全文获取类型
收费全文 | 7654篇 |
免费 | 202篇 |
国内免费 | 24篇 |
专业分类
化学 | 5782篇 |
晶体学 | 45篇 |
力学 | 70篇 |
数学 | 1115篇 |
物理学 | 868篇 |
出版年
2020年 | 77篇 |
2019年 | 73篇 |
2016年 | 147篇 |
2015年 | 146篇 |
2014年 | 114篇 |
2013年 | 258篇 |
2012年 | 244篇 |
2011年 | 324篇 |
2010年 | 183篇 |
2009年 | 192篇 |
2008年 | 293篇 |
2007年 | 301篇 |
2006年 | 274篇 |
2005年 | 306篇 |
2004年 | 285篇 |
2003年 | 231篇 |
2002年 | 199篇 |
2001年 | 112篇 |
2000年 | 103篇 |
1999年 | 110篇 |
1998年 | 109篇 |
1997年 | 129篇 |
1996年 | 129篇 |
1995年 | 124篇 |
1994年 | 112篇 |
1993年 | 123篇 |
1992年 | 109篇 |
1991年 | 108篇 |
1990年 | 85篇 |
1989年 | 109篇 |
1988年 | 119篇 |
1987年 | 105篇 |
1986年 | 113篇 |
1985年 | 138篇 |
1984年 | 107篇 |
1983年 | 109篇 |
1982年 | 112篇 |
1981年 | 100篇 |
1980年 | 107篇 |
1979年 | 96篇 |
1978年 | 88篇 |
1977年 | 85篇 |
1976年 | 82篇 |
1974年 | 95篇 |
1973年 | 86篇 |
1971年 | 75篇 |
1961年 | 141篇 |
1960年 | 195篇 |
1959年 | 102篇 |
1958年 | 115篇 |
排序方式: 共有7880条查询结果,搜索用时 8 毫秒
211.
Klaus Burger Gabor Radics Lothar Hennig Christoph B?ttcher Jan Spengler Fernando Albericio 《Monatshefte für Chemie / Chemical Monthly》2005,5(3):763-776
Starting from L-malic, L-citramalic, and rac. thiomalic acids routes to L-homoisoserine, 2-methyl-L-homoisoserine and rac. homoisocysteine have been developed. The new orthogonally protected and carboxy-activated building blocks are GABA as well as -hydroxy and -mercapto acid derivatives, suitable for the construction of peptide and depsipeptide surrogates. 相似文献
212.
213.
Jürgen Pebler Klaus Schmidt Kurt Dehnicke Prof. Dr. Johann Weidlein 《无机化学与普通化学杂志》1978,440(1):269-277
121Sb Mössbauer Spectra of Antimony (V) Compounds. II The Mössbauer resonance effect of 121Sb has been studied at 4.2 K in a series of 11 antimony(V) compounds which are in most cases bridged. Isomer shift and quadrupole splitting variations are considered in the light of results of X-ray and vibrational spectroscopy. Preparation and the vibrational spectra of [NMe4][SbCl4(n3)2] are described. Within the limitations of available structural data related tin compounds are compared with those of corresponding 119Sn Mössbauer spectra. 相似文献
214.
This paper presents the vacuum structures of aquacopper(II) bis(amino acid) complexes with glycine, sarcosine, N,N-dimethylglycine, and N-tert-butyl-N-methylglycine estimated using the B3LYP method. The differences between the B3LYP vacuum structures and experimental crystal structures suggested considerable influence of crystal lattice packing effects on the changes in the complexes' geometries. A previously developed molecular mechanics force field for modeling anhydrous copper(II) amino acidates was reoptimized to simulate these changes and predict the properties of both trans and cis anhydrous and aqua copper(II) amino acid complexes. The modeling included experimental molecular and crystal structures of 13 anhydrous and 10 aqua copper(II) amino acidates with the same atom types (Cu(II), C, H, N, and O) but various copper(II) coordination polyhedron geometries, crystal symmetries, and intermolecular interactions. The empirical parameters of the selected potential energy functions were optimized on the B3LYP vacuum copper(II) coordination geometries of three anhydrous copper(II) amino acidates and on experimental crystalline internal coordinates and unit cell dimensions of six anhydrous and six aqua copper(II) amino acid complexes. The respective equilibrium structures were calculated in vacuo and in simulated crystalline environment. The efficacy of the final force field, FFW, was examined. The total root-mean-square deviations between the experimental and theoretical crystal values were 0.018 A in the bond lengths, 2.2 degrees in the valence angles, 5.5 degrees in the torsion angles, and 0.395 A in the unit cell lengths. FFW reproduced the unit cell volumes in the range from -8.1 to 9.6%. The means of Cu to axial water oxygen distances were 2.4 +/- 0.1 A (experiment) and 2.6 +/- 0.1 A (FFW). This paper describes the ability of the molecular mechanics model and FFW force field to simulate the flexibility of the metal coordination polyhedron. The new force field proved effective in predicting the most stable molecular conformation of copper(II) amino acidato systems in vacuo. 相似文献
215.
