全文获取类型
收费全文 | 1297篇 |
免费 | 33篇 |
国内免费 | 5篇 |
专业分类
化学 | 1002篇 |
晶体学 | 9篇 |
力学 | 25篇 |
数学 | 125篇 |
物理学 | 174篇 |
出版年
2023年 | 11篇 |
2021年 | 27篇 |
2020年 | 30篇 |
2019年 | 15篇 |
2018年 | 12篇 |
2017年 | 17篇 |
2016年 | 35篇 |
2015年 | 23篇 |
2014年 | 24篇 |
2013年 | 70篇 |
2012年 | 72篇 |
2011年 | 75篇 |
2010年 | 45篇 |
2009年 | 33篇 |
2008年 | 44篇 |
2007年 | 66篇 |
2006年 | 62篇 |
2005年 | 48篇 |
2004年 | 31篇 |
2003年 | 28篇 |
2002年 | 31篇 |
2001年 | 13篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1996年 | 10篇 |
1995年 | 10篇 |
1994年 | 13篇 |
1993年 | 11篇 |
1991年 | 11篇 |
1990年 | 20篇 |
1989年 | 18篇 |
1988年 | 10篇 |
1987年 | 15篇 |
1985年 | 24篇 |
1984年 | 24篇 |
1983年 | 15篇 |
1982年 | 21篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1979年 | 20篇 |
1978年 | 23篇 |
1977年 | 15篇 |
1976年 | 18篇 |
1975年 | 14篇 |
1974年 | 11篇 |
1973年 | 20篇 |
1967年 | 8篇 |
1957年 | 8篇 |
1956年 | 28篇 |
1955年 | 18篇 |
排序方式: 共有1335条查询结果,搜索用时 15 毫秒
1.
2.
Summary Experiments and simulations prove that correlation chromatography can greatly reduce the disadvantage of a non-linear response of the chromatographic column. A factor that has been accepted as being an important source of error in correlation or multiplex chromatography, has been shown not to be. Separations affected, improve dramatically when correlation chromatography is used, and a substantial amount of correlation noise only arises when there is a large difference in separation between a conventional chromatogram and a correlogram.A model has been developed for simulating these nonlinearities. It is shown that, especially for correlation chromatography, the simulation results match the practical measurements very well. 相似文献
3.
Pascher W. Den Besten J. H. Caprioli D. Leijtens X. Smit M. van Dijk R. 《Optical and Quantum Electronics》2003,35(4-5):453-464
Based on a rigorous vectorial analysis, a fast travelling-wave Mach–Zehnder modulator is modelled and designed. The cross-section of the semiconductor layer stack and the lossy electrodes are carefully modelled using the method of lines in order to investigate propagation characteristics, velocity and losses. This yields an accurate microwave and optical field distribution to explain the behaviour of the component. In order to enhance the modulation efficiency, design curves are derived and the cross-sectional dimensions for minimum microwave loss are determined. The loss of the optimized modulator agrees very well with small-signal measurements up to 40 GHz and HFSS simulations. The layerstack of the fabricated device is suitable for integration with InP multi-wavelength lasers. 相似文献
4.
5.
Enrique Saldívar‐Guerra Jos Bonilla Gregorio Zacahua Martha Albores‐Velasco 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):6962-6979
Mechanisms and simulations of the induction period and the initial polymerization stages in the nitroxide‐mediated autopolymerization of styrene are discussed. At 120–125 °C and moderate 2,2,4,4‐tetramethyl‐1‐piperidinyloxy (TEMPO) concentrations (0.02–0.08 M), the main source of radicals is the hydrogen abstraction of the Mayo dimer by TEMPO [with the kinetic constant of hydrogen abstraction (kh)]. At higher TEMPO concentrations ([N?] > 0.1 M), this reaction is still dominant, but radical generation by the direct attack against styrene by TEMPO, with kinetic constant of addition kad, also becomes relevant. From previous experimental data and simulations, initial estimates of kh ≈ 1 and kad ≈ 6 × 10?7 L mol?1 s?1 are obtained at 125 °C. From the induction period to the polymerization regime, there is an abrupt change in the dominant mechanism generating radicals because of the sudden decrease in the nitroxide radicals. Under induction‐period conditions, the simulations confirm the validity of the quasi‐steady‐state assumption (QSSA) for the Mayo dimer in this regime; however, after the induction period, the QSSA for the dimer is not valid, and this brings into question the scientific basis of the well‐known expression kth[M]3 (where [M] is the monomer concentration and kth is the kinetic constant of autoinitiation) for the autoinitiation rate in styrene polymerization. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6962‐6979, 2006 相似文献
6.
