全文获取类型
收费全文 | 4937篇 |
免费 | 91篇 |
国内免费 | 16篇 |
专业分类
化学 | 3035篇 |
晶体学 | 37篇 |
力学 | 57篇 |
数学 | 687篇 |
物理学 | 1228篇 |
出版年
2020年 | 27篇 |
2019年 | 46篇 |
2017年 | 27篇 |
2016年 | 75篇 |
2015年 | 71篇 |
2014年 | 64篇 |
2013年 | 134篇 |
2012年 | 146篇 |
2011年 | 178篇 |
2010年 | 106篇 |
2009年 | 105篇 |
2008年 | 144篇 |
2007年 | 158篇 |
2006年 | 139篇 |
2005年 | 141篇 |
2004年 | 149篇 |
2003年 | 111篇 |
2002年 | 132篇 |
2001年 | 86篇 |
2000年 | 89篇 |
1999年 | 68篇 |
1998年 | 58篇 |
1997年 | 55篇 |
1996年 | 69篇 |
1995年 | 77篇 |
1994年 | 82篇 |
1993年 | 79篇 |
1992年 | 60篇 |
1991年 | 65篇 |
1990年 | 55篇 |
1989年 | 51篇 |
1988年 | 74篇 |
1987年 | 79篇 |
1986年 | 45篇 |
1985年 | 88篇 |
1984年 | 85篇 |
1983年 | 74篇 |
1982年 | 67篇 |
1981年 | 80篇 |
1980年 | 72篇 |
1979年 | 75篇 |
1978年 | 76篇 |
1977年 | 52篇 |
1976年 | 76篇 |
1975年 | 63篇 |
1974年 | 50篇 |
1973年 | 55篇 |
1972年 | 39篇 |
1971年 | 44篇 |
1932年 | 27篇 |
排序方式: 共有5044条查询结果,搜索用时 15 毫秒
81.
Rajapakshe A Gruhn NE Lichtenberger DL Basta R Arif AM Ernst RD 《Journal of the American Chemical Society》2004,126(43):14105-14116
Molecules of the form Cp(6,6-dmch)ZrX(2) (Cp = eta(5)-cyclopentadienyl, X = Cl, Br, I; 6,6-dmch = eta(5)-6,6-dimethylcyclohexadienyl) have been synthesized, and the molecular and electronic structures have been investigated. These molecules allow direct comparison of the bonding and properties of pentadienyl and cyclopentadienyl ligands in the same high-oxidation-state metal complexes. Unlike the well-known Cp(2)ZrX(2) analogues, these Cp(6,6-dmch)ZrX(2) molecules are intensely colored, indicating significantly different relative energies of the frontier orbitals. Also unusual, the average Zr-C distances to the 6,6-dmch pentadienyl ligand are about 0.1 A longer than the average Zr-C distances to the cyclopentadienyl ligand for these Zr(IV) complexes, opposite of what is observed for the Zr(II) complex Cp(2,6,6-tmch)Zr(PMe(3))(2) (tmch = eta(5)-2,6,6-trimethylcyclohexadienyl), reflecting a dramatic reversal in the favorability of the bonding depending on the metal oxidation state. The experimental and computational results indicate that the color of the Cp(6,6-dmch)ZrX(2) complexes is due to a 6,6-dmch ligand-to-metal charge-transfer band. Compared to the Cp(2)ZrX(2) analogues, the Cp(6,6-dmch)ZrX(2) molecules have a considerably less stable HOMO that is pentadienyl-based and an essentially unchanged metal-based LUMO. Also, the lowest unoccupied orbital of pentadienyl is stabilized relative to cyclopentadienyl and becomes a better potential delta electron acceptor, thus contributing to the differences in structure and reactivity of the low-valent and high-valent metal complexes. 相似文献
82.
3-Diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II) — Synthesis and Structure Bis-(N′, N′-diethyl-N-benzoylselenoureato)nickel(II) reacts with diphosgene in benzene to 3-diethylamino-5-phenyl-1,2,4-diselenazolium-tetrachloroniccolate(II). Its structure is confirmed by RKSA and ESCA. The compound consists of cations, which are planar fivemembered rings and of tetrahedral tetrachloroniccolate(II) anions. The complex is isomorphic with 3-diethylamino-5-phenyl-1,2,4-dithiazolium-tetrachloroniccolate(II). 相似文献
83.
