全文获取类型
收费全文 | 507篇 |
免费 | 26篇 |
国内免费 | 1篇 |
专业分类
化学 | 326篇 |
晶体学 | 2篇 |
力学 | 16篇 |
数学 | 94篇 |
物理学 | 96篇 |
出版年
2022年 | 4篇 |
2021年 | 13篇 |
2020年 | 7篇 |
2019年 | 15篇 |
2018年 | 6篇 |
2017年 | 6篇 |
2016年 | 13篇 |
2015年 | 17篇 |
2014年 | 17篇 |
2013年 | 28篇 |
2012年 | 39篇 |
2011年 | 43篇 |
2010年 | 26篇 |
2009年 | 19篇 |
2008年 | 27篇 |
2007年 | 36篇 |
2006年 | 24篇 |
2005年 | 31篇 |
2004年 | 23篇 |
2003年 | 13篇 |
2002年 | 18篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1984年 | 4篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1977年 | 3篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1970年 | 3篇 |
1966年 | 2篇 |
1923年 | 2篇 |
1913年 | 2篇 |
排序方式: 共有534条查询结果,搜索用时 203 毫秒
141.
Cong X Czerwieniec G McJimpsey E Ahn S Troy FA Lebrilla CB 《Journal of the American Society for Mass Spectrometry》2006,17(3):442-452
Gas-phase zwitterionic amino acids were formed in complexes of underivatized beta-cyclodextrin through reactions with a neutral base, n-propylamine. The reaction was performed in the analyzer cell of an electrospray ionization-Fourier transform mass spectrometer. Most of the natural amino acids were studied with three cyclodextrin hosts including alpha-, beta-, and gamma-cyclodextrin to understand better the structural features that lead to the stabilization of the zwitterionic complexes. Molecular dynamics calculations were performed to provide insight into the structural features of the complexes. The rate constants of the reactions were obtained through kinetic plots. Examination of both L- and D-enantiomers of the amino acid showed that the reaction was enantioselective. The reaction was then employed to analyze mixtures of Glu enantiomers naturally occurring in the bacteria Bacillus licheniformis. 相似文献
142.
A novel potential ligand has been designed where two beta-dialdimine units are linked by a xanthene backbone (H2Xanthdim). The synthesis proceeds via a double vinamidinium salt and the products of its hydrolysis (containing eneamine/malonaldehyde units), which were converted into H2Xanthdim via a reaction with 2,3-dimethylaniline. The reaction of H2Xanthdim with n-butyllithium yields ((Et2O)Li)2Xanthdim, which was isolated and crystallized. The crystal structures of both H2Xanthdim and its lithium salt are discussed. 相似文献
143.
Goettmann F Fischer A Antonietti M Thomas A 《Chemical communications (Cambridge, England)》2006,(43):4530-4532
The use of mesoporous graphitic C3N4 for the activation of benzene permitted to perform more sustainable Friedel-Crafts reactions by allowing to directly use carboxylic acids, alcohols and even quaternary ammoniums or urea as electrophiles. 相似文献
144.
Frederic Dorn 《Discrete Applied Mathematics》2010,158(7):800-808
We study some structural properties for tree-decompositions of 2-connected planar graphs that we use to improve upon the runtime of tree-decomposition based dynamic programming approaches for several NP-hard planar graph problems. E.g., we derive the fastest algorithm for Planar Dominating Set of runtime 3tw⋅nO(1), when we take the width tw of a given tree-decomposition as the measure for the exponential worst case behavior. We also introduce a tree-decomposition based approach to solve non-local problems efficiently, such as Planar Hamiltonian Cycle in runtime 6tw⋅nO(1). From any input tree-decomposition of a 2-connected planar graph, one computes in time O(nm) a tree-decomposition with geometric properties, which decomposes the plane into disks, and where the graph separators form Jordan curves in the plane. 相似文献
145.
146.
The Strategic Petroleum Reserve has not been used effectively to manage the consequences of oil shocks in the United States. The main reason is that political decision makers tend to hoard the reserves during crises and bureaucratic processes delay the sale of the reserves. Also, the enabling legislation focused on ameliorating shortages whereas disruptions result price spikes rather than shortages. We develop a Markov game of the buildup and drawdown of the reserve in which a public player aims to maximize consumer welfare at the same time private holders of inventory maximize their profit. The methodological contribution in this paper is the development of financial options to implement the public player’s optimal policy. We use the solution of this game to calculate the number and value of options necessary for the private marketplace to trigger the optimal buildup and drawdown of the reserve. 相似文献
147.
Poineau F Johnstone EV Weck PF Kim E Forster PM Scott BL Sattelberger AP Czerwinski KR 《Journal of the American Chemical Society》2010,132(45):15864-15865
Technetium trichloride has been synthesized by reaction of Tc(2)(O(2)CCH(3))(4)Cl(2) with HCl(g) at 300 °C. The mechanism of formation mimics the one described earlier in the literature for rhenium. Tc(2)(O(2)CCH(3))(2)Cl(4) [P1?; a = 6.0303(12) ?, b = 6.5098(13) ?, c = 8.3072(16) ?, α = 112.082(2)°, β = 96.667(3)°, γ = 108.792(3)°; Tc-Tc = 2.150(1) ?] is formed as an intermediate in the reaction at 100 °C. Technetium trichloride is formed above 250 °C and is isostructural with its rhenium homologue. The structure consists of Tc(3)Cl(9) clusters [R3?m; a = b = 10.1035(19) ?, c = 20.120(8) ?], and the Tc-Tc separation is 2.444(1) ?. Calculations on TcX(3) (X = Cl, Br) have confirmed the stability of TcCl(3) and suggest the existence of a polymorph of TcBr(3) with the ReBr(3) structure. 相似文献
148.
Caralp F Forst W Hénon E Bergeat A Bohr F 《Physical chemistry chemical physics : PCCP》2006,8(9):1072-1078
Based on recent detailed quantum mechanical computations of the mechanism of the title reaction and, this paper presents kinetics analysis of the overall rate constant and its temperature dependence, for which ample experimental data are available for comparison. The analysis confirms that the principal channel is the formation of acetonyl radical + H(2)O, while the channel leading to acetic acid is of negligible importance. It is shown that the unusual temperature dependence of the overall rate constant, as observed experimentally, is well accounted for by standard RRKM treatment that includes tunneling. This treatment is applied at the microcanonical level, with chemically activated distribution of entrance species, i.e. using a stationary rather than a thermal distribution that incorporates collisional energy transfer and competition between the redissociation and exit channel. A similar procedure is applied to the isotopic reaction acetone-d6 + OH with equally satisfying results, so that the experimental temperature dependence of the KIE (kinetic isotope effect) is perfectly reproduced. This very good agreement between calculation and experiment is obtained without any fitting to experimental values and without any adjustment of the parameters of calculation. 相似文献
149.
The Michael reaction between methyl 1-oxoindan-2-carboxylate and methyl vinyl ketone was achieved successfully by pumping solutions of the reactants in toluene through a fluid bed of Amberlyst A21 at 50 degrees C. The use of a fluid bed reactor is attractive as it allows gel-type beads, i.e. the type of bead used in most studies of polymer-supported (PS) organic reactions, to be used satisfactorily in a flow system. When polymer-supported cinchonidine was used in place of Amberlyst A21, the Michael product was obtained in high yield with an enantiomeric excess (ee) of 51%. This % ee is comparable to that achieved when the reaction was catalysed by cinchonidine itself. 相似文献
150.