Markus Neuenschwander Peter Bigler Klaus Christen Rudolf Iseli Rolf Kyburz Hansueli Mühle 《Helvetica chimica acta》1978,61(6):2047-2058
Chloroacylation and bromoacylation of carbonyl compounds: A forgotten carbonyl reaction. I. Scope of the reaction Aliphatic, α,β-unsaturated and aromatic aldehydes as well as aliphatic ketones react with acyl halides to (α-haloalkyl)esters. These bifunctional derivates contain two leaving groups of different reactivity. The scope of this scarcely of this scarcely known carbonyl reaction is discussed. 相似文献
216.
Yuriy G. Denisenko Victor V. Atuchin Maxim S. Molokeev Alexander E. Sedykh Nikolay A. Khritokhin Aleksandr S. Aleksandrovsky Aleksandr S. Oreshonkov Nikolai P. Shestakov Sergey V. Adichtchev Alexey M. Pugachev Elena I. Salnikova Oleg V. Andreev Illaria A. Razumkova Klaus Müller-Buschbaum 《Molecules (Basel, Switzerland)》2022,27(13)
Praseodymium sulfate was obtained by the precipitation method and the crystal structure was determined by Rietveld analysis. Pr2(SO4)3 is crystallized in the monoclinic structure, space group C2/c, with cell parameters a = 21.6052 (4), b = 6.7237 (1) and c = 6.9777 (1) Å, β = 107.9148 (7)°, Z = 4, V = 964.48 (3) Å3 (T = 150 °C). The thermal expansion of Pr2(SO4)3 is strongly anisotropic. As was obtained by XRD measurements, all cell parameters are increased on heating. However, due to a strong increase of the monoclinic angle β, there is a direction of negative thermal expansion. In the argon atmosphere, Pr2(SO4)3 is stable in the temperature range of T = 30–870 °C. The kinetics of the thermal decomposition process of praseodymium sulfate octahydrate Pr2(SO4)3·8H2O was studied as well. The vibrational properties of Pr2(SO4)3 were examined by Raman and Fourier-transform infrared absorption spectroscopy methods. The band gap structure of Pr2(SO4)3 was evaluated by ab initio calculations, and it was found that the valence band top is dominated by the p electrons of oxygen ions, while the conduction band bottom is formed by the d electrons of Pr3+ ions. The exact position of ZPL is determined via PL and PLE spectra at 77 K to be at 481 nm, and that enabled a correct assignment of luminescent bands. The maximum luminescent band in Pr2(SO4)3 belongs to the 3P0 → 3F2 transition at 640 nm. 相似文献
217.
218.
Mural inspection by vibration measurements with TV-holography 总被引:2,自引:0,他引:2
Thomas Fricke-Begemann Gerd Gülker Klaus D. Hinsch Holger Joost 《Optics and Lasers in Engineering》2000,32(6):537-548
A commonly encountered problem in the conservation of historical murals is the identification of sections in the plaster that have detached from the wall and thus threaten to fall off. Commonly, walls are inspected by the acoustic response to a gentle finger-tapping (percussion method). Since this is a costly and cumbersome technique, means for a more automatic inspection are searched for. A TV-holography system of increased sensitivity in combination with acoustic excitation of the object is shown to be a new and powerful tool for monitoring of loose areas. It has the advantage of non-contact and remote operation which, for example, is extremely useful in large buildings. Principles of the method, experimental results obtained at an artificial wall in the laboratory, and a thorough comparison of results from historical sites gained by the traditional percussion method and the new technique are presented. The latter shows very good agreement in the assessment of wall quality and thus is evidence of the suitability of the optical equipment for tasks in conservation. 相似文献
219.
220.