全文获取类型
收费全文 | 887篇 |
免费 | 62篇 |
专业分类
化学 | 769篇 |
晶体学 | 6篇 |
力学 | 11篇 |
数学 | 65篇 |
物理学 | 98篇 |
出版年
2023年 | 5篇 |
2022年 | 7篇 |
2021年 | 15篇 |
2020年 | 19篇 |
2019年 | 22篇 |
2018年 | 5篇 |
2017年 | 3篇 |
2016年 | 36篇 |
2015年 | 25篇 |
2014年 | 36篇 |
2013年 | 43篇 |
2012年 | 53篇 |
2011年 | 80篇 |
2010年 | 34篇 |
2009年 | 38篇 |
2008年 | 59篇 |
2007年 | 62篇 |
2006年 | 66篇 |
2005年 | 63篇 |
2004年 | 40篇 |
2003年 | 33篇 |
2002年 | 34篇 |
2001年 | 15篇 |
2000年 | 10篇 |
1999年 | 9篇 |
1998年 | 6篇 |
1997年 | 12篇 |
1996年 | 15篇 |
1995年 | 6篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 8篇 |
1991年 | 7篇 |
1990年 | 10篇 |
1989年 | 7篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1891年 | 1篇 |
1885年 | 1篇 |
1866年 | 2篇 |
排序方式: 共有949条查询结果,搜索用时 15 毫秒
61.
[reaction: see text] An unprecedented endo-selective and regioselective intermolecular Pauson-Khand reaction takes place when heterobimetallic (Mo-Co) complexes derived from N-(2-alkynoyl)oxazolidinones or sultams are heated in the presence of norbornadiene. 相似文献
62.
63.
Abstract— Irradiation of Haemophilus influenzae transforming DNA with 313 nm radiation in the presence of acetone leads to inactivation of transforming activity. Some of the lesions produced are substrate for photoreactivating enzyme and the dark-repair mechanism. In addition, other lesions are produced which, if their production is not prevented by the presence of EDTA during irradiation, render the DNA less photoreactivable. The possibility is discussed that, among others, single-strand breaks are responsible for this loss in photoreactivability. 相似文献
64.
The energy barriers for the addition to ethylene of a series of carbenes have been calculated at an ab initio level. using the STO-3G and 3-21G basis sets. It is shown that the usual extrapolation of experiment results, which predicts that the reactivity of carbenes decreases when increasing its nucleophilic character, is not valid. 相似文献
65.
66.
67.
Single and double metallic layer-containing ruthenium dendrimers. Synthesis and catalytic properties
Angurell I Muller G Rocamora M Rossell O Seco M 《Dalton transactions (Cambridge, England : 2003)》2004,(16):2450-2457
The reaction of a series of phosphanyl-terminated carbosilane dendrimers displaying only one phosphorus ligand per arm with [RuCl(2)(p-cymene)](2) resulted in the grafting of RuCl(p-cymene) moieties on the periphery of the dendrimer. In these species, the chloride ligand is easily displaced by the organic bases pyridine, 4-cyanopyridine and 4,4[prime or minute]-bipyridine to afford new cationic metallodendrimers. NMR studies have confirmed the chirality of the ruthenium centre. The species containing 4,4[prime or minute]-bipyridine reacts through the uncoordinated pyridyl nitrogen with a new equivalent of [RuCl(2)(p-cymene)](2) or [RhCl(CO)(2)](2) to lead to homo- or hetero-bimetallic layer-containing dendrimeric systems. The ruthenodendrimers were tested as catalysts in the transfer hydrogenation of cyclohexanone by propan-2-ol and their activity compared with that of some analogous mononuclear ruthenium(ii) complexes. 相似文献
68.
To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order M?ller-Plesset perturbation theory, fourth-order M?ller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values. 相似文献
69.
Ganzález-Lafont A Moreno M Lluch JM 《Journal of the American Chemical Society》2004,126(40):13089-13094
Variational transition state theory has been used to calculate the kinetic isotope effects affecting product ratios in the reaction between (1)O(2) and d(6)-tetramethylethylene. The minimum energy path on the potential energy surface for this process reaches a valley-ridge inflection point and then bifurcates leading to the two final products. Using canonical variational transition state theory, two distinct dynamical bottlenecks were located corresponding to the H- and the D-abstraction, respectively. The calculated KIE at 263 K turns out to be 1.126. Analogously, a H/T KIE of 1.17 at the same temperature has been found for the reaction of (1)O(2) with the tritiated derivative of tetramethylethylene. 相似文献
70.
Angurell I Martínez-Ruiz I Rossell O Seco M Gómez-Sal P Martin A 《Chemical communications (Cambridge, England)》2004,(15):1712-1713
Tri(N-pyrrolyl)phosphine reacted with the sigma/pi complex [Pd(mu-Cl)(COD-MeO)]2 to give the octa-cycle [Pd(mu-Cl)[P(pyrl)3]]8 containing four Pd(I)-Pd(I) unbridged bonds. 相似文献