全文获取类型
收费全文 | 1029篇 |
免费 | 22篇 |
国内免费 | 6篇 |
专业分类
化学 | 709篇 |
晶体学 | 5篇 |
力学 | 45篇 |
数学 | 127篇 |
物理学 | 171篇 |
出版年
2024年 | 1篇 |
2023年 | 5篇 |
2022年 | 14篇 |
2021年 | 24篇 |
2020年 | 14篇 |
2019年 | 28篇 |
2018年 | 30篇 |
2017年 | 17篇 |
2016年 | 38篇 |
2015年 | 23篇 |
2014年 | 33篇 |
2013年 | 85篇 |
2012年 | 56篇 |
2011年 | 75篇 |
2010年 | 56篇 |
2009年 | 36篇 |
2008年 | 66篇 |
2007年 | 49篇 |
2006年 | 64篇 |
2005年 | 67篇 |
2004年 | 54篇 |
2003年 | 35篇 |
2002年 | 34篇 |
2001年 | 13篇 |
2000年 | 18篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 15篇 |
1996年 | 14篇 |
1995年 | 3篇 |
1994年 | 11篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 1篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 8篇 |
1981年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有1057条查询结果,搜索用时 15 毫秒
41.
Victor N. Khrustalev Mikhail Yu. Antipin Irina V. Borisova Valery V. Lunin Ghassoub Rima 《Journal of organometallic chemistry》2004,689(2):478-483
The reaction of equimolar quantities of LiOCH2CH2NMe2 and E14(OCH2CH2NMe2)2 (E14=Ge, Sn) in ether yielded new ate complexes [LiE14(OCH2CH2NMe2)3]2 (E14=Ge (1), Sn (2)) with bidentate ligands. The compounds 1 and 2 are white crystalline substances which are highly soluble in THF and pyridine and very sensitive to the traces of oxygen and moisture. The structures of these compounds are studied by X-ray diffraction analysis. The ate complexes 1 and 2 are powerful nucleophiles and may be employed as ligands (neutral) in the coordination chemistry of the transition metals. The electronegative O-substituents at the divalent E14 atoms render them less oxidizable than alkyl- or aryl-substituted derivatives, and the bidentate ligands, owing to intramolecular donor-acceptor interactions, make them more thermodynamically stable compared to monodentate ligands. 相似文献
42.
Tsirelson Vladimir Abramov Yury Zavodnik Valery Stash Adam Belokoneva Elena Stahn Jochen Pietsch Ullrich Feil Dirk 《Structural chemistry》1998,9(4):249-254
The critical points in the model electron density distributions of LiF, NaF, NaCl, and MgO crystals, constructed from accurate X-ray diffraction data, are determined. For LiF and MgO they are compared with those obtained from a Hartree–Fock electron density calculation. Both experiment and theory show the same type of critical points on the bond lines. The topological features in areas between structural units, where the electron density is low and near-uniform, turn out to be model dependent and cannot be established well with the data available. Topological analysis of procrystals (hypothetical systems consisting of spherical atoms or ions placed on the same sites as atoms in real crystal) show that (3, –1) critical points, usually connected with bonding interaction, are observed on interatomic lines in these nonbonded systems as well. 相似文献
43.
Sergey I. Vdovenko Igor I. Gerus Natalia V. Lutenko Valery P. Kukhar Jacek Wjcik 《Journal of Molecular Structure》2007,840(1-3):125-132
Spatial structure of six β-substituted enones, with common structure R1O–CR2CH–COCF3, were R1 = C2H5, R2 = H (ETBO); R1 = R2 = CH3 (TMPO); R1 = C2H5, R2 = C6H5 (ETPO); R1 = C2H5, R2 = 4- O2NC6H4 (ETNO); R1 = C2H5, R2 = C(CH3)3 (ETDO) were investigated by 1H and 19F NMR, infrared spectroscopy and AM1 calculations. NMR spectra revealed that enones (MBO), (ETBO) and (TMPO) are exclusively (3E) isomers, whereas in (ETPO), (ETNO) and especially in (ETDO) the percentage of (3Z) isomers is significant and depends on the nature of solvents. Conformational behaviour of studied enones are determined by the rotation around of CC double bond, C–C and C–O single bonds (correspondingly trifluoroacetyl and alkoxy groups), and (EZZ) conformer being the most stable in all cases. IR spectra revealed that with the exception of (ETDO) (EZZ) conformer is most populated in all cases. Bulky substituents like phenyl or tert-butyl group at β-position of enone result in the equilibrium mainly between (EZZ) and (ZZZ) forms, whereas β-hydrogen and β-methyl substituents determine the equilibrium between (EZZ) and (EEZ) or (EZE) conformers. 相似文献
44.
