |
1973年 | 1篇 |
1970年 | 2篇 |
1963年 | 2篇 |
1962年 | 1篇 |
1957年 | 2篇 |
1938年 | 2篇 |
1933年 | 1篇 |
1930年 | 2篇 |
排序方式: 共有192条查询结果,搜索用时 328 毫秒
41.
Cristina Paradisi Hilkka Kenttmaa Quang T. Le Marjorie C. Caserio 《Journal of mass spectrometry : JMS》1988,23(7):521-526
A Fourier transform–ion cyclotron resonance study of thioacyl compounds as binary mixtures with unsaturated hydrocarbons has revealed that thioacetylium ions CH3CS+ generated by electron fragmentation fail to thioacyl-ate even the most reactive aromatic hydrocarbons. Among the hydrocarbons studied, only 3-hexyne and 2,4-dimethyl-2,5-hexadiene were observed to react with CH3CS+. Apart from proton-transfer reactions, the major ionic reaction of thioesters with arenes, alkynes and alkenes is condensation of the molecular ion of one component, usually the ester, with a neutral molecule of the other, resulting in the cleavage of the S? Calkyl bond of the thioester. The nature of this reaction is discussed and a possible mechanism is suggested. 相似文献
42.
Marjorie J. Vold 《Journal of colloid and interface science》1982,90(2):543-545
Data from visual inspection, microscopic observations through a polarizing microscope, and dilatometry on sealed samples have been used to draw a phase diagram for this two-component system that differs from the one originally published on the basis of the same data. The difference lies in the recognition of a mesophase existing in a composition region intermediate between that of the cylindrical (middle) and lamellar (neat) phases. The problems of accounting for these three types of structures include their very narrow miscibility gaps with each other, their extraordinary thermal stability, and the possible absence of any region of direct binary equilibrium between the middle and neat phases. 相似文献
43.
A theoretical investigation of the properties of the Si3C4, Si4C3, and Si4C4 clusters is reported. Systematic explorations of the potential energy surfaces of the three clusters are performed using a combination of ab initio molecular dynamics and local energy minimizations using density functional theory. A large number of isomers with a large variety of geometries has been found. The geometries, energies, and vibrational frequencies yielded are discussed. Furthermore, a quantitative analysis of the interatomic distances, angles, and coordination numbers observed, as well as the conclusions on the bonding properties, are presented. The cluster properties are then compared to those of solid SiC and of the smaller Si-C clusters (with size up to 6) obtained in a previous study. Analysis of our results and comparison with bulk properties show that even clusters as small as Si3C4, Si4C3, and Si4C4 exhibit properties similar to those of the amorphous bulk, in particular as for the structures and bonds formed by C atoms. 相似文献
44.
W. Mc K. Martin W. O. Whitcomb A. Schulerud J. W. Bowen W. Kranz Th. Ruemele H. Kühl H. H. Bunzell Marjorie Kenyon H. Joergensen Th. Biéchy E. Berliner H. Simons H. O. Triebold C. H. Bailey G. E. Holm G. R. Greenbank A. Heiduschka R. Fischer 《Analytical and bioanalytical chemistry》1933,92(11-12):446-451
45.
46.
47.
48.
We present a computational investigation into the nature of bonds formed by f-elements in materials. The paper presents an example of the incorporation of rare earth elements (REE) and actinides in minerals derived from fluorapatite: Ca(10)(PO(4))(6)F(2). These minerals, called britholites, allow many substitutions on all three Ca, P, and F sites and are considered as potential host phases for radioactive elements separated from nuclear waste. REE and actinides have very similar physical and chemical properties, but REE are not radioactive and much more easily handled. REE are, therefore, very often used as a surrogate for actinides in experimental studies. The representative elements of rare earths and actinides chosen for this first investigation are cerium and uranium, respectively. We have studied all the various configurations of Ca(9)X(PO(4))(6)(-)(y)()(SiO(4))(y)()F(2), where X stands for Ce(3+), Ce(4+), U(3+), and U(4+), and y is equal to 1 and 2 for three-time and four-time charged cations, respectively. Calculations have been performed within the density functional theory (DFT) framework according to the computation scheme determined in a previous study. The analysis of the energies of the various configurations shows that the incorporation of all the cations considered stabilizes the apatitic structure. This stabilization, however, is greater for four-time charged cations than for three-time charged ones, which shows that Ce and U are both preferentially substituted in the +IV oxidation state. In addition, the substitution in one of the two cationic sites of the apatitic structure is always more favorable. Then, the geometry analysis shows a larger decrease in size of this cationic site for U than for Ce, as well as different volume variations for Ce and U substitutions in the two cationic sites. This cannot be explained by steric effects alone. Finally, the electronic density analysis yields three essential results: U and Ce form significantly covalent bonds, U forms bonds more covalent than Ce, and finally four-time charged cations form more covalent bonds than three-time charged ones. The comparison of these results with the formation enthalpies of the various phases shows a positive correlation between the covalence degree of the bonds formed by the f-element and the stability of the structure. In addition, our results prove that Ce- and U-bearing britholites exhibit very similar energetic, structural, and electronic properties. Ce, therefore, appears to be a good simulant for U. 相似文献
49.
The ability to discriminate between sounds with different spectral shapes was evaluated for normal-hearing and hearing-impaired listeners. Listeners discriminated between a standard stimulus and a signal stimulus in which half of the standard components were decreased in level and half were increased in level. In one condition, the standard stimulus was the sum of six equal-amplitude tones (equal-SPL), and in another the standard stimulus was the sum of six tones at equal sensation levels re: audiometric thresholds for individual subjects (equal-SL). Spectral weights were estimated in conditions where the amplitudes of the individual tones were perturbed slightly on every presentation. Sensitivity was similar in all conditions for normal-hearing and hearing-impaired listeners. The presence of perturbation and equal-SL components increased thresholds for both groups, but only small differences in weighting strategy were measured between the groups depending on whether the equal-SPL or equal-SL condition was tested. The average data suggest that normal-hearing listeners may rely more on the central components of the spectrum whereas hearing-impaired listeners may have been more likely to use the edges. However, individual weighting functions were quite variable, especially for the HI listeners, perhaps reflecting difficulty in processing changes in spectral shape due to hearing loss. Differences in weighting strategy without changes in sensitivity suggest that factors other than spectral weights, such as internal noise or difficulty encoding a reference stimulus, also may dominate performance. 相似文献
50.
Peter E. Maligres Marjorie S. Waters Steven A. Weissman J. Christopher McWilliams Stephanie Lewis Jennifer Cowen Robert A. Reamer R. P. Volante Paul J. Reider David Askin 《Journal of heterocyclic chemistry》2003,40(2):229-241
The synthesis of ras farnesyl‐protein transferase inhibitor 1 is described on a multi‐kilogram scale. Retrosynthetic analysis reveals chloromethylimidazole 2 and a piperazinone 3 as viable precursors. The 1,5‐disubstituted imidazole system was regioselectively assembled via an improved Marckwald imidazole synthesis. A new imidazole dethionation procedure has been developed to convert the Marckwald mercaptoim‐idazole product to the desired imidazole. This methodology was found to be tolerant of a variety of functional groups providing good to excellent yields of 1,5‐disubstituted imidazoles. A new Mitsunobu cycliza‐tion strategy was developed to prepare the arylpiperazinone fragment 3 . 相似文献