全文获取类型
收费全文 | 1114篇 |
免费 | 48篇 |
国内免费 | 10篇 |
专业分类
化学 | 809篇 |
晶体学 | 1篇 |
力学 | 15篇 |
数学 | 200篇 |
物理学 | 147篇 |
出版年
2023年 | 9篇 |
2022年 | 14篇 |
2021年 | 27篇 |
2020年 | 30篇 |
2019年 | 21篇 |
2018年 | 27篇 |
2017年 | 17篇 |
2016年 | 49篇 |
2015年 | 31篇 |
2014年 | 34篇 |
2013年 | 55篇 |
2012年 | 87篇 |
2011年 | 85篇 |
2010年 | 51篇 |
2009年 | 48篇 |
2008年 | 93篇 |
2007年 | 80篇 |
2006年 | 84篇 |
2005年 | 68篇 |
2004年 | 57篇 |
2003年 | 38篇 |
2002年 | 37篇 |
2001年 | 15篇 |
2000年 | 6篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 12篇 |
1996年 | 10篇 |
1995年 | 8篇 |
1994年 | 4篇 |
1993年 | 7篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有1172条查询结果,搜索用时 15 毫秒
91.
The Newman-Kwart thermal rearrangement of two 2,4-disubstituted O-arylthiocarbamates, prepared from the corresponding phenols, is reported. Clean conversion to the S-arylthiocarbamates in high yields was observed. The rearrangement appears to be facilitated by the presence of electron-withdrawing substituents in the 2- and 4-positions of the aromatic ring. 相似文献
92.
Javier A. Cabeza Prof. Ignacio del Río Prof. Enrique Pérez‐Carreño Prof. Vanessa Pruneda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(18):5425-5436
The cationic cluster complexes [Ru3(μ‐H)(μ‐κ2N,C‐L1 Me)(CO)10]+ ( 1 +; HL1 Me=N‐methylpyrazinium), [Ru3(μ‐H)(μ‐κ2N,C‐L2 Me)(CO)10]+ ( 2 +; HL2 Me=N‐methylquinoxalinium), and [Ru3(μ‐H)(μ‐κ2‐N,C‐L3 Me)(CO)10]+ ( 3 +; HL3 Me=N‐methyl‐1,5‐naphthyridinium), which contain cationic N‐heterocyclic ligands, undergo one‐electron reduction processes to become short lived, ligand‐centered, trinuclear, radical species ( 1 – 3 ) that end in the formation of an intermolecular C? C bond between the ligands of two such radicals, thus leading to neutral hexanuclear derivatives. These dimerization processes are selective, in the sense that they only occur through the exo face of the bridging ligands of trinuclear enantiomers of the same configuration, as they only afford hexanuclear dimers with rac structures (C2 symmetry). The following are the dimeric products that have been isolated by using cobaltocene as reducing agent: [Ru6(μ‐H)2{μ6‐κ4N2,C2‐(L1 Me)2}(CO)18] ( 5 ; from 1 +), [Ru6(μ‐H)2{μ6‐κ4N2,C2‐(L2 Me)2}(CO)18] ( 6 ; from 2 +), and [Ru6(μ‐H)2{μ4‐κ8N2,C6‐(L3 Me)2}(CO)18] ( 7 ; from 3 +). The structures of the final hexanuclear products depend on the N‐heterocyclic ligand attached to the starting materials. Thus, although both trinuclear subunits of 5 and 6 are face‐capped by their bridging ligands, the coordination mode of the ligand of 5 is different from that of the ligand of 6 . The trinuclear subunits of 7 are edge‐bridged by its bridging ligand. In the presence of moisture, the reduction of 3 + with cobaltocene also affords a trinuclear derivative, [Ru3(μ‐H)(μ‐κ2N,C‐L3′ Me)(CO)10] ( 8 ), whose bridging ligand (L3′ Me) results from the formal substitution of an oxygen atom for the hydrogen atom (as a proton) that in 3 + is attached to the C6 carbon atom of its heterocyclic ligand. The results have been rationalized with the help of electrochemical measurements and DFT calculations, which have also shed light on the nature of the odd‐electron species, 1 – 3 , and on the regioselectivity of their dimerization processes. It seems that the sort of coupling reactions described herein requires cationic complexes with ligand‐based LUMOs. 相似文献
93.
