全文获取类型
收费全文 | 384篇 |
免费 | 5篇 |
国内免费 | 5篇 |
专业分类
化学 | 206篇 |
晶体学 | 6篇 |
力学 | 9篇 |
数学 | 91篇 |
物理学 | 82篇 |
出版年
2019年 | 4篇 |
2016年 | 6篇 |
2015年 | 5篇 |
2014年 | 7篇 |
2013年 | 17篇 |
2012年 | 7篇 |
2011年 | 14篇 |
2010年 | 12篇 |
2009年 | 13篇 |
2008年 | 17篇 |
2007年 | 10篇 |
2006年 | 20篇 |
2005年 | 15篇 |
2004年 | 9篇 |
2003年 | 14篇 |
2002年 | 10篇 |
2001年 | 9篇 |
2000年 | 15篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 6篇 |
1983年 | 12篇 |
1982年 | 6篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 3篇 |
1976年 | 8篇 |
1975年 | 7篇 |
1974年 | 3篇 |
1973年 | 4篇 |
1972年 | 6篇 |
1970年 | 4篇 |
1969年 | 6篇 |
1962年 | 3篇 |
1937年 | 3篇 |
1935年 | 2篇 |
1920年 | 2篇 |
排序方式: 共有394条查询结果,搜索用时 15 毫秒
1.
Automated separation and measurement of radioxenon for the Comprehensive Test Ban Treaty 总被引:2,自引:0,他引:2
T. W. Bowyer K. H. Abel C. W. Hubbard A. D. McKinnon M. E. Panisko R. W. Perkins P. L. Reeder R. C. Thompson R. A. Warner 《Journal of Radioanalytical and Nuclear Chemistry》1998,235(1-2):77-82
A fully automatic radioxenon sampler/analyzer (ARSA) has been developed and demonstrated for the collection and quantitative
measurement of the four xenon radionuclides,131mXe(11.9 d),133mXe(2.2 d),133Xe(5.2 d), and135Xe(9.1 hr), in the atmosphere. These radionuclides are important signatures in monitoring for compliance to a Comprehensive
Test Ban Treaty (CTBT). Activity ratios of these radionuclides permit source attribution. Xenon, continuously and automatically
separated from the atmosphere, is automatically analyzed by electron-photon coincidence spectrometry providing a lower limit
of detection of about 100 μBq/m3. The demonstrated detection limit is about 100 times better than achievable with reported laboratory-based procedures for
the short-time collection intervals of interest. 相似文献
2.
The synthesis of [(CH3)ClGaN3]4 (1) with a heterocyclic cyclooctane-like structure and [(CH3)BrGaN3]3 (2) with a trimeric structure has been demonstrated. X-ray structural determinations reveal that 1 and 2 consist of Ga4N4 eight-membered rings and Ga3N3 six-membered rings, respectively, in which the Ga atoms are bridged by the alpha nitrogens of the azide groups. [(CH3)ClGaN3]4 crystallizes in the tetragonal space group P42(1)c with a = 11.017(4) A, c = 8.699(7) A, and Z = 8. [(CH3)BrGaN3]3 crystallizes in the triclinic space group P1 with a = 8.1080(10) A, b = 9.9390(13) A, c = 10.4439(13) A, alpha = 86.069(3) degrees, beta = 86.771(3) degrees, gamma = 80.829(2) degrees, and Z = 6. The reaction of 1 and 2 with LiGaH4 yields [(CH3)HGaN3]x, which is a new low-temperature source of GaN. 相似文献
3.
Wender PA Hegde SG Hubbard RD Zhang L 《Journal of the American Chemical Society》2002,124(18):4956-4957
(-)-Laulimalide (1), a structurally novel macrolide isolated in trace amounts from marine sponges, promotes abnormal tubulin polymerization and apoptosis in vitro, with a similar mode of action to that of Taxol(R), but with potentially less susceptibility to multidrug resistance. Herein, a flexible and convergent asymmetric synthesis of (-)-laulimalide is described. This synthesis featured a highly diastereoselective Sakurai reaction of 2 with 3 and a regioselective macrolactonization of an unprotected vicinal diol. Laulimalide was synthesized in 25 steps (longest linear; 36 overall) in 3.5% overall yield, providing a uniquely short and efficient route to 1 and its analogues. 相似文献
4.
Roger J. Greathead Rod S. Mason Keith R. Jennings Janet A. Page Robert J. Pryce 《Journal of mass spectrometry : JMS》1985,20(2):110-114
The behaviour of gibberellic acid (GA3) under electron impact and chemical ionization conditions has been examined. The tendency of GA3 to undergo pyrolysis by the loss of the elements of water and carbon dioxide has been identified. Two methods of sample introduction can be used to minimize the occurrence of this pyrolysis. Accurate mass measurement allows the composition of the pyrolysis product to be determined and metastable techniques confirm the structure of this product to be epi-allogibberic acid rather than its isomer allogibberic acid. This result corrects a misconception in the literature and illustrates the advantage of metastable methods compared with accurate mass measurements, for the determination of small structural differences within a molecule. 相似文献
5.
