全文获取类型
收费全文 | 1977篇 |
免费 | 114篇 |
国内免费 | 1篇 |
专业分类
化学 | 1463篇 |
晶体学 | 7篇 |
力学 | 30篇 |
数学 | 217篇 |
物理学 | 375篇 |
出版年
2024年 | 8篇 |
2023年 | 23篇 |
2022年 | 67篇 |
2021年 | 83篇 |
2020年 | 73篇 |
2019年 | 106篇 |
2018年 | 103篇 |
2017年 | 82篇 |
2016年 | 131篇 |
2015年 | 93篇 |
2014年 | 97篇 |
2013年 | 135篇 |
2012年 | 134篇 |
2011年 | 162篇 |
2010年 | 94篇 |
2009年 | 71篇 |
2008年 | 110篇 |
2007年 | 101篇 |
2006年 | 104篇 |
2005年 | 85篇 |
2004年 | 59篇 |
2003年 | 49篇 |
2002年 | 43篇 |
2001年 | 17篇 |
2000年 | 14篇 |
1999年 | 12篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1990年 | 2篇 |
1988年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有2092条查询结果,搜索用时 0 毫秒
91.
Elena A. Shalamova Yeosan Lee Garam Chung Artem N. Semakin Jinho Oh Alexey Yu. Sukhorukov Dmitry E. Arkhipov Sema L. Ioffe Sergey E. Semenov 《Tetrahedron letters》2014
A general strategy for the assembly of previously unknown tris(β,β,γ-oximinoalkyl)amines from aliphatic nitro compounds and methyl vinyl ketone is described. The strategy involves N,N-bis(siloxy)enamines as key intermediates. The latter are accessible by double silylation of alkylnitro compounds. Nickel(II) and copper(II) complexes of tris(β,β,γ-oximinoalkyl)amines are prepared and structurally characterized. 相似文献
92.
Yury Kostyukevich Alexey Kononikhin Alexander Zherebker Igor Popov Irina Perminova Eugene Nikolaev 《Analytical and bioanalytical chemistry》2014,406(26):6655-6664
We report a simple approach for enumeration of non-labile oxygen atoms in individual molecules of dissolved organic matter (DOM), using acid-catalyzed 16O/18O exchange and ultrahigh-resolution Fourier-transform ion-cyclotron-resonance mass spectrometry (FTICR-MS). We found that by dissolving DOM in H2 18O at 95 °C for 20 days it is possible to replace all oxygen atoms of DOM molecules (excluding oxygen from ether groups) with 18O. The number of exchanges in each molecule can be determined using high-resolution FTICR. Using the proposed method we identified the number of non-labile oxygen atoms in 231 molecules composing DOM. Also, using a previously developed hydrogen–deuterium (H/D)-exchange approach we identified the number of labile hydrogen atoms in 450 individual molecular formulas. In addition, we observed that several backbone hydrogen atoms can be exchanged for deuterium under acidic conditions. The method can be used for structural and chemical characterization of individual DOM molecules, comparing different DOM samples, and investigation of biological pathways of DOM in the environment. 相似文献
93.
94.
In Shutov et al. (Comput Methods Appl Mech Eng 265:213–225, 2013), the numerical time integration of a famous large strain model of Maxwell fluid type has been considered. The underlying model is based on the multiplicative decomposition of the deformation gradient and includes a Neo-Hookean hyperelasticity relation as well as an incompressible viscous flow rule. Shutov et al. presented a time stepping algorithm for implicit time integration of the inelastic flow rule, which is based on Euler backward time discretisation, prevents error accumulation and is iteration free. In this contribution, the basic idea of the this approach is applied to more general models of multiplicative viscoelasticity. Here, extended hyperelastic relations including general functions of the first principal invariant of deformation tensors are regarded. An efficient time stepping algorithm is derived, where only one scalar equation for one scalar unknown has to be solved within every time step. The approach is applied to a specific viscoelastic model. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
95.
The Prandtl number is evaluated for the three-dimensional hard-sphere and one-component plasma fluids, from the dilute weakly coupled regime up to a dense strongly coupled regime near the fluid-solid phase transition. In both cases, numerical values of order unity are obtained. The Prandtl number increases on approaching the freezing point, where it reaches a quasi-universal value for simple dielectric fluids of about ≃1.7. Relations to two-dimensional fluids are briefly discussed. 相似文献
96.
Maxim A. Gorlach Mingzhao Song Alexey P. Slobozhanyuk Andrey A. Bogdanov Pavel A. Belov 《固体物理学:研究快报》2016,10(12):900-904
Employing nonlocal homogenization approach, we investigate the properties of a metamaterial consisting of parallel metallic wires with dielectric coating. We demonstrate that manipulation of dielectric contrast between wire dielectric shell and host material at fixed frequency results in dynamic switching of metamaterial dispersion regime from elliptic to the hyperbolic one, i.e. the topological transition takes place. It is proved that such transition can be induced by the variation of the metamaterial temperature. Our findings thus pave a way to the implementation of a tunable ‘elliptic‐hyperbolic’ metamaterial. 相似文献
97.
