全文获取类型
收费全文 | 4569篇 |
免费 | 218篇 |
国内免费 | 140篇 |
专业分类
化学 | 3082篇 |
晶体学 | 53篇 |
力学 | 102篇 |
综合类 | 12篇 |
数学 | 628篇 |
物理学 | 1050篇 |
出版年
2023年 | 28篇 |
2022年 | 34篇 |
2021年 | 41篇 |
2020年 | 72篇 |
2019年 | 72篇 |
2018年 | 58篇 |
2017年 | 61篇 |
2016年 | 121篇 |
2015年 | 101篇 |
2014年 | 124篇 |
2013年 | 222篇 |
2012年 | 240篇 |
2011年 | 246篇 |
2010年 | 156篇 |
2009年 | 169篇 |
2008年 | 198篇 |
2007年 | 232篇 |
2006年 | 177篇 |
2005年 | 199篇 |
2004年 | 159篇 |
2003年 | 117篇 |
2002年 | 126篇 |
2001年 | 81篇 |
2000年 | 107篇 |
1999年 | 102篇 |
1998年 | 75篇 |
1997年 | 89篇 |
1996年 | 86篇 |
1995年 | 57篇 |
1994年 | 78篇 |
1993年 | 78篇 |
1992年 | 78篇 |
1991年 | 51篇 |
1990年 | 41篇 |
1989年 | 46篇 |
1988年 | 42篇 |
1987年 | 52篇 |
1986年 | 67篇 |
1985年 | 59篇 |
1984年 | 48篇 |
1983年 | 50篇 |
1982年 | 67篇 |
1981年 | 41篇 |
1980年 | 63篇 |
1979年 | 46篇 |
1978年 | 42篇 |
1977年 | 45篇 |
1976年 | 47篇 |
1975年 | 46篇 |
1974年 | 27篇 |
排序方式: 共有4927条查询结果,搜索用时 15 毫秒
71.
19F and 31P NMR spectroscopy were used to study the kinetics of the hydrolysis of LiPF6 in the homogenous solvent system propylene carbonate (PC)—dimethyl carbonate (DMC)—H2O. It was found that the main products of the hydrolysis are HF, LiPO2F2 and Li2PO3F. The content of POF3 and PF5 was negligibly low. We set up a hypothesis that the main factor determining the rate of the process is the so-called ‘secondary’ catalytic effect, caused by solvated H+ ions. 相似文献
72.
Peter Pfortner M. G. Weller Reinhard Niessner 《Analytical and bioanalytical chemistry》1998,360(2):192-198
The potential of the earlier reported sandwich-immunoassay principle for the detection of nitroaromatic residues bound to humic acids was examined. A synthetic conjugate derived by coupling a 2,4,6-trinitrotoluene derivative to humic acid was used as a model substance for bound nitroaromatic residues. Spectrophotometric determination gave a content of 14 ± 1.6 μmol/g TNT-derivative in the synthetic conjugate, which was used as a calibration standard. Extensive blocking optimization was necessary to establish the sandwich-immunoassay. Experiments were carried out to check the selectivity of the developed test system. Trace amounts of 2,4,6-trinitrotoluene (25 μg/L) suppressed the assay signal completely by blocking the antibody binding sites. This was a proof for the excellent selectivity of the assay. The potential of quantitative determinations was examined with dilution experiments. During assay optimization strong non-immunological interactions between various proteins and humic acids were observed. This led to a significant improvement of the original sandwich-immunoassay, where the humic acid antibody was substituted by basic proteins. More sensitive calibration curves with higher signal intensities were achieved. This new immunoassay seems to be the method of choice for further immunological investigations of bound residues. 相似文献
73.
The energy transfer between argon atoms and ozone complexes O3*, excited in the region of the dissociation threshold, is calculated for fixed temperatures (100 K< or =T < or =2500 K) using classical trajectories. The internal energy of ozone is resolved in terms of vibrational and rotational energies. For all temperatures, energy flows from O3* to Ar. The vibrational energy transfer, relative to k(B)T, is very small below 500 K, but gradually increases towards high temperatures. The relative rotational energy transfer, on the other hand, monotonously decreases with T; around 1100 K it falls below the relative vibrational energy transfer. Thermally averaged cross sections for vibrational and rotational energy transfers are also calculated. The implications for the stabilization of ozone complexes in the energy transfer model are discussed. 相似文献
74.
不熔化沥青球在低速流化床中炭化和活化的初步研究 总被引:5,自引:0,他引:5
不熔化沥青球在低速流化床中炭化和活化的初步研究乔文明,王克温,凌立成,刘朗周承泽,王瑾,郑斌(中国科学院山西煤炭化学研究所,太原030001)(上海太平洋化工(集团)公司焦化总厂,200241)关键词低速流化床,活化,炭化,球形活性炭由于球形活性炭,... 相似文献
75.