Microchimica Acta - Mit der turbidimetrischen Strychninnitrat-Methode für Phosphorspurenbestimmung nach der Version von Hegedüs und Dvorszky kann man nur dann ausgezeichnete... 相似文献
7.
For a series of substituted arylsulfenyl chlorides the stereochemistry of AdE-reactions with a series of substituted Z- and E-β-deuterostyrenes has been elucidated. Non-stereospecific reaction was observed only for the pair 2,4-dinitrobenzenesulfenyl chloride-p-methoxystyrene; for all the other reactants the reaction proceeded in a strictly stereospecific manner. 相似文献
8.
Anton M. ter Laak Hendrik Timmerman Rob Leurs Paul H. J. Nederkoorn Martine J. Smit Gabriëlle M. Donné-Op den Kelder 《Journal of computer-aided molecular design》1995,9(4):319-330
Summary A modelling study has been carried out, investigating the binding of histamine (Hist), 2-methylhistamine (2-MeHist) and 2-phenylhistamine (2-PhHist) at two postulated agonistic binding sites on transmembrane domain 5 (TM5) of the histamine H1-receptor. For this purpose a conformational analysis study was performed on three particular residues of TM5, i.e., Lys200, Thr203 and Asn207, for which a functional role in binding has been proposed. The most favourable results were obtained for the interaction between Hist and the Lys200/Asn207 pair. Therefore, Lys200 was subsequently mutated and converted to an alanine, resulting in a 50-fold decrease of H1-receptor stimulation by histamine. Altogether, the data suggest that the Lys200/Asn207 pair is important for activation of the H1-receptor by histamine. In contrast, analogues of 2-PhHist seem to belong to a distinct subclass of histamine agonists and an alternative mode of binding is proposed in which the 2-phenyl ring binds to the same receptor location as one of the aromatic rings of classical histamine H1-antagonists. Subsequently, the binding modes of the agonists Hist, 2-MeHist and 2-PhHist and the H1-antagonist cyproheptadine were evaluated in three different seven--helical models of the H1-receptor built in homology with bacteriorhodopsin, but using three different alignments. Our findings suggest that the position of the carboxylate group of Asp116 (TM3) within the receptor pocket depends on whether an agonist or an antagonist binds to the protein; a conformational change of this aspartate residue upon agonist binding is expected to play an essential role in receptor stimulation.Abbreviations 2-MeHist
2-methylhistamine
- 2-PEA
2-pyridyl-ethylamine
- 2-PhHist
2-phenylhistamine
- CHO
Chinese hamster ovary
- Eint
interaction energy
- Estr
strain energy
- GES
global energy structure
- gpH1R
guinea pig H1-receptor
- GPCR
G-protein coupled receptor
- Hist
histamine
- N
proximal nitrogen
- N
tele nitrogen
- TM
transmembrane domain
- WT
wild type 相似文献
9.
Norman H. Tennent Sophia R. Su Craig A. Poffenberger Andrew Wojcicki 《Journal of organometallic chemistry》1975,102(4):C46-C48
The reaction of Na[η5-C5H5Fe(CO)2] with large excess of SO2 in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5). 相似文献
10.
The synthesis of squaric acid N-hydroxylamide esters 5 and amides 6 from dimethyl squarate 2a is described. These derivatives are analogues of the naturally occurring iron(III) chelator hydroxamic acid. On the basis of a comparative reactivity study, a concerted retro-Cope mechanism for the formation of the N-hydroxylamide esters 5 by reaction of dimethyl squarate with hydroxylamines is proposed. A preliminary iron(III) binding study of these hydroxamic acid analogues is presented, demonstrating binding of iron(III) to amides 6 in aqueous solutions, while the esters 5 did not show any sign of metal ion binding. 13C NMR spectroscopic data (chemical shift and spin-lattice relaxation time determination) of these and related derivatives delineate the resonance structures predominant in these molecules. The resonance structures of the derivatives rationalize their spectroscopic data, chemical reactivity, and iron(III) binding properties. Single-crystal X-ray structure analyses of squaric acid N-hydroxylamide ester 5b and squaric acid N-hydroxylamide amide 6c confirm their connectivity and provide structural evidence supporting the spectroscopically derived conclusions. The squaric acid N-hydroxylamides are potentially useful in the construction of chemosensors for iron(III). 相似文献