全文获取类型
收费全文 | 436篇 |
免费 | 0篇 |
国内免费 | 4篇 |
专业分类
化学 | 265篇 |
力学 | 38篇 |
数学 | 90篇 |
物理学 | 47篇 |
出版年
2023年 | 4篇 |
2022年 | 2篇 |
2021年 | 10篇 |
2020年 | 5篇 |
2019年 | 4篇 |
2018年 | 8篇 |
2017年 | 7篇 |
2016年 | 6篇 |
2015年 | 5篇 |
2014年 | 9篇 |
2013年 | 16篇 |
2012年 | 23篇 |
2011年 | 26篇 |
2010年 | 19篇 |
2009年 | 16篇 |
2008年 | 35篇 |
2007年 | 33篇 |
2006年 | 25篇 |
2005年 | 14篇 |
2004年 | 19篇 |
2003年 | 23篇 |
2002年 | 27篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 12篇 |
1995年 | 10篇 |
1994年 | 7篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有440条查询结果,搜索用时 234 毫秒
51.
Lyskawa J Sallé M Balandier JY Le Derf F Levillain E Allain M Viel P Palacin S 《Chemical communications (Cambridge, England)》2006,(21):2233-2235
The formation of the two dimeric species [(TTF)2]+* and (TTF+*)2 can be monitored by complexation of Na+ on a calix[4]arene-TTF assembly. 相似文献
52.
Corral I Mó O Yáñez M Salpin JY Tortajada J Moran D Radom L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(26):6787-6796
The gas-phase reactions between Ca(2+) and glycine ([Ca(gly)](2+)) have been investigated through the use of mass spectrometry techniques and B3-LYP/cc-pWCVTZ density functional theory computations. The major peaks observed in the electrospray MS/MS spectrum of [Ca(gly)](2+) correspond to the formation of the [Ca,C,O(2),H](+), NH(2)CH(2) (+), CaOH(+), and NH(2)CH(2)CO(+) fragment ions, which are produced in Coulomb explosion processes. The computed potential energy surface (PES) shows that not only are these species the most stable product ions from a thermodynamic point of view, but they may be produced with barriers lower than for competing processes. Carbon monoxide is a secondary product, derived from the unimolecular decomposition of some of the primary ions formed in the Coulomb explosions. In contrast to what is found for the reactions of Ca(2+) with urea ([Ca(urea)](2+)), minimal unimolecular losses of neutral fragments are observed for the gas-phase fragmentation processes of [Ca(gly)](2+), which is readily explained in terms of the topological differences between their respective PESs. 相似文献
53.
Electronic structures of electron-rich octahedrally condensed transition-metal chalcogenide clusters
The electronic structures of some electron-rich octahedrally condensed transition-metal chalcogenide clusters are analyzed with the aid of extended Hückel and density functional molecular orbital calculations. A simple orbital approach is developed to analyze the electron counts of these clusters, which do not obey any existing electron-counting rules. Different electron counts are allowed, depending upon the nature of the metal. Optimal counts are discussed. Metal-metal bonding is generally weak in these species. Consequently, their structural arrangements are mainly governed by metal-ligand interactions. 相似文献
54.
Vega A Calvo V Spodine E Zárate A Fuenzalida V Saillard JY 《Inorganic chemistry》2002,41(13):3389-3395
The reaction of the organometallic carboxylic acid HOOCCCHCo(2)(CO)(6) with copper(II) methoxide leads to a new inorganometallic cluster; Cu(3)[mu(2)-(CCHCo(2)(CO)(6))](3). This cluster has a triangular core of copper(I) centers surrounded by three CCHCo(2)(CO)(6) fragments. The structure of the cluster has short Cu-Cu and Cu-Co distances (average 2.500 and 2.540 A, respectively). DFT calculations provide a rationalization of the peculiar bonding in this cluster. 相似文献
55.
Boutreau L Léon E Salpin JY Amekraz B Moulin C Tortajada J 《European journal of mass spectrometry (Chichester, England)》2003,9(4):377-390
The analytical distinction of the most common isomeric underivatized hexoses was investigated by means of mass spectrometry experiments. Electrospray ionization and tandem mass spectrometry were used in the analysis of silver and copper-coordinated monosaccharides (D-glucose, D-galactose, D-fructose, O-methyl-alpha-D-glucose and O-methyl-beta-D-glucose). The results show that cationization by Ag(+) allows the differentiation of the three first monosaccharides while the complexes formed by association of Cu(+) with these three monosacharides display a similar reactivity that prevents stereoisomer distinction. Unlike copper, silver adduct-ions of both alpha and beta anomeric O-methyl-D-glucoses exhibit specific decomposition patterns (i.e. a loss of methanol for the alpha-anomer and a loss of silver hydride for the beta-anomer), which allow an easy characterization. A theoretical survey of selected complexes, based on the use of DFT calculations were carried out on both anomers in order to rationalize the experimental findings. 相似文献
56.