Erik J. Faber Dr. Wouter Sparreboom Wilrike Groeneveld Louis C. P. M. de Smet Dr. Johan Bomer Wouter Olthuis Dr. Han Zuilhof Dr. Ernst J. R. Sudhölter Prof. Piet Bergveld Prof. Albert van den Berg Prof. 《Chemphyschem》2007,8(1):101-112
The electrochemical behavior of Si--C linked organic monolayers is studied in electrolyte-insulator-Si devices, under conditions normally encountered in potentiometric biosensors, to gain fundamental knowledge on the behavior of such Si electrodes under practical conditions. This is done via titration experiments, Mott-Schottky data analysis, and data fitting using a site-binding model. The results are compared with those of native SiO(2) layers and native SiO(2) layers modified with hexamethyldisilazane. All samples display pH sensitivity. The number of Si--OH groups on the alkylated samples is calculated to be less than 0.7 % of that of a pure SiO(2) insulator, which still causes a pH sensitivity of approximately 25 mV per pH unit in the pH range: 4-7. The alkylated samples hardly suffer from response changes during up- and down-going titrations, which indicates that very little oxide is additionally formed during the measurements. The pK(a) values of all samples with monolayers (4.0-4.4) are lower than that of native SiO(2) (6.0). The long-term drift (of approximately 1 mV h(-1)) is moderate. The results indicate that biosensors composed of alkylated Si substrates are feasible if a cross-sensitivity towards pH in the sensor signal is taken into account. 相似文献
84.
85.
Harro Lentz Ernst Ulrich Franck 《Angewandte Chemie (International ed. in English)》1978,17(10):728-730
Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described. 相似文献
86.
E. Hensel R. Groetzschel E. Richter 《Journal of Radioanalytical and Nuclear Chemistry》1988,122(2):321-326
Silicon nitride hard coatings on tool steel produced by ion beam mixing following sputter or vapour deposition were investigated by RBS and Vickers microhardness measurements. Atomic mixing in the coating/steel interface region resulting in an improved adhesion and in a significant increase of the microhardness of the surface layers was found. Ion beam mixing with gas ions and high fluences leads to blistering of the implanted atoms in the silicon nitride layer. 相似文献
87.
88.
Joachim G. Liehr Richard M. Caprioli John H. Beynon Roger P. Morgan Wilhelm J. Richter 《Journal of mass spectrometry : JMS》1980,15(3):157-160
The oxygen rearrangement in molecular ions of 3-phenylpropionates has been investigated with the aid of mass analyzed ion kinetic energy spectra. Elimination of an allyl radical followed by expulsion of ketene from the molecular ion of allyl 3-phenylpropionate is shown to result in formation of protonated benzaldehyde. The oxygen rearrangement has been found to be inoperative in ionized methyl 3-methyl-3-phenylbutyrate. [M ? CH3 ? CH2CO]+ ions in the spectrum of the latter compound are formed by elimination of the 3-methyl substituent and subsequent methoxy migration. 相似文献
89.
A novel approach to the preparation of perfluorotail-functionalized triarylphosphines using a p-silyl substituent as the branching point has been developed. This approach enabled the attachment of between three and nine perfluorotails per phosphorus atom, resulting in the production of highly fluorous tris[p-(1H,1H,2H, 2H-perfluoroalkylsilyl)aryl]phosphines, P[C(6)H(4)-p-SiMe(3)(-)(n)()(CH(2)CH(2)C(x)()F(2)(x)()(+1))(n)()](3) (n = 1, 2, 3; x = 6, 8), containing between 50 and 67 wt % fluorine. (31)P NMR studies indicate that the phosphorus atoms, and consequently the sigma-donor and pi-acceptor properties of these phosphines, are not influenced by the electron-withdrawing perfluoroalkyltails. The fluorous triarylphosphines are readily soluble in fluorous solvents and display fluorous phase preference in several fluorous biphasic systems. The phase partitioning of these fluorous ligands, as well as their donor properties, is discussed in relation to their potential for fluorous biphasic catalyst separation. 相似文献
90.
K. Nomura H. Reuther E. Richter Y. Ujihira 《Journal of Radioanalytical and Nuclear Chemistry》1995,190(2):299-313
Changes in the magnetic structure of Fe–Si–Al films due to Al and N ion implantation were studied by57Fe Conversion Electron Mössbauer Spectrometry (CEMS). The peaks of the magnetic sextets due to the crystalline films became broader by implantation with 5×1016 Al/cm2, suggesting the formation of amorphous phases. In the CEM spectrum of one sample with large grains implanted with 1×1017 Al/cm2 a crystalline -Fe phase appeared. N implantation with the same dose did not amorphize the sample but the components with high magnetic hyperfine fields were enhanced. 相似文献