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61.
Viscosimetric detection in size-exclusion chromatography (SEC/GPC): The Goldwasser method and beyond
Size-exclusion chromatography (SEC or GPC) is the most widely used separation method to characterize polymers. The high level of complexity of most polymeric materials necessitates the use of not only concentration-sensitive detection but also structure-sensitive detection. Viscometry is usually used in conjunction with a concentration-sensitive detector and universal calibration to determine molecular weights of polymers. Goldwasser proposed to use a viscometer as a single detector to determine number-average molecular weights, M(n) (ACS Symposium Series, 521, 143). The method is particularly of interest when concentration-sensitive detection is not available, because the sample is isorefractive or not UV-absorbing, or because composition is not constant (copolymers). It has known very little applications so far. It actually does not only allow determining M(n), but also the number hydrodynamic volume distribution. This opens a wider range of applications for the Goldwasser method. Size-exclusion chromatography only yields inaccurate molecular weight distributions for some complex branched polymers. Hydrodynamic volume distributions have then a strong potential for comparative studies owing to their far higher accuracy. Our experimental tests highlight the fact that the method is highly sensitive to noise and careful optimization of the injection concentration is needed, but number distribution can be obtained as well as M(n). 相似文献
62.
Damien Montange Michel Bérard Martin Demarchi Patrice Muret Sarah Piédoux Jean Pierre Kantelip Bernard Royer 《Journal of mass spectrometry : JMS》2010,45(6):670-677
The anticancer drug capecitabine and its metabolites [including the active metabolite 5‐fluorouracil (5‐FU)] display high pharmacokinetic inter‐patient variability. Such variability, which may lead to treatment failure or toxicity, could need drug concentration measurement to individualize dosing regimen. However, usual assay methods are often long and fastidious. A simultaneous and cost‐effective method was thus developed for the determination of the concentrations of these compounds in human plasma. Compounds were extracted via a classic liquid–liquid extraction. Chromatographic analysis was performed on a C18 reverse phase column with detection by atmosphere pressure chemical ionization LC‐MS/MS. Our method allows a good chromatographic separation of the compounds and was fully validated following Food and Drug Administration (FDA) recommendations (good selectivity, no carry‐over, linearity of the calibration curves without weighting, deviations from nominal concentrations of standard samples lower than 15%, intra‐ and inter‐assay precision and accuracy lower than 15%). Recovery and stability were also acceptable following the FDA guidelines. A matrix effect impairing the determination of 5‐FU was avoided by using a stable isotopic derivative of 5‐FU as internal standard. Interestingly, this method allows detection of TetraHydroUridine, an inhibitor of ex vivo degradation of metabolites, which is essential for the stability, the adequate conditioning of blood samples and for good laboratory practice, essential in routine determination. This method seems usable to routinely determine concentrations of capecitabine and its metabolites in blood and may be helpful in further studies aiming at performing therapeutic drug monitoring. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
63.
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
64.
彩色数字全息研究中,用球面波为重建波及角谱衍射公式进行波前重建是一种有效的方法.然而,重建图像上通常伴有强烈的零级衍射干扰.本文通过理论分析,对波前重建过程作了重要改进.用改进后的方法进行彩色数字全息的实验研究表明,重建彩色图像的质量获得显著改善.
关键词:
彩色数字全息
波前重建
零级衍射干扰 相似文献
65.
The preparation and NMR analysis of 2,3-di-O-benzyl arabinofuranosides have been described. In DMSO-d6, the sugar adopts a conformation in which the hydroxyl groups are in an equatorial position; the equilibrium composition is determined by steric factors. In CDCl3, the sugar adopts a conformation in which the intramolecular hydrogen bonding plays an important role in determining the equilibrium composition. The use of 2,3-di-O-benzyl arabinose in the synthesis of oligoarabinofuranosides enabled the synthesis of α- or β-linked furanosides. 相似文献
66.
67.
Leyla Pehlivan Stéphane Laval Patrice Demonchaux Marc Lemaire 《Tetrahedron letters》2010,51(15):1939-10974
An efficient reduction of the nitro group with a catalytic amount of Fe(acac)3 and TMDS in THF at 60 °C affording the corresponding amine is described. 相似文献
68.
Hussein El-Kashef Pascal Rathelot Patrice Vanelle Sylvain Rault 《Monatshefte für Chemie / Chemical Monthly》2007,138(5):469-476
Summary. 2-Amino-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carbonitrile was converted into the corresponding 2-(pyrrol-1-yl) derivative, followed by reduction of the latter
compound into the corresponding amine. This amine and its acyl, aroyl, and arylidene derivatives were used as synthons in
the synthesis of several title compounds. 相似文献
69.
70.
Multinuclear NMR spectroscopy, relaxation and diffusion measurements were used recently to extract dynamical information on the long-time mobility of the water molecules and the neutralizing counterions condensed within the electrostatic well in the vicinity of the basal surface of clay particles. Multi-scale numerical modeling was used to interpret the NMR relaxation measurements and illustrate the interdependency between the solvent and ionic mobility and the organization of the anisotropic clay particles within the colloidal dispersions. 相似文献