Cador O Cattey H Halet JF Meier W Mugnier Y Wachter J Saillard JY Zouchoune B Zabel M 《Inorganic chemistry》2007,46(2):501-509
The novel cluster anion [Co(11)Te(5)(CO)15]- ([3]-) has been isolated and structurally characterized as part of the salt [Cp*(2)Nb(CO)2][3] (Cp* = C(5)Me(5)). The cobalt-centered Co10 pentagonal prism is surrounded by a shell of two mu5-Te, three mu4-Te ligands, and 15 CO groups in terminal, symmetrical, and sigma-semibridging bonding modes. The hybrid carbonyl-telluride character of the ligand shell is reflected in the solid state by a one-dimensional assembly of polyhedral prisms along a backbone of [Cp*(2)Nb(CO)2]+ cations. Electrochemical studies reveal the presence of four redox couples of [3]n (n = -1 to -5). The electronic structures of various metal-centered and empty pentagonal-prismatic (PP) M10 clusters (M = Co, Ni) are calculated and compared to those of pentagonal-antiprismatic (PA) M10 structures. Closed-shells of 152 and 156 metal valence electrons, respectively, are found to determine the electronic structures and chemical properties of these geometries. From these considerations, magnetic properties have been predicted. They have been verified for the [Co(11)Te(7)(CO)10]- cluster anion, which exhibits a singlet-triplet gap of 0.318 kcal/mol. 相似文献
57.
Trujillo C Lamsabhi AM Mó O Yáñez M Salpin JY 《Organic & biomolecular chemistry》2008,6(20):3695-3702
The structures and relative stabilities of the complexes formed by uracil and its sulfur derivatives, namely, 2-thio-, 4-thio, and 2,4-dithio-uracil when interacting with Ca(2+) in the gas phase have been analyzed by means of density functional theory (DFT) calculations carried out at the B3LYP/6-311++G(3df,2p)//B3LYP/6-31+G(d,p) level. For uracil and 2,4-dithiouracil, where the two basic sites are the same, Ca(2+) attachment to the heteroatom at position 4 is preferred. However, for the systems where both types of basic centers, a carbonyl or a thiocarbonyl group, are present, Ca(2+)-oxygen association is favored. The most stable complexes correspond to structures with Ca(2+) bridging between the heteroatom at position 2 of the 4-enol (or the 4-enethiol) tautomer and the dehydrogenated ring nitrogen, N3. The enhanced stability of these enolic forms is two-fold, on the one hand Ca(2+) interacts with two basic sites and on the other triggers a significant aromatization of the ring. Besides, Ca(2+) association has a clear catalytic effect on the tautomerization processes which connect the oxo-thione forms with the enol-enethiol tautomers. Hence, although the enol-enethiol tautomers of uracil and its thio derivatives should not be observed in the gas phase, the corresponding Ca(2+) complexes are the most stable species and should be accessible, because the tautomerization barriers are smaller than the Ca(2+) binding energies. 相似文献
58.
Jean-Yves Sanchez Fannie Alloin Cristina Iojoiu 《Journal of fluorine chemistry》2006,127(11):1471-1478
This contribution has been partly adapted from a special lecture intended to commemorate the Nobel prize, awarded one century ago, to Henri Moissan. It, is focused on fluorinated and perfluorinated molecules and macromolecules used in electrochemical energy sources, i.e. storage and conversion of energy. The latter, which figure indisputably among New Energy Technologies, include lithium batteries and fuel cells based on polymeric membranes both of which have tremendous development potential in terms of performances, safety and cost reductions. The advantages inherent in fluorine, in particular its electron-withdrawing effect and the oxidation stability that it provides to the carbon-fluorine bond, make it an asset in the search for new organic molecular and macromolecular anions with extensive delocalization of the negative charge, usable both in lithium batteries and fuel cells. As for fluorinated and perfluorinated macromolecule backbones, they are currently the reference material in fuel cell ionomeric membranes but some of them are also good candidates for use in lithium-ion batteries. This paper, far from being exhaustive, also emphasizes the economic aspects that influence material selection and also govern the future of basic research. 相似文献
59.
Henri Patin Gerard Mignani Christian Mahe Jean-Yves Le Marouille Alain Benoit Daniel Grandjean 《Journal of organometallic chemistry》1980,193(1):93-103
103Rh Chemical shifts of a variety of mono- and di-nuclear rhodium carbonyl complexes are reported together with the modifications to the probe and decoupler unit of a JEOL PS-100 PFT spectrometer which enable these 103Rh-decoupled 13C NMR measurements to be made. These data are discussed in conjunction with 13C NMR data on other rhodium carbonyls. 相似文献
60.
Functionalization at C-2 and C-5 of N-benzenesulfonyl-4-azaindole 1 was performed by lithiation reactions and original palladium-catalyzed chemistry. It led to very useful new substituted 4-azaindole derivatives in fair to high yields. 相似文献