全文获取类型
收费全文 | 13155篇 |
免费 | 1367篇 |
国内免费 | 1155篇 |
专业分类
化学 | 9854篇 |
晶体学 | 144篇 |
力学 | 475篇 |
综合类 | 84篇 |
数学 | 1976篇 |
物理学 | 3144篇 |
出版年
2024年 | 25篇 |
2023年 | 204篇 |
2022年 | 354篇 |
2021年 | 453篇 |
2020年 | 497篇 |
2019年 | 442篇 |
2018年 | 398篇 |
2017年 | 340篇 |
2016年 | 652篇 |
2015年 | 584篇 |
2014年 | 683篇 |
2013年 | 905篇 |
2012年 | 1178篇 |
2011年 | 1281篇 |
2010年 | 866篇 |
2009年 | 807篇 |
2008年 | 954篇 |
2007年 | 888篇 |
2006年 | 790篇 |
2005年 | 654篇 |
2004年 | 567篇 |
2003年 | 376篇 |
2002年 | 323篇 |
2001年 | 184篇 |
2000年 | 158篇 |
1999年 | 170篇 |
1998年 | 107篇 |
1997年 | 99篇 |
1996年 | 115篇 |
1995年 | 73篇 |
1994年 | 71篇 |
1993年 | 56篇 |
1992年 | 52篇 |
1991年 | 44篇 |
1990年 | 44篇 |
1989年 | 32篇 |
1988年 | 26篇 |
1987年 | 27篇 |
1986年 | 19篇 |
1985年 | 28篇 |
1984年 | 21篇 |
1983年 | 15篇 |
1982年 | 9篇 |
1981年 | 7篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1975年 | 6篇 |
1974年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
三(2-苯并咪唑亚甲基)胺硝酸镍(Ⅱ)配合物的合成及结构 总被引:5,自引:0,他引:5
三(2-苯并咪唑亚甲基)胺简称NTB与Ni(Ⅱ)的硝酸盐形成配合物C28H35N9O9S2Ni。本文报道其合成,红外光谱及晶体结构。该化合物为三斜晶系,空间P1↑-,a=9.650(3),b=12.716(2),c=14.436A,α=11.46(2),β=91.66(3),γ=97.55(2)°,V=1718(2)A^3,Z=2,F(000)=793,Dc=1.48g/cm^3,Mr=764.1 相似文献
52.
DFT computational study of the mechanism of allyl halides carbonylation catalyzed by nickel tetracarbonyl 总被引:1,自引:0,他引:1
Bottoni A Miscione GP Novoa JJ Prat-Resina X 《Journal of the American Chemical Society》2003,125(34):10412-10419
A theoretical investigation at the DFT(B3LYP) level on the carbonylation reaction of allyl bromide catalyzed by nickel tetra-carbonyl Ni(CO)(4) is discussed. The computational results show the following: (i) Three main steps characterize the catalytic cycle: (a) an oxidative addition step, (b) a carbonylation step, and (c) a reductive elimination step where the acyl product is obtained and the catalyst is regenerated. (ii) Both Ni(CO)(3) and Ni(CO)(4) complexes can behave as "active" catalytic species. (iii) The oxidative addition leads to the formation of either eta(3) or eta(1)-allyl nickel complexes, which are involved in a fast equilibrium. (iv) The carbonylation occurs much more easily on the eta(1) than on the eta(3) intermediates. 相似文献
53.
Paital AR Mitra T Ray D Wong WT Ribas-Ariño J Novoa JJ Ribas J Aromí G 《Chemical communications (Cambridge, England)》2005,(41):5172-5174
Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized. 相似文献
54.
Hu H Qiao M Xie F Fan K Lei H Tan D Bao X Lin H Zong B Zhang X 《The journal of physical chemistry. B》2005,109(11):5186-5192
The desulfurization of thiophene on Raney Ni and rapidly quenched skeletal Ni (RQ Ni) has been studied in ultrahigh vacuum (UHV) by X-ray photoelectron spectroscopy (XPS). The Raney Ni or RQ Ni can be approximated as a hydrogen-preadsorbed polycrystalline Ni-alumina composite. It is found that thiophene molecularly adsorbs on Raney Ni or RQ Ni at 103 K. At 173 K, thiophene on alumina is desorbed, while thiophene in direct contact with the metallic Ni in Raney Ni undergoes C-S bond scission, leading to carbonaceous species most probably in the metallocycle-like configuration and atomic sulfur. On RQ Ni, the temperature for thiophene dissociation is about 100 K higher than that on Raney Ni. The lower reactivity of RQ Ni toward thiophene is tentatively attributed to lattice expansion of Ni crystallites in RQ Ni due to rapid quenching. The existence of alumina and hydrogen may block the further cracking of the metallocycle-like species on Raney Ni and RQ Ni at higher temperatures, which has been the dominant reaction pathway on Ni single crystals. By 473 K, the C 1s peak has disappeared, leaving nickel sulfide on the surface. 相似文献
55.
Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me2Si{3-But-C5H3Rh(C2H4)2}2] By reaction of [{(C2H4)2RhCl}2] with Na2[Me2Si(C5H4)2] or with Li2[Me2Si(3-But-C5H3)2] in THF the dinuclear silylene bridged complexes [Me2Si{C5H4Rh(C2H4)2}2] 1 and [Me2Si{3-But-C5H3Rh(C2H4)2}2] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η3:η3 benzene complex [Me2Si(C5H4Rh2)2C6H6] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 . 相似文献
56.
The properties of the triplet excited state of [60] fullerene-containing cyclic sulphoxide have been investigated by time-resolved absorption spectroscopy. Transient absorption bands of [60] fullerene-containing cyclic sulphoxide showed two decay-components, which wrer attributed to triplet excited states of different spin multiplicity. The properties of photoexcited states of [60] fullerene-containing cyclic sulphoxide are also reported. 相似文献
57.
构筑了MgO部分稳定的ZrO2基固体电解质电化学电池测量EAF的实验装置,测定了Sm2CuO4的标准Gibbs生成自由能。结果表明化合物RE2CuO23(RE=La,Nd,Sm,Eu)随着镧系元素离子半径减小,热力学稳定性下降,并用晶体场理论解释了这一规律。 相似文献
58.
Serrano MC Portolés MT Vallet-Regí M Izquierdo I Galletti L Comas JV Pagani R 《Macromolecular bioscience》2005,5(5):415-423
Tissue engineering offers the potential of providing vessels that can be used to replace diseased and damaged native blood vessels. The endothelization of a synthetic vascular graft minimizes the failures associated with blood clotting and platelet activation. The aim of this study was to culture vascular-derived endothelial and smooth muscle cells on both untreated and NaOH-treated poly(epsilon-caprolactone) (PCL) films, a biocompatible and bio-resorbable polymer, and to evaluate the behavior of both cell types as a preliminary study for vascular graft development. PCL films were prepared by hot pressing; characterized by DSC, IR, SEM, and scanning force microscopy; and treated with NaOH to increase the surface hydrophilicity before cell culture. Endothelial and smooth muscle cells, isolated from pig cava vein, were characterized by immunofluorescence and confocal microscopy studies of endothelial nitric oxide synthase and alpha-smooth muscle actin. Good adhesion, growth, viability and morphology of both the endothelial and smooth muscle cells on PCL films were obtained, but a light stimulation of mitochondrial activity was observed during short culture times. NaOH treatment improved the adhesion and enhanced the proliferation in both cell types. This verified the possible use of this modified polymer as a support in the preparation of a synthetic vascular graft. [Diagram: see text] SEM micrograph of smooth muscle cells cultured on NaOH-treated PCL film. (Original magnification: 1000x). 相似文献
59.
ZHOU Cheng-He Juan F.Miravet M.Isabel Burguete Santiago V.Luis BAI Xue YUAN Yong 《有机化学》2004,24(Z1):380
Polynitrogen receptors such as bis-histidine peptides possess strong ability to bind metals, which play much important roles in medicinal, bioinorganic, bioorganic, biomimetic and supramolecular chemistry. In order to investigate the interaction of these hosts with a variety of neutral, cationic and anionic guests, several techniques, for example, NMR,potentiometric tirations and monocrystal X-ray diffraction have been employed. Among them NMR is a powerful technique for unraveling the structure of polynitrogen receptors as long as they are in solution where the rapid tumbling of molecules averages out the anisotropies such as chemical shift and dipole-dipole interactions. General 1H NMR approach has been widely used for the study of host-guest interaction, but it is difficult for the accurate measurement in complexes structures, particularly metal complexes structures in which how the polynitrogen receptors bind metal, and which nitrogen binds metal and so on. 相似文献
60.
A fluorogenic probe for bacteria imaging was reported. The binding with anionic bacterial surfaces disassembled the self-assembly probe to turn-on the fluorescence and shift pyrene monomer/excimer ratiometric signals. 相似文献