45.
Bromberg L Temchenko M Alakhov V Hatton TA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1590-1598
Spherical particles of 50-100 mum size composed of poly(acrylic acid) networks covalently bonded to Pluronic polyether copolymers were tested for swelling in aqueous media. The microgels were cross-linked either by permanent ethylene glycol dimethacrylate (EGDMA) cross-links alone or by EDGMA together with reversible disulfide or biodegradable azoaromatic cross-links. Optimum conditions for a rapid, diffusion-limited swelling of the pH- and temperature-sensitive microgels with nondegradable cross-links were found. The microgels cross-linked by disulfide groups and equilibrium-swollen in the buffer solution exhibited degradation-limited kinetics of swelling under physiological conditions, with a first-order reaction constant, k(1), linearly proportional to the concentration of reducing agents such as dithiotreitol and tris(2-carboxyethyl)phosphine (TCEP). A severalfold faster swelling in the presence of more powerful reducing agent, TCEP, was observed, indicating the chemical specificity of the microgel swelling. The reoxidation of the thiol groups into disulfide cross-links by sodium hypochlorite led to the restoration of the microgels' diameter measured prior to the reduction-reoxidation cycle, which confirms the shape memory of the microgels. Enzymatically degradable azoaromatic cross-links enabled slow microgel swelling due to degradation of the cross-links by azoreductases from the rat intestinal cecum. The low rate of swelling of the Pluronic-containing microgels can enable sustained drug release in colon-specific drug delivery. 相似文献
46.
The boundary of the zone in which sputtered atoms are thermalized in the substrate–target drift space during the ion-plasma magnetron deposition of films is determined theoretically and experimentally. A comparison of the thicknesses of films deposited on the front and back sides of substrates situated at different distances from the target makes it possible to divide the flow of atoms sputtered toward substrates into direct and diffusion flows and to determine the dimensions of the spatial zone in which sputtered atoms are thermalized. The experimental data are in quantitative agreement with the results of a statistical simulation of the thermalization process of atomic particles during the ion-plasma deposition. This simulation enables optimization of the technology of defect-free growth of films with uniform thickness on substrates with complex 3D configuration. 相似文献
47.
Oleg G. Salnikov Kirill V. Kovtunov Danila A. Barskiy Valery I. Bukhtiyarov Robert Kaptein Igor V. Koptyug 《Applied magnetic resonance》2013,44(1-2):279-288
Parahydrogen-induced polarization has been successfully used for a kinetic study of propylene hydrogenation over a Pt/Al2O3 catalyst. It was shown that the reaction orders with respect to hydrogen are different for the pairwise and the non-pairwise hydrogen addition and are equal to 0.7 and 0.1, respectively. This observation of different reaction orders confirms the coexistence of different types of active sites which are responsible for the overall and the pairwise hydrogen addition to the propylene C=C double bond. Moreover, 0.7 reaction order with respect to H2 for pairwise hydrogen addition indicates that the contribution of pairwise addition depends on the concentration of molecular hydrogen. Therefore, this observation can be developed into a practical tool for producing fluids with highly polarized nuclear spins by changing the hydrogen concentration. 相似文献
48.
Vera I. Filyakova Nadezhda S. Boltacheva Marina G. Pervova Valery N. Charushin 《Mendeleev Communications》2021,31(3):388-389
- Download : Download high-res image (44KB)
- Download : Download full-size image
49.
Yubing Dong Amand Faessler Thomas Gutsche Valery E. Lyubovitskij 《Few-Body Systems》2013,54(7-10):1011-1014
The new resonances X(3872) and Λ c (2940) are considered as weakly bound states of other hadrons in a molecule scenario using phenomenological Lagrangians. 相似文献
50.