Thilo Berkenbusch Andy Ch. Laungani Reinhard Brückner Manfred Keller 《Tetrahedron letters》2004,45(52):9517-9520
4-tert-Butyl-2-cyclohexen-1-one dimerizes in THF solution via its kinetic enolate, leading to di-tert-butylditwistane 8 in up to 36% yield (−78 °C → room temp., protonolysis, flash chromatography). X-ray crystallography shows that 8 incorporates one R and one S enantiomer of the starting ketone; none of the diastereomeric ditwistanes epi-8, epi’-8 or iso-8 was isolated. This means that the formation of 8 proceeds with mutual kinetic resolution and 100% induced diastereoselectivity. 相似文献
76.
Assembly of a supramolecular cube, [(Cp*WS3Cu3)8 Cl8(CN)12Li4] from a preformed incomplete cubane-like compound [PPh4][Cp*WS3(CuCN)3 总被引:2,自引:0,他引:2
Lang JP Xu QF Chen ZN Abrahams BF 《Journal of the American Chemical Society》2003,125(42):12682-12683
A supramolecular cube has been formed by linking WS3Cu3 clusters with bidentate ligands. Eight WS3Cu3 clusters, which have an incomplete cubane-like structure, serve as the three connecting nodes of the cube, while 12 bridging cyanide anions coordinated to copper centers lie along the edges of the cube. Eight chloride anions and four lithium cations are located inside the cube. 相似文献
77.
Antonio Currao Nantko Feiken Alceo Macchioni Reinhard Nesper Paul S. Pregosin Gerald Trabesinger 《Helvetica chimica acta》1996,79(6):1587-1591
The ligand (6,6′-dimethoxybiphenyl-2,2′-diyl)bis[3,5-di(tert-butyl)phenylphosphine] ( 1 ) forms an unexpectedly stable hydrido-bis-solvento complex of composition [RuH(isopropanol)2( 1 )]BF4, ( 2 ) under the conditions used in the enantioselective hydrogenation of pyrones. The structure of 2 , determined by X-ray diffraction, represents the first well-characterized chiral five-coordinate bis-phosphine ruthenium-hydride complex stable as a solvento complex, and provides a structural link in the enantioselective pyrone hydrogenation cycle catalyzed by [Ru(OAc)2( 1 )]. Using the arene complex [RuH(p-cymene)( 1 )]BF4 ( 3 ), the chiral pocket of coordinated 1 is shown to be relatively rigid, via NMR spectroscopy. This is reflected in restricted rotation about one of the four P–[3,5-di(tert-butyl)phenyl] P? Cipso bonds at room temperature. 相似文献
78.
79.
Guang‐Fei Liu Lin‐Lin Li Yong Zhang Jian‐Ping Lang Seik Weng Ng 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(1):m1-m3
The title compound, [Cu(ClO4)2(C4H9N3O2)2][Cu(C4H9N3O2)2(CH4O)2](ClO4)2·2CH3OH, comprises two independent CuII species lying on different inversion sites. In the Cu complexes, a distorted octahedral geometry arises (from basic square‐planar N4 coordination) from the weak coordination of two perchlorate ions (as Cu—O) in one species and two methanol molecules in the other (also as Cu—O). Interactions between the O atoms of the perchlorate anions or methanol groups and the imide or amine NH groups afford an extensive intermolecular hydrogen‐bonding network. 相似文献
80.
Bis-(2,4,5-triphenylimidazolyls) result from the dimerization of 2,4,5-triphenylimidazolyls and from the nucleophilic attack of 2,4,5-triphenylimidazole anions upon 2,4,5-triphenylimidazolylium cations. The isomeric bis-imidazolyls consist of imidazole and isoimidazole systems. Imidazoles undergo only anodic oxidation, isoimidazoles only cathodic reduction. Therefore the bis-imidazolyls may be analyzed from their electrochemical behaviour. Bis-(2,4,5-triphenylimidazolyl)-1,2′ and bis-(2,4,5-triphenylimidazolyl)-1,4′ undergo reductive bond cleavage in an ē.c?.ē. mechanism from which 2,4,5-triphenyl-imidazole anions result. The electrochemical properties of one of the bis-imidazolyls agree with that of 1,4,5-triphenyl-2-(2,4,5-triphenylisoimidazolyl-4)-imidazole and not with that of bis-(2,4,5-triphenylimidazolyl)-2,4′ as reported in literature. 相似文献