Krauter H Muschik CA Jensen K Wasilewski W Petersen JM Cirac JI Polzik ES 《Physical review letters》2011,107(8):080503
Entanglement is a striking feature of quantum mechanics and an essential ingredient in most applications in quantum information. Typically, coupling of a system to an environment inhibits entanglement, particularly in macroscopic systems. Here we report on an experiment where dissipation continuously generates entanglement between two macroscopic objects. This is achieved by engineering the dissipation using laser and magnetic fields, and leads to robust event-ready entanglement maintained for 0.04 s at room temperature. Our system consists of two ensembles containing about 10(12) atoms and separated by 0.5 m coupled to the environment composed of the vacuum modes of the electromagnetic field. By combining the dissipative mechanism with a continuous measurement, steady state entanglement is continuously generated and observed for up to 1 h. 相似文献
94.
95.
96.
A problem of decision making under uncertainty in which the choice must be made between two sets of alternatives instead of two single ones is considered. A number of choice rules are proposed and their main properties are investigated, focusing particularly on the generalizations of stochastic dominance and statistical preference. The particular cases where imprecision is present in the utilities or in the beliefs associated to two alternatives are considered. 相似文献
97.
Marvin J. Núñez María L. Kennedy Ignacio A. JiménezIsabel L. Bazzocchi 《Tetrahedron》2011,67(17):3030-3033
Uragogin and blepharodin were isolated from Crossopetalum uragoga and Maytenus magellanica, respectively. They represent the first examples of a triterpene-neolignan ester and a heptacyclic arylpropanoid-nor-triterpenephenol, hetero-Diels-Alder adducts built with dioxane bridges. Their proposed biosynthetic route is discussed. 相似文献
98.
We have studied the magnetic and electronic properties of double perovskites A2FeReO6 with A=Ba and Ca using ab initio methods based on density functional theory. It has been shown that when changing Ba by Ca the system undergoes a metal–insulator transition coincidentally to a structural phase transition, even if conduction band fillings are not significantly changed. Our results suggest that only considering a quite large correlation term on the Re site could explain an insulating character for Ca2FeReO6. Instead, we found that small correlations could induce a bad metallic behavior as suggested in more recent experiments. 相似文献
99.
Gabriel Chuchani Ignacio Martín Alexandra Rotinov Rosa M. Domínguez 《国际化学动力学杂志》1990,22(12):1249-1255
Elimination kinetics of 2-bromohexane and 2-bromo-4-methylpentane in the gas phase were examined over the temperature range of 310–360°C and pressure range of 46–213 torr. The reactionsin seasoned, static reaction vessels, and in the presence of the free radical inhibitor cyclohexene, are homogeneous, unimolecular, and follow first order rate laws. The overall rate coefficients are described by the following Arrhenius equations: For 2-bromohexane, log??1(s?1) = (13.08 ± 0.70) ? (185.7 ± 8.2) kJ mol?1 (2.303RT)?1; for 2-bromo-4-methylpentane, log??1(s?1) = (13.08 ± 0.33) ? (183.4 ± 3.8) kJ mol?1 (2.303RT)?1. The electron releasing effect of alkyl groups influences the overall elimination rates. The olefin products isomerize in the presence of HBr gas until an equilibrium mixture is reached. 相似文献
100.
QM/MM modeling of the hydroxylation of the androstenedione substrate catalyzed by cytochrome P450 aromatase (CYP19A1) 下载免费PDF全文
Ignacio Viciano Raquel Castillo Sergio Martí 《Journal of computational chemistry》2015,36(23):1736-1747
CYP19A1 aromatase is a member of the Cytochrome P450 family of hemeproteins, and is the enzyme responsible for the final step of the androgens conversion into the corresponding estrogens, via a three‐step oxidative process. For this reason, the inhibition of this enzyme plays an important role in the treatment of hormone‐dependent breast cancer. The first catalytic subcycle, corresponding to the hydroxilation of androstenedione, has been proposed to occur through a first hydrogen abstraction and a subsequent oxygen rebound step. In present work, we have studied the mechanism of the first catalytic subcycle by means of hybrid quantum mechanics/molecular mechanics methods. The inclusion of the protein flexibility has been achieved by means of Free Energy Perturbation techniques, giving rise to a free energy of activation for the hydrogen abstraction step of 13.5 kcal/mol. The subsequent oxygen rebound step, characterized by a small free energy barrier (1.5 kcal/mol), leads to the hydroxylated products through a highly exergonic reaction. In addition, an analysis of the primary deuterium kinetic isotopic effects, calculated for the hydrogen abstraction step, reveals values (~10) overpassing the semiclassical limit for the C? H, indicating the presence of a substantial tunnel effect. Finally, a decomposition analysis of the interaction energy for the substrate and cofactor in the active site is also discussed. According to our results, the role of the enzymatic environment consists of a transition state stabilization by means of dispersive and polarization effects. © 2015 Wiley Periodicals, Inc. 相似文献