全文获取类型
收费全文 | 1032篇 |
免费 | 43篇 |
国内免费 | 7篇 |
专业分类
化学 | 722篇 |
力学 | 27篇 |
数学 | 168篇 |
物理学 | 165篇 |
出版年
2023年 | 19篇 |
2022年 | 9篇 |
2021年 | 34篇 |
2020年 | 25篇 |
2019年 | 29篇 |
2018年 | 11篇 |
2017年 | 15篇 |
2016年 | 40篇 |
2015年 | 40篇 |
2014年 | 45篇 |
2013年 | 68篇 |
2012年 | 67篇 |
2011年 | 69篇 |
2010年 | 39篇 |
2009年 | 45篇 |
2008年 | 41篇 |
2007年 | 55篇 |
2006年 | 41篇 |
2005年 | 47篇 |
2004年 | 39篇 |
2003年 | 27篇 |
2002年 | 28篇 |
2001年 | 13篇 |
2000年 | 3篇 |
1999年 | 18篇 |
1998年 | 10篇 |
1997年 | 11篇 |
1996年 | 15篇 |
1995年 | 10篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 4篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 13篇 |
1985年 | 9篇 |
1984年 | 3篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1980年 | 10篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 7篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1972年 | 6篇 |
1971年 | 5篇 |
1967年 | 6篇 |
1966年 | 7篇 |
排序方式: 共有1082条查询结果,搜索用时 0 毫秒
11.
Ksenia Shilyaeva Nils Elander Evgeny Yarevsky 《International journal of quantum chemistry》2007,107(6):1301-1315
Peaks in collision cross sections are often interpreted as resonances. The complex dilation method, as well as other methods relying on analytic continuation of the scattering formalism, can be used to clarify whether these structures are true resonances in the sense that they are poles of the S‐matrix and the associated Green function. The performance of the Mittag–Leffler expansion and T‐matrix Green function expansion methods are formally and computationally compared. The two methods are applied to two model potentials. Eigenenergies, s‐wave residues, and cross sections are computed with both methods. The resonance contributions to the cross sections are further analyzed by removing the residue contributions from the Mittag–Leffler and Green function expansion sums, respectively. It is suggested that the contribution of a resonance to a cross section should be defined through its S‐matrix residue. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
12.
We have calculated the self-consistent Green's function for a number of atoms and diatomic molecules. This Green's function is obtained from a conserving self-energy approximation, which implies that the observables calculated from the Green's functions agree with the macroscopic conservation laws for particle number, momentum, and energy. As a further consequence, the kinetic and potential energies agree with the virial theorem, and the many possible methods for calculating the total energy all give the same result. In these calculations we use the finite temperature formalism and calculate the Green's function on the imaginary time axis. This allows for a simple extension to nonequilibrium systems. We have compared the energies from self-consistent Green's functions to those of nonselfconsistent schemes and also calculated ionization potentials from the Green's functions by using the extended Koopmans' theorem. 相似文献
13.
George N Pick H Vogel H Johnsson N Johnsson K 《Journal of the American Chemical Society》2004,126(29):8896-8897
The specific and covalent labeling of fusion proteins with synthetic molecules opens up new ways to study protein function in the living cell. Here we present a novel method that allows for the specific and exclusive extracellular labeling of proteins on the surfaces of live cells with a large variety of synthetic molecules including fluorophores, protein ligands, or quantum dots. The approach is based on the specific labeling of fusion proteins of acyl carrier protein with synthetic molecules through post-translational modification catalyzed by phosphopantetheine transferase. The specificity and versatility of the labeling should allow it to become an important tool for studying and manipulating cell surface proteins and for complementing existing approaches in cell surface engineering. 相似文献
14.