The currently operating X-ray imaging observatories provide us with an exquisitely detailed view of the Megaparsec-scale plasma atmospheres in nearby galaxy clusters. At z<0.05, the Chandra 's 1″ angular resolution corresponds to linear resolution of less than a kiloparsec, which is smaller than some interesting linear scales in the intracluster plasma. This enables us to study the previously unseen hydrodynamic phenomena in clusters: classic bow shocks driven by the infalling subclusters, and the unanticipated “cold fronts,” or sharp contact discontinuities between regions of gas with different entropies. The ubiquitous cold fronts are found in mergers as well as around the central density peaks in “relaxed” clusters. They are caused by motion of cool, dense gas clouds in the ambient higher-entropy gas. These clouds are either remnants of the infalling subclusters, or the displaced gas from the cluster's own cool cores. 相似文献
98.
Pyranoside‐into‐Furanoside Rearrangement: New Reaction in Carbohydrate Chemistry and Its Application in Oligosaccharide Synthesis 下载免费PDF全文
Dr. Vadim B. Krylov Dmitry A. Argunov Dmitry Z. Vinnitskiy Stella A. Verkhnyatskaya Dr. Alexey G. Gerbst Dr. Nadezhda E. Ustyuzhanina Dr. Andrey S. Dmitrenok Prof. Dr. Johannes Huebner Prof. Dr. Otto Holst Prof. Dr. Hans‐Christian Siebert Prof. Dr. Nikolay E. Nifantiev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(50):16516-16522
Great interest in natural furanoside‐containing compounds has challenged the development of preparative methods for their synthesis. Herein a novel reaction in carbohydrate chemistry, namely a pyranoside‐into‐furanoside (PIF) rearrangement permitting the transformation of selectively O‐substituted pyranosides into the corresponding furanosides is reported. The discovered process includes acid‐promoted sulfation accompanied by rearrangement of the pyranoside ring into a furanoside ring followed by solvolytic O‐desulfation. This process, which has no analogy in organic chemistry, was shown to be a very useful tool for the synthesis of furanoside‐containing complex oligosaccharides, which was demonstrated by synthesizing disaccharide derivatives α‐D ‐Galp‐(1→3)‐β‐D ‐ Galf ‐OPr, 3‐O‐s ‐lactyl‐β‐D ‐ Galf ‐(1→3)‐β‐D ‐Glcp‐OPr, and α‐L ‐ Fucf ‐(1→4)‐β‐D ‐GlcpA‐OPr related to polysaccharides from the bacteria Klebsiella pneumoniae and Enterococcus faecalis and the brown seaweed Chordaria flagelliformis. 相似文献
99.
Transalkylation of Higher Trifluoromethylated Fullerenes with C70: A Pathway to New Addition Patterns of C70(CF3)8 下载免费PDF全文
Nikita M. Belov Marina G. Apenova Alexey V. Rybalchenko Eugenia V. Borkovskaya Dr. Natalia S. Lukonina Dr. Alexey A. Goryunkov Dr. Ilya N. Ioffe Prof. Dr. Sergey I. Troyanov Prof. Dr. Lev N. Sidorov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1126-1133
We report three new isomers of C70(CF3)8, structurally related to p7mp‐C70(CF3)10, that are inaccessible by direct trifluoromethylation, but can be easily identified among the products of the transalkylation of higher trifluoromethylfullerenes with C70. The reported compounds are characterized by UV/Vis, 1 D and 2 D COSY 19F NMR spectroscopy, and DFT calculations. A rather unusual addition pattern is observed in p6,i‐C70(CF3)8 in which one addend is attached remotely from the others; polarization of the adjacent unsaturated bonds by the addend makes the molecule readily oxidizable. 相似文献
100.
Martin Heise Bertold Rasche Dr. Anna Isaeva Dr. Alexey I. Baranov Prof. Dr. Michael Ruck Konrad Schäfer Prof. Dr. Rainer Pöttgen Jens‐Peter Eufinger Prof. Dr. Jürgen Janek 《Angewandte Chemie (International ed. in English)》2014,53(28):7344-7348
Nanoparticles of Bi3Ir, obtained from a microwave‐assisted polyol process, activate molecular oxygen from air at room temperature and reversibly intercalate it as oxide ions. The closely related structures of Bi3Ir and Bi3IrOx (x≤2) were investigated by X‐ray diffraction, electron microscopy, and quantum‐chemical modeling. In the topochemically formed metallic suboxide, the intermetallic building units are fully preserved. Time‐ and temperature‐dependent monitoring of the oxygen uptake in an oxygen‐filled chamber shows that the activation energy for oxide diffusion (84 meV) is one order of magnitude smaller than that in any known material. Bi3IrOx is the first metallic oxide ion conductor and also the first that operates at room temperature. 相似文献