全文获取类型
收费全文 | 3660篇 |
免费 | 113篇 |
国内免费 | 11篇 |
专业分类
化学 | 2771篇 |
晶体学 | 24篇 |
力学 | 83篇 |
数学 | 376篇 |
物理学 | 530篇 |
出版年
2023年 | 19篇 |
2022年 | 93篇 |
2021年 | 105篇 |
2020年 | 53篇 |
2019年 | 72篇 |
2018年 | 43篇 |
2017年 | 45篇 |
2016年 | 115篇 |
2015年 | 99篇 |
2014年 | 108篇 |
2013年 | 174篇 |
2012年 | 208篇 |
2011年 | 231篇 |
2010年 | 145篇 |
2009年 | 135篇 |
2008年 | 229篇 |
2007年 | 231篇 |
2006年 | 174篇 |
2005年 | 215篇 |
2004年 | 160篇 |
2003年 | 142篇 |
2002年 | 120篇 |
2001年 | 76篇 |
2000年 | 44篇 |
1999年 | 55篇 |
1998年 | 30篇 |
1997年 | 52篇 |
1996年 | 47篇 |
1995年 | 39篇 |
1994年 | 43篇 |
1993年 | 37篇 |
1992年 | 26篇 |
1991年 | 24篇 |
1990年 | 30篇 |
1989年 | 27篇 |
1988年 | 28篇 |
1987年 | 29篇 |
1986年 | 18篇 |
1985年 | 34篇 |
1984年 | 22篇 |
1983年 | 19篇 |
1982年 | 18篇 |
1981年 | 18篇 |
1980年 | 18篇 |
1979年 | 14篇 |
1978年 | 16篇 |
1977年 | 11篇 |
1976年 | 11篇 |
1975年 | 14篇 |
1974年 | 11篇 |
排序方式: 共有3784条查询结果,搜索用时 15 毫秒
1.
Triesterase and Promiscuous Diesterase Activities of a Di‐CoII‐Containing Organophosphate Degrading Enzyme Reaction Mechanisms 下载免费PDF全文
Dr. Marta E. Alberto Gaspar Pinto Prof. Nino Russo Dr. Marirosa Toscano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3736-3745
The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐CoII derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear CoII center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered. 相似文献
2.
Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells 下载免费PDF全文
Dr. Donatella Diana Anna Russomanno Dr. Lucia De Rosa Dr. Rossella Di Stasi Dr. Domenica Capasso Dr. Sonia Di Gaetano Dr. Alessandra Romanelli Dr. Luigi Russo Dr. Luca D. D'Andrea Prof. Roberto Fattorusso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):91-95
In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast 15N‐edited NMR spectroscopic experiments. To this aim, 15N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including 15N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2. 相似文献
3.
Rosa Erra-Balsells 《Journal of heterocyclic chemistry》1987,24(4):1117-1120
The electron impact mass spectrometric fragmentation pathways for several 2-methyl-, 3-methyl-, 2,3-dimethyl-, 2-aryl- and 3-phenylindole derivatives were investigated. An interesting relationship between the substitution pattern in the framework of the indole derivatives and the fragmentation patterns was observed. 相似文献
4.
A. Di Maio A. Rocco P. Ferraro M. De Rosa P. De Natale S. De Nicola A. Finizio G. Pierattini G. Coppola M. Iodice V. Striano 《Optics and Lasers in Engineering》2007,45(3):385
In view of the growing interest for non-destructive tests of materials, geodynamical monitoring and in general remote sensing, there is a great effort to bring practical optical sensors from research labs to industrial and environmental applications. In this paper, we employ digital holographic technique as an efficient tool for evaluating the strain measurement capability of fiber Bragg gratings (FBG). A cantilever beam has been employed as a test structure under loading test. The strain measurements results obtained by fiber-based sensors have been compared to those obtained by using full-field digital holographic technique and point-wise strain gauge sensors glued on the same cantilever beam. A simple theoretical model is also presented to interpret and compare the experimental results coming from different techniques. 相似文献
5.
