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81.
Leroux YR Hui F Noël JM Roux C Downard AJ Hapiot P 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):11222-11228
The electroreduction of functionalized aryldiazonium salts combined with a protection-deprotection method was evaluated for the fabrication of organized mixed layers covalently bound onto carbon substrates. The first modification consists of the grafting of a protected 4-((triisopropylsilyl)ethynyl)benzene layer onto the carbon surface on which the introduction of a second functional group is possible without altering the first grafted functional group. After deprotection, we obtained an ultrathin robust layer presenting high densities of both active ethynylbenzene groups (available for "click" chemistry) and the second functional group. The strategy was successfully demonstrated using azidomethylferrocene to react with ethynyl moieties in the binary film by "click" chemistry, and NO(2)-phenyl as the second functional group. Two possible modification pathways with different orderings of the various steps were considered to show the influence and importance of the protection-deprotection process on the final surface obtained. Using mild conditions for the grafting of the second layer maintains a concentration of active ethynyl groups similar to that obtained for a one-component monolayer while achieving a high surface concentration of the second modifier. Considering the wide range of functional aryldiazonium salts that could be electrodeposited onto carbon surfaces and the versatility and specificity of the "click" chemistry, this approach appears very promising for the preparation of mixed layers in well-controlled conditions without altering the reactivity of either functional group. 相似文献
82.
This work is focused on studying the grafting of gold nanoparticles (Np) on a cystamine self-assembled monolayer on gold, in order to build sensitive immunosensors. The synthesis and deposition of gold nanoparticles, 13 and 55 nm sizes, were characterised by combining Polarisation Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS), X-ray Photoelectron Spectroscopy (XPS) Surface Enhanced Raman Scattering (SERS), and Atomic Force Microscopy (AFM) which all indicated the formation of a dispersed layer of nanoparticles. This observation is explained by the compromise between the high reactivity of amine-terminated layers towards gold, and interparticle repulsions. Nps were then functionalised with antibody probes, and the recognition by an anti-rIgG was assayed both on planar and Np gold surfaces.The important result is that nanoparticles of 55 nm are preferable for the following reasons: they enable to build a denser and well dispersed layer and they increase both the number of receptors (IgGs) and their accessibility. Beside these geometric improvements, a net enhancement of the Raman signal was observed on the 55 nm nanoparticle layer, making this new platform promising for optical detection based biosensors. 相似文献
83.
Bourlès E Isaac M Lebrun C Latour JM Sénèque O 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13762-13772
The reactivity of a series of Zn(Cys)(4) zinc finger model peptides towards H(2)O(2) and O(2) has been investigated. The oxidation products were identified by HPLC and ESI-MS analysis. At pH<7.5, the zinc complexes and the free peptides are oxidised to bis-disulfide-containing peptides. Above pH 7.5, the oxidation of the zinc complexes by H(2)O(2) also yields sulfinate- and sulfonate-containing overoxidised peptides. At pH 7.0, monitoring of the reactions between the zinc complexes and H(2)O(2) by HPLC revealed the sequential formation of two disulfides. Several techniques for the determination of the rate constant for the first oxidation step corresponding to the attack of H(2)O(2) by the Zn(Cys)(4) site have been compared. This rate constant can be reliably determined by monitoring the oxidation by HPLC, fluorescence, circular dichroism or absorption spectroscopy in the presence of excess ethyleneglycol bis(2-aminoethyl ether)tetraacetic acid. In contrast, monitoring of the release of zinc with 4-(2-pyridylazo)resorcinol or of the thiol content with 5,5'-dithiobis(2-nitrobenzoate) did not yield reliable values of this rate constant for the case in which the formation of the second disulfide is slower than the formation of the first. The kinetic measurements clearly evidence a protective effect of zinc on the oxidation of the cysteines by both H(2)O(2) and O(2), which points to the fact that zinc binding diminishes the nucleophilicity of the thiolates. In addition, the reaction between the zinc finger and H(2)O(2) is too slow to consider zinc fingers as potential sensors for H(2)O(2) in cells. 相似文献
84.
