全文获取类型
收费全文 | 464篇 |
免费 | 3篇 |
国内免费 | 1篇 |
专业分类
化学 | 266篇 |
晶体学 | 1篇 |
力学 | 17篇 |
数学 | 93篇 |
物理学 | 91篇 |
出版年
2023年 | 1篇 |
2022年 | 2篇 |
2021年 | 6篇 |
2020年 | 7篇 |
2019年 | 6篇 |
2018年 | 5篇 |
2017年 | 5篇 |
2016年 | 11篇 |
2015年 | 8篇 |
2014年 | 13篇 |
2013年 | 24篇 |
2012年 | 37篇 |
2011年 | 38篇 |
2010年 | 29篇 |
2009年 | 18篇 |
2008年 | 28篇 |
2007年 | 43篇 |
2006年 | 34篇 |
2005年 | 18篇 |
2004年 | 16篇 |
2003年 | 15篇 |
2002年 | 25篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1983年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1975年 | 1篇 |
1968年 | 1篇 |
1937年 | 3篇 |
1882年 | 1篇 |
排序方式: 共有468条查询结果,搜索用时 181 毫秒
1.
Gary W. Breton Lauren A. Hahn Kenneth L. Martin 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(9):1208-1212
Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C25H30N4O4, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl3). A tentative reaction pathway for its dissociation based on 1H NMR spectral evidence is provided. 相似文献
2.
Wen Li Edita Mjekiqi Wessel Douma Xin Wang Dr. Oksana Kavatsyuk Prof. Dr. Ronnie Hoekstra Dr. Jean-Christophe Poully Dr. Thomas Schlathölter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(70):16114-16119
Vacuum ultraviolet photoionization of a gas-phase oligonucleotide anion leads to the formation of a valence hole. This hole migrates towards an energetically favorable site where it can weaken bonds and ultimately lead to bond cleavage. We have studied Vacuum UV photoionization of deprotonated oligonucleotides containing the human telomere sequence dTTAGGG and G-quadruplex structures consisting of four dTGGGGT single strands, stabilized by NH4+ counter ions. The oligonucleotide and G-quadruplex anions were confined in a radiofrequency ion trap, interfaced with a synchrotron beamline and the photofragmentation was studied using time-of-flight mass spectrometry. Oligonucleotide 12-mers containing the 5'-TTAGGG sequence were found to predominantly break in the GGG region, whereas no selective bond cleavage region was observed for the reversed 5'-GGGATT sequence. For G-quadruplex structures, fragmentation was quenched and mostly non-dissociative single and double electron removal was observed. 相似文献
3.
Letters in Mathematical Physics - We present a new sum rule for Clebsch–Gordan coefficients using generalized characters of irreducible representations of the rotation group. The identity is... 相似文献
4.
The Ising‐Kac model is a variant of the ferromagnetic Ising model in which each spin variable interacts with all spins in a neighborhood of radius γ ? 1 for around its base point. We study the Glauber dynamics for this model on a discrete two‐dimensional torus for a system size and for an inverse temperature close to the critical value of the mean field model. We show that the suitably rescaled coarse‐grained spin field converges in distribution to the solution of a nonlinear stochastic partial differential equation. This equation is the dynamic version of the quantum field theory, which is formally given by a reaction‐diffusion equation driven by an additive space‐time white noise. It is well‐known that in two spatial dimensions such equations are distribution valued and a Wick renormalization has to be performed in order to define the nonlinear term. Formally, this renormalization corresponds to adding an infinite mass term to the equation. We show that this need for renormalization for the limiting equation is reflected in the discrete system by a shift of the critical temperature away from its mean field value.© 2016 by the authors. Communications on Pure and Applied Mathematics is published by Wiley Periodicals, Inc., on behalf of the Courant Institute of Mathematics. 相似文献
5.
Any positive matrix M partitioned in four n-by-n blocks satisfies the unitarily invariant norm inequality , where ω is the width of the numerical range of . Some related inequalities and a reverse Lidskii majorization are given. 相似文献
6.