Dinesh Topwal U. Manju Sugata Ray S. Raj D. D. Sarma S. R. Krishnakumar M. Bertolo S. La Rosa G. Cautero 《Journal of Chemical Sciences》2006,118(1):87-92
Disordered Sr2FeMoO6 shows a drastic reduction in saturation magnetization compared to highly ordered samples, moreover magnetization as a function
of the temperature for different disordered samples shows qualitatively different behaviours. We investigate the origin of
such diversity by performing spatially resolved photoemission spectroscopy on various disordered samples. Our results establish
that extensive electronic inhomogeneity, arising most probably from an underlying chemical inhomogeneity in disordered samples, is
responsible for the observed magnetic inhomogeneity. It is further pointed out that these inhomogeneities are connected with
composition fluctuations of the type Sr2Fe1+x
Mo1-x
O6 with Fe-rich (x > 0) and Mo-rich (x < 0) regions.
Dedicated to Prof J Gopalakrishnan on his 62nd birthday. 相似文献
6.
A difference between the thermal behaviour of the isotropic and liquid-crystalline state of sonicated DNA in aqueous salt solution containing poly(ethyleneglycol)(PEG) has been demonstrated. On cooling, a different degree of renaturation of thermally denaturated DNA is observed between samples which form the isotropic state and more concentrated samples which on cooling form the cholesteric state. 相似文献
7.
Giovanni Tartarini Alessandra Lena Davide Passaro Lorenzo Rosa Stefano Selleri Pier Faccin Enrico Maria Fabbri 《Optical and Quantum Electronics》2006,38(9-11):869-876
A comprehensive numerical tool has been developed for the evaluation of the performances of Radio over Fiber (RoF) links intended for wireless signal distribution.At the transmitter end an appropriate set of rate equations allows to model the optical source as a solitary laser or as an appropriately injection locked laser. The optical channel is modeled putting into account the combined effect of fiber dispersion, laser source non ideal performances (e.g. non-linear effects, frequency chirp), and quadratic detection of the receiving photodiode. The simulation model developed can be a useful tool at the design stage allowing a preliminary evaluation of the characteristics of real RoF links. 相似文献
8.
We show that every arithmetically Cohen-Macaulay two-codimensional subscheme ofP
n can be deformed to a reduced union of two-codimensional linear subvarieties. This problem (classical for curves with the name of Zeuthen problem) was solved for curves by F.Gaeta. 相似文献
9.
V. Vittoria R. Russo F. De Candia P. L. Magagnini B. Bresci 《Journal of Polymer Science.Polymer Physics》1991,29(9):1163-1168
The transport properties of a side-chain liquid-crystalline polymer forming a smectic A phase have been investigated using dichloromethane as a permeant. Samples differing in the isotropization enthaoly were analyzed. A. Correlation between this thermal parameter and sorption has been found, while the diffusion coefficient is substantially the same in all samples. The results obtained can be explained in terms of a biphasis model in which a disordered permeable phase is present within the liquid-crystalline phase, which is impermeable to the diffusant molecules. 相似文献
10.
Ilaria Fratoddi Chiara Battocchio Alessandra L. Groia Maria V. Russo 《Journal of polymer science. Part A, Polymer chemistry》2007,45(15):3311-3329
The reactivity of square planar palladium(II) and platinum(II) complexes in trans or cis configuration, namely trans or cis‐[dichlorobis(tributylphosphine)platinum(II)] and trans‐[dichlorobis(tributylphosphine)palladium(II)] with 1,1′‐bis(ethynyl) 4,4′‐biphenyl, DEBP, leading to π‐conjugated organometallic oligomeric and polymeric metallaynes, was investigated by a systematic variation of the reaction conditions. The formation of polymers and oligomers with defined chain length [? M(PBu3)2 (C?C? C6H4? C6H4? C?C? )]n (n = 3–10 for the oligomers, n = 20–50 for the polymers) depends on the configuration of the precursor Pt(II) and Pd(II) complexes, the presence/absence of the catalyst CuI, and the reaction time. A series of model reactions monitored by XPS, GPC, and NMR 31P spectroscopy showed the route to modulate the chain growth. As expected, the nature of the transition metal (Pt or Pd) and the molecular weight of the polymers markedly influence the photophysical characteristics of the polymetallaynes, such as optical absorption and emission behavior. Polymetallaynes with nanostructured morphology could be obtained by a simple casting procedure of polymer solutions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3311–3329, 2007 相似文献