85.
Corrêa da Costa R Buffeteau T Del Guerzo A McClenaghan ND Vincent JM 《Chemical communications (Cambridge, England)》2011,47(29):8250-8252
The Ru(bipy)(3) dication is efficiently and reversibly transferred into perfluorocarbons due to the formation of a highly fluorophillic hydrogen-bonded fluorous carboxylate-carboxylic acid counter-anion, whilst retaining key luminescence and photosensitizer characteristics, for example in singlet oxygen production. 相似文献
86.
Canioni R Marchal-Roch C Leclerc-Laronze N Haouas M Taulèlle F Marrot J Paul S Lamonier C Paul JF Loridant S Millet JM Cadot E 《Chemical communications (Cambridge, England)》2011,47(22):6413-6415
{Mo(132)} Keplerate anion reacts with tellurites to give a soluble precursor to produce in hydrothermal conditions single-phase M1 MoVTeO light-alkanes oxidation catalyst. Characterization of this Te-containing intermediate by single-crystal X-ray diffraction, (125)Te NMR, UV-visible and redox titration reveals a molybdotellurite anion as a crown-capped Keggin derivative. 相似文献
87.
88.
The accuracy of tomographic particle image velocimetry for measurements of a turbulent boundary layer 总被引:1,自引:0,他引:1
Callum Atkinson Sebastien Coudert Jean-Marc Foucaut Michel Stanislas Julio Soria 《Experiments in fluids》2011,50(4):1031-1056
To investigate the accuracy of tomographic particle image velocimetry (Tomo-PIV) for turbulent boundary layer measurements,
a series of synthetic image-based simulations and practical experiments are performed on a high Reynolds number turbulent
boundary layer at Reθ = 7,800. Two different approaches to Tomo-PIV are examined using a full-volume slab measurement and a thin-volume “fat” light
sheet approach. Tomographic reconstruction is performed using both the standard MART technique and the more efficient MLOS-SMART
approach, showing a 10-time increase in processing speed. Random and bias errors are quantified under the influence of the
near-wall velocity gradient, reconstruction method, ghost particles, seeding density and volume thickness, using synthetic
images. Experimental Tomo-PIV results are compared with hot-wire measurements and errors are examined in terms of the measured
mean and fluctuating profiles, probability density functions of the fluctuations, distributions of fluctuating divergence
through the volume and velocity power spectra. Velocity gradients have a large effect on errors near the wall and also increase
the errors associated with ghost particles, which convect at mean velocities through the volume thickness. Tomo-PIV provides
accurate experimental measurements at low wave numbers; however, reconstruction introduces high noise levels that reduces
the effective spatial resolution. A thinner volume is shown to provide a higher measurement accuracy at the expense of the
measurement domain, albeit still at a lower effective spatial resolution than planar and Stereo-PIV. 相似文献
89.
We investigate the stability and control of a plane, laminar jet impinging on a flat plate in a channel, a geometry used to cool down a hot wall with a cold air jet in many industrial configurations. The global stability analysis indicates that, even for a strong confinement, the two-dimensional (2-D) steady flow is unstable to three-dimensional (3-D), steady perturbations. In the simplest limit case where dilatation effects are neglected, we show that the development of the instability induces a significant spanwise modulation of the heat flux at the impacted wall. To control the leading global mode, we propose adjoint-based 3-D harmonic and 2-D steady forcing in the bulk or at the wall. We show for instance that the unstable mode is controllable using a spanwise uniform blowing at the upper wall, in a specific domain corresponding to the footprint of the upper recirculating bubble. These techniques are applied to a novel open-loop control, in which we introduce into the flow a small airfoil, modelled by the lift force it exerts on the flow. 相似文献
90.