Wolfgang A. Herrmann Martina Flöel Cornelia Weber John L. Hubbard Adolf Schäfer 《Journal of organometallic chemistry》1985,286(3):369-397
The eighteen new μ-alkylidene ruthenium complexes 5a–r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η5-C5H5)Ru(μ-NO)]2 (3) either with the diazoalkanes oxidizing agent (e.g., MnO2), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO2)[(η5-C5H5)Ru(NO)]2 (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges.Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH2)[(η5-C5H5)Ru(NO)]2 (5a) and (μ-CHCH3)[(η5-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by 1H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH2)(μ-H){(η5C5H5)Ru(NO)}2]+Br? (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c. 相似文献
6.
Thermodynamic and kinetic parameters have been established for the reaction between the carbon acid, 4-nitrophenylnitromethane,
(4-NPNM), and the base N’-n-propyl-N,N-di-n-propylbenzimidamide, (N’PDPBA), in mesitylene and in chlorobenzene. In some cases deuteron transfer from 4-(D2)NPNM to the base has also been studied. In addition, some results for the proton transfer reaction in tetrahydrofuran have
been collected. Spectrophotometric methods have been employed to monitor the ion-pair product, which is solvatochromic. In
general the solvent dependence of the parameters is as expected, but there is some indication of specific solvation. The kinetic
isotope effects of 11 and 8 in mesitylene and chlorobenzene, respectively, are larger than those predicted classically. However,
as is discussed the n-propyl group on the secondary nitrogen of the base may serve to reduce the extent of tunneling compared
to that in an unsubstituted analogue by a steric effect. 相似文献
7.
Conclusions In the photolysis of films of polyarylates F-1 and D-9, together with destruction and structuration, there is a formation of light-absorbing o-hydroxyketone and quinoid structures in the polymers, which determines the self-stabilization of the polyesters; moreover, the basic photochemical processes take place in a thin surface layer.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2302–2304 October, 1969 相似文献
8.
Baurin N Aboul-Ela F Barril X Davis B Drysdale M Dymock B Finch H Fromont C Richardson C Simmonite H Hubbard RE 《Journal of chemical information and computer sciences》2004,44(6):2157-2166
We have designed four generations of a low molecular weight fragment library for use in NMR-based screening against protein targets. The library initially contained 723 fragments which were selected manually from the Available Chemicals Directory. A series of in silico filters and property calculations were developed to automate the selection process, allowing a larger database of 1.79 M available compounds to be searched for a further 357 compounds that were added to the library. A kinase binding pharmacophore was then derived to select 174 kinase-focused fragments. Finally, an additional 61 fragments were selected to increase the number of different pharmacophores represented within the library. All of the fragments added to the library passed quality checks to ensure they were suitable for the screening protocol, with appropriate solubility, purity, chemical stability, and unambiguous NMR spectrum. The successive generations of libraries have been characterized through analysis of structural properties (molecular weight, lipophilicity, polar surface area, number of rotatable bonds, and hydrogen-bonding potential) and by analyzing their pharmacophoric complexity. These calculations have been used to compare the fragment libraries with a drug-like reference set of compounds and a set of molecules that bind to protein active sites. In addition, an analysis of the overall results of screening the library against the ATP binding site of two protein targets (HSP90 and CDK2) reveals different patterns of fragment binding, demonstrating that the approach can find selective compounds that discriminate between related binding sites. 相似文献
9.
Alousy A. Blundell N.J. Burgess J. Hubbard C.D. van Eldik R. 《Transition Metal Chemistry》2002,27(3):244-252
The solvatochromism of several dicyano-bis-diimine-iron(II) complexes in various binary aqueous solvent mixtures has been established, at 25 °C. A solvent sensitivity scale has been developed for these complexes. The solvatochromic properties of two tricyano-terdentate ligand iron(II) complexes in several solvents have also been determined, as have those of a series of tetracyano-diimine complexes in DMSO–water media. These results have been analysed and systematic but varied trends of solvation were demonstrated. Piezochromic parameters for two complexes have been obtained and are discussed in the context of a solvatochromism/piezochromism correlation. 相似文献
10.
RU Chang Bi Zbigniew Dauter Eleanor Dodson Guy Dodson Federico Gordiano Rod Hubbard Colin Reynolds 《Journal of Chemical Sciences》1983,92(4-5):473-483
Insulin modified by the removal of its 5 B chain C terminal residues is monomeric but remains substantially potent. The crystal
structures of the beef and insulin (dpi) with two molecules in the asymmetric unit has been determined by x-ray analysis. The 3-dimensional structure ofdpi proves to be generally similar to that of native molecule in 2Zn insulin. More detailed comparison reveals that the slight
differences in the two independent molecules of beefdpi are distributed uniformly throughout the structure in contrast to insulin in 2Zn insulin, where the structural changes are
concentrated in specific regions.
The loss of symmetry in thedpi crystal appears to be the inability of the A9 serine to pack effectively in the C2 cell. The efficient packing of the sheepdpi molecule whose crystal structure has also been determined and where A9 is glycine supports this conclusion. 相似文献