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51.
In situ attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy has gained considerable attention as a powerful tool for exploring processes occurring at solid/liquid and solid/liquid/gas interfaces as encountered in heterogeneous catalysis and electrochemistry. Understanding of the molecular interactions occurring at the surface of a catalyst is not only of fundamental interest but constitutes the basis for a rational design of heterogeneous catalytic systems. Infrared spectroscopy has the exceptional advantage to provide information about structure and environment of molecules. In the last decade, in situ ATR-FT-IR has been developed rapidly and successfully applied for unraveling processes occurring at solid/liquid interfaces. Additionally, the kinetics of complex reactions can be followed by quantifying the concentration of products and reactants simultaneously in a non-destructive way. In this tutorial review we discuss some key aspects which have to be taken into account for successful application of in situ ATR-FT-IR to examine solid/liquid catalytic interfaces, including different experimental aspects concerned with the internal reflection element, catalyst deposition, cell design, and advanced experimental methods and spectrum analysis. Some of these aspects are illustrated using recent examples from our research. Finally, the potential and some limitations of ATR will be elucidated. 相似文献
52.
Zhou L Tan CK Jiang X Chen F Yeung YY 《Journal of the American Chemical Society》2010,132(44):15474-15476
A novel amino-thiocarbamate-catalyzed bromolactonization of unsaturated carboxylic acids has been developed. The scope of the reaction is evidenced by 22 examples of γ-lactones with up to 99% yield and 93% ee. The protocol was applied in the enantioselective synthesis of the key intermediates of VLA-4 antagonists. 相似文献
53.
Gomila A Le Poul N Cosquer N Kerbaol JM Noël JM Reddy MT Jabin I Reinaud O Conan F Le Mest Y 《Dalton transactions (Cambridge, England : 2003)》2010,39(48):11516-11518
We report the self-induced "electroclick" immobilization of the [Cu(II)(6-ethynyl-TMPA)(H(2)O)](2+) complex, by its simple electro-reduction, onto a mixed azidoundodecane-/decane-thiol modified gold electrode. The redox response of the grafted [Cu(II/I)(TMPA)] at the modified electrode is fully reversible indicating no Cu coordination change and a fast electron transfer. 相似文献
54.
Magali Bonne Stéphane Pronier Fabien Can Xavier Courtois Sabine Valange Jean-Michel Tatibouët Sébastien Royer Patrice Marécot Daniel Duprez 《Solid State Sciences》2010,12(6):1002-1012
Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO2/SiO2 nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (~2–3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ~10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO2/SiO2 solids are promising in term of thermal stability. 相似文献
55.
Lameiras P Boudesocque L Mouloungui Z Renault JH Wieruszeski JM Lippens G Nuzillard JM 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,212(1):161-168
NMR of weakly polar analytes in an apolar ultraviscous solvent has recently been proposed for mixture analysis as a pertinent alternative to the DOSY experiment. The present article reports the first use of glycerol and glycerol carbonate as polar solvents for the NMR analysis of a model mixture of dipeptides. This work demonstrates the high potentiality of these solvents for the analysis of mixtures made of polar and potentially bioactive compounds. Medium-sized molecules slowly reorient in glycerol and glycerol carbonate under particular temperature conditions, so that solute resonances may show spin diffusion in NOESY spectra, thus opening the way to mixture analysis. Glycerol and glycerol carbonate have turned out to be ultraviscous solvents of choice for the individualization of four structurally close mixed dipeptides: Leu-Val, Leu-Tyr, Gly-Tyr and Ala-Tyr by means of 1D and 2D NOESY experiments. Selective sample excitation and signal detection were implemented to eliminate the intense proton signals of the non-deuterated solvents. Moreover, the recording of a multiplet selective 2D NOESY-TOCSY has shown that the analytical power of NMR in highly viscous solvents is not limited to the extraction of mixture component 1D subspectra but may also yield some supplementary information about atom connectivity within components. 相似文献
56.
Landrieu I Lacosse L Leroy A Wieruszeski JM Trivelli X Sillen A Sibille N Schwalbe H Saxena K Langer T Lippens G 《Journal of the American Chemical Society》2006,128(11):3575-3583
The phosphorylation of the neuronal Tau protein modulates both its physiological role of microtubule binding and its aggregation into paired helical fragments observed in Alzheimer's diseased neurons. However, detailed knowledge of the role of phosphorylation at specific sites has been hampered by the analytical difficulties to evaluate the level of site-specific phosphate incorporation. Even with recombinant kinases, mass spectrometry and immunodetection are not evident for determining the full phosphorylation pattern in a qualitative and quantitative manner. We show here that heteronuclear NMR spectroscopy on a 15N labeled Tau sample modified by the cAMP dependent kinase allows identification of all phosphorylation sites, measures their level of phosphate integration, and yields kinetic data for the enzymatic modification of the individual sites. Filtering through the 15N label discards the necessity of any further sample purification and allows the in situ monitoring of kinase activity at selected sites. We finally demonstrate that the NMR approach can equally be used to evaluate potential kinase inhibitors in a straightforward manner. 相似文献
57.
Gilbert Dana Feiga Weisbuch Brigitte Lo Cicero Jean-Michel Drancourt Jacqueline Mercier 《Tetrahedron》1985,41(7):1241-1249
We show that the four studied 4-hydrindenones (with or without a methyl substituant at C3 or C7a) give by hydrogenation on Raney nickel or on Pd/C, in various solvants, the cis 4-hydrindanones, by a kinetically controlled process. During the hydrogenation, the double bond can migrate only in the positions conjugated to the carbonyl group.In contrast, when the carbonyle is protected as a dioxolanne, the double bond is free to migrate around the five membered ring. In spite of this mobility the optical purity of the saturated dioxolannes formed is high. In the case of the (+)3-methyl Δ3(3a) 4-hydrindenone, the enantiomeric hydrindanones obtained by direct hydrogenation or with isomerization of the double bond are not the same. Therefore, the optical purity of the product is low, but its value allows an estimation of the relative importance of the two reaction pathways. 相似文献
58.
59.
Bouchoul Nassim Fourré Elodie Tatibouët Jean-Michel Batiot-Dupeyrat Catherine 《Plasma Chemistry and Plasma Processing》2019,39(3):713-727
Plasma Chemistry and Plasma Processing - The coupling of catalyst and nonthermal plasma for the dry reforming of methane was investigated with a special attention to the textural and structural... 相似文献
60.