全文获取类型
收费全文 | 1166篇 |
免费 | 57篇 |
国内免费 | 1篇 |
专业分类
化学 | 938篇 |
晶体学 | 3篇 |
力学 | 10篇 |
数学 | 79篇 |
物理学 | 194篇 |
出版年
2023年 | 10篇 |
2022年 | 10篇 |
2021年 | 20篇 |
2020年 | 34篇 |
2019年 | 29篇 |
2018年 | 17篇 |
2017年 | 8篇 |
2016年 | 32篇 |
2015年 | 27篇 |
2014年 | 52篇 |
2013年 | 46篇 |
2012年 | 76篇 |
2011年 | 67篇 |
2010年 | 47篇 |
2009年 | 51篇 |
2008年 | 55篇 |
2007年 | 53篇 |
2006年 | 51篇 |
2005年 | 51篇 |
2004年 | 37篇 |
2003年 | 29篇 |
2002年 | 27篇 |
2001年 | 28篇 |
2000年 | 19篇 |
1999年 | 13篇 |
1998年 | 12篇 |
1997年 | 12篇 |
1996年 | 10篇 |
1995年 | 17篇 |
1994年 | 19篇 |
1993年 | 15篇 |
1992年 | 11篇 |
1991年 | 7篇 |
1990年 | 11篇 |
1989年 | 9篇 |
1988年 | 17篇 |
1987年 | 10篇 |
1986年 | 7篇 |
1985年 | 10篇 |
1984年 | 16篇 |
1983年 | 9篇 |
1982年 | 11篇 |
1981年 | 14篇 |
1980年 | 12篇 |
1979年 | 7篇 |
1978年 | 11篇 |
1977年 | 9篇 |
1975年 | 9篇 |
1973年 | 5篇 |
1966年 | 7篇 |
排序方式: 共有1224条查询结果,搜索用时 15 毫秒
1.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides 下载免费PDF全文
Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
2.
Tanja Vidaković-Koch Tamara Miličić Luka A. Živković Hoon Seng Chan Ulrike Krewer Menka Petkovska 《Current Opinion in Electrochemistry》2021
The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them. 相似文献
3.
4.
5.
We consider a vertex model on the simple-quartic lattice defined by line graphs on the lattice for which there is always an odd number of lines incident at a vertex. This is the odd 8-vertex model which has eight possible vertex configurations. We establish that the odd 8-vertex model is equivalent to a staggered8-vertex model. Using this equivalence we deduce the solution of the odd8-vertex model when the weights satisfy a free-fermion condition. It is found that the free-fermion model exhibits no phase transitions in the regime of positive vertex weights. We also establish the complete equivalence of the free-fermion odd 8-vertex model with the free-fermion 8-vertex model solved by Fan and Wu. Our analysis leads to several Ising model representations of thefree-fermion model with pure 2-spin interactions. 相似文献
6.
7.
Ab initio Hartree–Fock band structure and molecular calculations have been performed to study the electronic structure of LiN3 in a monoclinic C 2/m crystal structure. The total energy, band structure, density of states, and charge densities are computed. The calculated lattice energy (energy to separate the ions infinitely apart) of 8.6 eV agrees very well with 8.45 eV deduced from Madelung and London polarizability energies. The calculated split of the N 1s core bands of 5.0 eV compares favorably with the experimental X-ray photoelectron value of 4.4 eV. This good agreement is not contributed to crystalline environment effects as proposed in earlier MO studies of N where the best values obtained were 5.1, 5.8, and 6.3 eV, but to the quality of the nitrogen core basis set. The calculated valence density of states supports one of two competing interpretations that peak III observed in the X-ray photoelectron spectrum arises from contaminations or other extrinsic states. 相似文献
8.
W. Kunz J. Barthel L. Klein T. Cartailler P. Turq B. Reindl 《Journal of solution chemistry》1991,20(9):875-891
A variety of methods has been used for the study of lithium bromide solutions in acetonitrile yielding by their combination reliable information on different levels of approximation. Osmotic coefficients based on precise vapor pressure measurements are reproduced by CM (chemical model) and HNC (hypernetted chain) calculations and by BD (brownian dynamics) simulations. The results of neutron scattering experiments are treated with the help of HNC and BD methods. Hartree-Fock calculations on isolated LiBr pairs and solvated lithium ions yield reliable particle distances and reveal the geometry of the lithium solvation sphere. 相似文献
9.
Slootweg JC Vlaar MJ Vugts DJ Eichelsheim T Merhai W de Kanter FJ Schakel M Ehlers AW Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4808-4818
Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents. 相似文献
10.
The synthesis of glycopeptides carrying tumour-associated antigens is of interest for cancer diagnosis and treatment. Here, a very efficient route lo disaccharide threonine building block 8 is presented which allows the introduction of the sialyl-Tn antigen into a peptide. The syntheses of the undecapeptide and the sialyl-Tn-containing glycoundecapeptide, which are a part of the repeating unit of MUC1, were performed by solid-phase synthesis with an allylic anchor cleavable under neutral conditions. After detachment from the resin, the peptide and the glycopeptide arc completely deprotected giving the target compounds 13 and 15 , respectively. 相似文献