全文获取类型
收费全文 | 1257篇 |
免费 | 56篇 |
国内免费 | 2篇 |
专业分类
化学 | 778篇 |
晶体学 | 3篇 |
力学 | 52篇 |
数学 | 218篇 |
物理学 | 264篇 |
出版年
2023年 | 25篇 |
2022年 | 36篇 |
2021年 | 53篇 |
2020年 | 34篇 |
2019年 | 41篇 |
2018年 | 30篇 |
2017年 | 23篇 |
2016年 | 55篇 |
2015年 | 63篇 |
2014年 | 46篇 |
2013年 | 68篇 |
2012年 | 105篇 |
2011年 | 98篇 |
2010年 | 64篇 |
2009年 | 41篇 |
2008年 | 62篇 |
2007年 | 63篇 |
2006年 | 73篇 |
2005年 | 57篇 |
2004年 | 40篇 |
2003年 | 50篇 |
2002年 | 34篇 |
2001年 | 10篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 4篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 4篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 7篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1955年 | 2篇 |
1891年 | 2篇 |
排序方式: 共有1315条查询结果,搜索用时 250 毫秒
11.
Emilio San-Fabián José Pérez-Jordá Federico Moscardó 《Theoretical chemistry accounts》1990,77(3):207-212
Summary The correlation energy of two- and four-isoelectronic series, a representative example for which the existing spin-density functionals fails, is calculated using the Colle and Salvetti method, considering mono- and multideterminantal wave functions. The results are in agreement with experimental data, and show the potentiality of this method when it is applied to wave functions including the most relevant configurational features. Also, results for the ionization energies and electron affinities of first- and second-row atoms are reported. 相似文献
12.
Ilaria AdamoFabio Benedetti Federico BertiGiorgio Nardin Stefano Norbedo 《Tetrahedron letters》2003,44(51):9095-9097
4-Acyl-1H-1,2,3-triazoles are formed from diethylaluminum azide and α′-(N,N-dibenzylamino)-α,β-unsaturated ketones by [3+2] cycloaddition of azide, followed by 1,5 hydride transfer to the β carbon of the triazoline side chain and fragmentation of the tertiary amino group promoted by coordination of the latter to the Lewis acid. The structure of a triazole product is confirmed by X-ray crystallography. 相似文献
13.
Antonio Da Settimo Giampaolo Primofiore Bertacchi Maria Cristina Federico Da Settimo Anna Maria Marini 《Journal of heterocyclic chemistry》1995,32(3):941-945
The Ullmann reaction of 8-aminotheophylline or 8-aminocaffeine with 2-chlorobenzoic acid and of 8-bromotheophylline with ethyl-2-aminobenzoate afforded derivatives of three new heterocyclic systems: purino[7,8-α]quinazoline-5,9,11(6H,8H,10H)-trione, purino[8,9-b]quinazoline-2,4,11(1H,3H,5H)-trione and purino[8,7-b]quinazoline-2,4,6(1H,3H,11H)-trione, respectively. 相似文献
14.
Patrizia Ciminiello Carmela Dell'Aversano Martino Forino Federico Umberto Santelia Emmanuel N. Pitsinos 《Tetrahedron》2006,62(33):7738-7743
The analysis of a batch of toxic mussels (Mytilus galloprovincialis) from the Northern Adriatic Sea led to the isolation of a novel oxazinin, oxazinin-4. Its structure including the relative stereochemistry has been elucidated through extensive NMR analysis. A synthetic route to oxazinins has been crucial in establishing the absolute stereochemistry of oxazinin-4 and for reassigning the absolute C-2 configuration of oxazinin-1 and -2 previously isolated from toxic shellfish and stereostructurally characterized. 相似文献
15.
Federico Sánchez-Bringas Ana Irene Ramírez-Galarza 《Annals of Global Analysis and Geometry》1995,13(2):129-140
LetM be a compact orientable surface,I:M R4 an immersion of classC
r
and
a normal unitary smooth vector field. We prove that in the space of pairs (I,
) the family of pairs all whose umbilical points are Darbouxian is generic. 相似文献
16.
17.
Unrestricted Hartree-Fock calculations with large basis sets, including d-functions, and the estimation of the correlation energy, show that the potential energy surface for the Li-CO2 complex is built from the crossing of two states, each of them corresponding to a different electron arrangement. One has a strong ionic character and the other is of van der Waals type. Each portion of the energy surface presents a minimum, which is stable in respect to the dissociation limit. 相似文献
18.
Izquierdo S Rúa F Sbai A Parella T Alvarez-Larena A Branchadell V Ortuño RM 《The Journal of organic chemistry》2005,70(20):7963-7971
[Chemical reaction: See text] Several derivatives of (+)- and (-)-2-aminocyclobutane-1-carboxylic acid, 1, have been prepared through enantiodivergent synthetic sequences. The stereoselective synthesis of free amino acid (+)-1 has been achieved, and this product has been fully characterized for the first time. Stereocontrolled alternative synthetic methodologies have been developed for the preparation of bis(cyclobutane) beta-dipeptides in high yields. Among them, enantio and diastereomers have been synthesized. beta,beta- and beta,delta-Dimers resulting from the coupling of a cyclobutane residue and a linear amino acid have also been prepared. The ability of the cyclobutane ring as a structure-promoting unit both in the monomers and in the dimers has been manifested. The NMR structural study and DFT theoretical calculations evidence the formation of strong intramolecular hydrogen bonds giving rise to cis-fused [4.2.0]octane structural units that confer high rigidity on these molecules both in solution and in the gas phase. The contribution of a cis-trans conformational equilibrium derived from the rotation around the carbamate N-C(O) bond has also been observed, the trans form being the major conformer. In the solid state, this equilibrium does not exist, and moreover, intermolecular hydrogen bonds are present. 相似文献
19.
Barone V Bencini A Gatteschi D Totti F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(21):5019-5027
Density functional theory (DFT) was applied to describe the magnetic and electron-transfer properties of dinuclear systems containing the [MnO2Mn]n+ core, with n=0,1,2,3,4. The calculation of the potential energy surfaces (PESs) of the mixed-valence species (n=1,3) allowed the classification of these systems according to the extent of valence localization as Class II compounds, in the Robin-Day classification scheme. The fundamental frequencies corresponding to the asymmetric breathing vibration were also computed. 相似文献
20.
Starting from trifluoromethyl β-dicarbonyl compounds, a rare loss of CF3CO was observed in the amination reactions performed under heterogeneous conditions using NsONHCO2Et as the aminating agent and CaO or NaH as the base, while corresponding nonfluorinated β-dicarbonyl compounds under analogous conditions give non deacylated aminated compounds. This reaction can facilitate a direct synthesis of N-substituted α-amino esters or α-amino ketones. 相似文献