Dr. Marwa Abdelmouleh Dr. Mathieu Lalande Edith Nicol Dr. Gilles Frison Prof. Dr. Guillaume van der Rest Dr. Jean-Christophe Poully 《Chemphyschem》2021,22(12):1243-1250
These last decades, it has been widely assumed that 18-crown-6-ether (CE) plays a spectator role during the chemical processes occurring in isolated host-guest complexes between peptides or proteins and CE after activation in mass spectrometers. Our present experimental and theoretical results challenge this hypothesis by showing that CE can abstract a proton or a protonated molecule from protonated peptides after activation by collisions in argon or electron capture/transfer. Furthermore, thanks to comparison between experimental and calculated values of collision cross-sections, we demonstrate that CE can change binding site after electron transfer. We also propose detailed mechanisms for these processes. 相似文献
7.
Dieter Schemeth Jean-Christophe Noël Thomas Jakschitz Matthias Rainer Richard Tessadri Christian W. Huck Günther K. Bonn 《Analytica chimica acta》2015
In this study we report the novel polymeric resin poly(N-vinyl imidazole/ethylene glycol dimethacrylate) for the purification and isolation of phenolic acids. The monomer to crosslinker ratio and the porogen composition were optimized for isolating phenolic acids diluted in acetonitrile at normal phase chromatography conditions, first. Acetonitrile serves as polar, aprotic solvent, dissolving phenolic acids but not interrupting interactions with the stationary phase due to the approved Hansen solubility parameters. The optimized resin demonstrated high loading capacities and adsorption abilities particularly for phenolic acids in both, acetonitrile and aqueous solutions. The adsorption behavior of aqueous standards can be attributed to ion exchange effects due to electrostatic interactions between protonated imidazole residues and deprotonated phenolic acids. Furthermore, adsorption experiments and subsequent curve fittings provide information of maximum loading capacities of single standards according to the Langmuir adsorption model. Recovery studies of the optimized polymer in the normal-phase and ion-exchange mode illustrate the powerful isolation properties for phenolic acids and are comparable or even better than typical, commercially available solid phase extraction materials. In order to prove the applicability, a highly complex extract of rosemary leaves was purified by poly(N-vinyl imidazole/ethylene glycol dimethacrylate) and the isolated compounds were identified using UHPLC–qTOF-MS. 相似文献
8.
9.
Factors affecting the dimerization of persistent nitrogen‐centered 1‐phenyl urazole radicals to tetrazanes 下载免费PDF全文
1‐Phenyl urazole radicals are persistent air‐stable nitrogen‐centered radicals that engage in an equilibrium with the corresponding N―N tetrazane dimers in solution. While the equilibrium typically weakly favors the dimer form, for some 1‐phenyl urazole radicals bearing substituents at the ortho position of the benzene ring, the equilibrium instead strongly favors the dimer form. With the recent surge of interest in the properties and potential applications of heterocyclic radicals, the factors that affect this equilibrium are important to determine. We examined the effect of the extent of ortho substitution (none, 1, or 2 substituents) on the equilibrium by experimentally using variable temperature 1H nuclear magnetic resonance and UV‐visible spectroscopy in addition to supporting computational investigations at the (U)B3LYP/6‐311G(d,p) level of theory. We confirmed that the equilibrium generally favored the dimer in all cases. However, the equilibrium was more favorable towards dimer formation for urazole radicals substituted with 1 and 2 ortho substituents on the aromatic ring. The activation enthalpies for dissociation of singly substituted dimers were greater than that for dimers without ortho substituents, but lower than that for doubly substituted dimers. The greater preference for dimer formation for the ortho‐substituted urazole radicals is attributed to a greater enthalpic advantage for N―N bond formation. This advantage may be traced to a higher concentration of spin density on the urazole unit of the radicals and a lesser deformation energy required for N―N bond formation. 相似文献
10.