Bihlmeier A Gonsior M Raabe I Trapp N Krossing I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5041-5051
The unexpected but facile preparation of the silver salt of the least coordinating [(RO)3Al‐F‐Al(OR)3]? anion (R=C(CF3)3) by reaction of Ag[Al(OR)4] with one equivalent of PCl3 is described. The mechanism of the formation of Ag[(RO)3Al‐F‐Al(OR)3] is explained based on the available experimental data as well as on quantum chemical calculations with the inclusion of entropy and COSMO solvation enthalpies. The crystal structures of (RO)3Al←OC4H8, Cs+[(RO)2(Me)Al‐F‐Al(Me)(OR)2]?, Ag(CH2Cl2)3+[(RO)3Al‐F‐Al(OR)3]? and Ag(η2‐P4)2+[(RO)3Al‐F‐Al(OR)3]? are described. From the collected data it will be shown that the [(RO)3Al‐F‐Al(OR)3]? anion is the least coordinating anion currently known. With respect to the fluoride ion affinity of two parent Lewis acids Al(OR)3 of 685 kJ mol?1, the ligand affinity (441 kJ mol?1), the proton and copper decomposition reactions (?983 and ?297 kJ mol?1) as well as HOMO level and HOMO–LUMO gap and in comparison with [Sb4F21]?, [Sb(OTeF5)6]?, [Al(OR)4]? as well as [B(RF)4]? (RF=CF3 or C6F5) the [(RO)3Al‐F‐Al(OR)3]? anion is among the best weakly coordinating anions (WCAs) according to each value. In contrast to most of the other cited anions, the [(RO)3Al‐F‐Al(OR)3] anion is available by a simple preparation in conventional inorganic laboratories. The least coordinating character of this anion was employed to clarify the question of the ground state geometry of the Ag(η2‐P4)2+ cation (D2h, D2 or D2d?). In agreement with computational data and NMR spectra it could be shown that the rotation along the Ag‐(P‐P‐centroid) vector has no barrier and that the structure adopted in the solid state depends on packing effects which lead to an almost D2h symmetric Ag(η2‐P4)2+ cation (0 to 10.6° torsion) for the more symmetrical [Al(OR)4]? anion, but to a D2 symmetric Ag(η2‐P4)2+ cation with a 44° twist angle of the two AgP2 planes for the less symmetrical [(RO)3Al‐F‐Al(OR)3]? anion. This implies that silver back bonding, suggested by quantum chemical population analyses to be of importance, is only weak. 相似文献
15.
Moses Salci Evgeny Yarevsky Sergey B. Levin Nils Elander 《International journal of quantum chemistry》2007,107(2):464-468
A three‐dimensional finite element method is applied to the ground states of the symmetric and asymmetric atomic helium trimers 4He3 and 4He2–3He. Three different He–He interaction potentials of hard‐core nature were studied. Two extrapolation procedures based on the convergence properties of the finite element method are investigated. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
16.
Christine N. Morrison Kathleen E. Prosser Ryjul W. Stokes Anna Cordes Nils Metzler-Nolte Seth M. Cohen 《Chemical science》2022,13(32):9450
Correction for ‘Expanding medicinal chemistry into 3D space: metallofragments as 3D scaffolds for fragment-based drug discovery’ by Christine N. Morrison et al., Chem. Sci., 2020, 11, 1216–1225, https://doi.org/10.1039/C9SC05586J.The authors regret that in the original article, inhibitory values reported for some metallofragments were incorrect. Unfortunately, DMSO stock solutions of reportedly active ferrocene-based metallofragments were found to decompose in the presence of light, which resulted in inaccurate inhibition values. The authors maintain that the core conclusions of the paper are accurate and the utility of three-dimensional metal complexes for fragment-based drug discovery has merit.In the original article, ‘class A’ metallofragments are comprised of ferrocene derivatives (Fig. 1). Some of these ferrocene fragments (specifically those containing carbonyl groups) are reported as broadly inhibiting several protein targets. It was noted in our original report that the ferrocene scaffold was likely promiscuous due to its lipophilicity and potential redox activity, but that it might still serve as a useful metallofragment for fragment-based drug discovery (FBDD) campaigns. However, re-evaluation of these compounds against the influenza endonuclease (PAN) failed to reproduce our original inhibition results for the class A metallofragments using freshly prepared stocks, indicating a problem with the materials used in the original study.Open in a separate windowFig. 1Chemical structures of class A metallofragments.Several compounds from class A were originally reported as having near complete (100%) inhibition against PAN endonuclease at an inhibitor concentration of 200 μM (and2).2). However, when re-evaluated under identical conditions, using freshly prepared DMSO stock solutions, inhibition was only observed with one fragment of this class (A22, Fig. 1), with the previously reported highly active fragments (A4, A7–A21, Compound A1 A2 A3 A4 A5 A7 A8 A9 A10 A11 Reported 12 ± 6 <1 <1 45 ± 14 8 ± 7 103 ± 5 103 ± 4 53 ± 5 46 ± 7 90 ± 5 Corrected 3 ± 10 n.d. 18 ± 3 6 ± 3 21 ± 5 9 ± 3 10 ± 5 4 ± 2 16 ± 4 10 ± 7